US010991749B2

( 12) United States Patent ( 10) Patent No .: US 10,991,749 B2

Oota et al . (45) Date of Patent : Apr. 27, 2021
( 54 ) STRUCTURE , COMPOSITION FOR ( 56 ) References Cited
FORMING NEAR - INFRARED
TRANSMITTING FILTER LAYER , AND U.S. PATENT DOCUMENTS
OPTICAL SENSOR
2011/0049661 Al 3/2011 Maehara et al .
( 71 ) Applicant: FUJIFILM Corporation, Tokyo ( JP ) 2011/0298074 Al 12/2011 Funao
(Continued )
( 72 ) Inventors: Kazuya Oota , Haibara -gun (JP ) ; FOREIGN PATENT DOCUMENTS
Masahiro Mori , Haibara - gun ( JP )
( 73 ) Assignee : FUJIFILM Corporation , Tokyo ( JP ) CN 106057833 A 10/2016
JP 10-268123 A 10/1998
( * ) Notice: Subject to any disclaimer, the term of this ( Continued )
patent is extended or adjusted under 35
U.S.C. 154 ( b ) by 0 days. OTHER PUBLICATIONS
( 21 ) Appl. No .: 16 /576,466 Japanese Office Action for Japanese Application No. 2019-506964 ,
dated Sep. 1 , 2020 , with English translation .
(22 ) Filed : Sep. 19 , 2019 (Continued )
( 65 ) Prior Publication Data
US 2020/0013821 A1 Jan. 9 , 2020 Primary Examiner David P Porta
Assistant Examiner Meenakshi S Sahu
Related U.S. Application Data (74 ) Attorney, Agent, or Firm Birch , Stewart, Kolasch
( 63 ) Continuation of application No. PCT/JP2018 /011356 , & Birch , LLP
filed on Mar. 22 , 2018 .
( 30 ) Foreign Application Priority Data ( 57 ) ABSTRACT

Mar. 24 , 2017 ( JP ) JP2017-059429 Provided is a structure capable of detecting near -infrared

light with good sensitivity. Also provided are a composition
( 51 ) Int. Ci. for forming a near -infrared transmitting filter layer used in
HOIL 27/146 ( 2006.01 ) the structure and an optical sensor capable of detecting
HOIL 31/0216 ( 2014.01 ) near - infrared light with good sensitivity. This structure 101
GO2B 5/20 ( 2006.01 ) has a support 1 , a partition wall 2 provided on the support
(52) U.S. CI . 1 , and a near - infrared transmitting filter layer 11 that shields
CPC HOTL 27/14649 (2013.01 ) ; G02B 5/208 visible light and transmits at least a portion of near - infrared
(2013.01 ) ; HOIL 27/14645 ( 2013.01 ) ; HOIL
light, provided in a region partitioned by the partition wall
31/02164 (2013.01) 2 , in which the refractive index of the partition wall 2 is
smaller than the refractive index of the near - infrared trans
( 58 ) Field of Classification Search mitting filter layer 11 at at least a portion of the wavelengths
CPC HO1L 27/14649 ; HOLL 31/02164 ; HOIL of the near - infrared light transmitted by the near - infrared
27/14645 ; HO1L 27/14643 ; HOIL transmitting filter layer 11 .
27/1462 ; HO1L 27/14623 ; G02B 5/208 ;
GO2B 5/201
See application file for complete search history . 21 Claims , 9 Drawing Sheets
101
50

H1 2 H2

11
 US 10,991,749 B2
Page 2

( 56 ) References Cited WO WO 2016/194527 A1 12/2016

WO WO 2017/038252 A1 3/2017
U.S. PATENT DOCUMENTS WO WO 2018/062130 A1 4/2018
2012/0196388 A1 * 8/2012 Tanaka HOIL 51/56 OTHER PUBLICATIONS
438/16
2012/0235263 A1 9/2012 Ogita et al. Korean Office Action for corresponding Korean Application No.
2012/0267745 A1 10/2012 Tsuji 10-2019-7027224 , dated Oct. 14 , 2020 , with English translation .
2015/0130007 A1 5/2015 Kawamura Japanese Office Action , dated Jun . 2 , 2020 , for corresponding
2016/0301897 A1 10/2016 Huang et al. Japanese Application No. 2019-506964 , with an English machine
2017/0317131 A1 11/2017 Shimada et al. translation .
2017/0317132 Al 11/2017 Hatakeyama et al . Japanese Office Action for corresponding Japanese Application No.
2018/0118865 A1 * 5/2018 Arayama GO3F 7/322 2019-506964 , dated Mar. 10 , 2020 , with English translation .
2019/0221596 Al 7/2019 Oota et al . International Preliminary Report on Patentability and English trans
FOREIGN PATENT DOCUMENTS lation of the Written Opinion of the International Searching Author
ity (Forms PCT/ IB/326 , PCT /IB/373 , and PCT /ISA / 237 ) for Inter
JP 2009-111225 A 5/2009
national Application No. PCT/JP2018/ 011356 , dated Oct. 3 , 2019 .
JP 2011-71483 A 4/2011 International Search Report (Form PCT/ ISA / 210 ) for International
JP 2011-258728 A 12/2011 Application No. PCT/JP2018 /011356 , dated Jun . 5 , 2018 , with
JP 2012-209542 A 10/2012 English translation .
JP 2012-227478 A 11/2012 Chinese Office Action and Search Report for corresponding Chinese
JP 2015-92521 A 5/2015 Application No. 2018800 19464.3 , dated Jan. 5 , 2021 , with English
JP 2016-201524 A 12/2016 translation of the Office Action .
WO WO 2016/117596 A1 7/2016
Wo WO 2016/117597 A1 7/2016 * cited by examiner
U.S. Patent Apr. 27, 2021 Sheet 1 of 9 US 10,991,749 B2

FIG . 1
101
50

H1 2 H2

11

FIG . 2.

102

50

21 11
U.S. Patent Apr. 27, 2021 Sheet 2 of 9 US 10,991,749 B2

FIG . 3
30 103

33 32 31 50

munt..

2
1

22 22 22. 11

FIG . 4

30 104

33 32 31 50

2
4

22 22 22
U.S. Patent Apr. 27, 2021 Sheet 3 of 9 US 10,991,749 B2

FIG . 5
105
22 22 22 50

33 32 31 11
30

FIG . 6
106

50

NA 2
wy

33 32 31 11

30
U.S. Patent Apr. 27, 2021 Sheet 4 of 9 US 10,991,749 B2

FIG . 7
30 107

33 32 31 50

3
2.
1

22 22 22 11

FIG . 8
30 108

33 32 31 50

2
2 1

2a 2a 2
22 22. 22 11
U.S. Patent Apr. 27, 2021 Sheet 5 of 9 US 10,991,749 B2

FIG . 9
30 109

33 32 31 50

w4

2
2
2
22 2b 2b 11

FIG . 10

30 110

33 32 31 50

2
port 1

22 11
U.S. Patent Apr. 27, 2021 Sheet 6 of 9 US 10,991,749 B2

FIG . 11
30 111

33 32 31 50

2
1

22 22 22 11

FIG . 12

30 112
50
33 32 31

A 22 22 22 11
N

1
U.S. Patent Apr. 27, 2021 Sheet 7 of 9 US 10,991,749 B2

FIG . 13
30 113

33 32 31 50

2.
1

22 22 22
41 41 41 11

FIG . 14

114
30

42 33 32 31 50

~2

22 22 22 22 11
U.S. Patent Apr. 27, 2021 Sheet 8 of 9 US 10,991,749 B2
FIG . 15
30 115

31 50
33 32

2
1

22 22 22 11

FIG . 16
30 116

33 32 31 50

22 22 22 11
U.S. Patent Apr. 27, 2021 Sheet 9 of 9 US 10,991,749 B2

FIG . 17
30 117

33 32 31 50 41

2
1

22 22 22 11

FIG . 18

30 118

33 32 31 50

2
5
1

22 22 22 11
 US 10,991,749 B2
1 2
STRUCTURE , COMPOSITION FOR sensitivity. Further, another object of the present invention is
FORMING NEAR - INFRARED to provide a composition for forming a near - infrared trans
TRANSMITTING FILTER LAYER , AND mitting filter layer which can be used in the above-men
OPTICAL SENSOR tioned structure, and an optical sensor capable of detecting
near - infrared light with good sensitivity.
CROSS - REFERENCE TO RELATED According to the studies conducted by the present inven
APPLICATIONS tors , it was found that it is possible to detect near - infrared
light with high sensitivity by increasing light collecting
This application is a Continuation of PCT International 10
properties for the near - infrared with a use of a structure
Application No. PCT/JP2018/ 011356 filed on Mar. 22 , which will be described below , thereby leading to comple
2018 , which claims priority under 35 U.S.C § 119 ( a ) to tion of the present invention . Accordingly, the present inven
Japanese Patent Application No. 2017-059429 filed on Mar. tion provides the following aspects .
24 , 2017. Each of the above application ( s) is hereby < b > A structure comprising:
expressly incorporated by reference , in its entirety, into the a support;
present application . 15
a partition wall provided on the support; and
BACKGROUND OF THE INVENTION a near - infrared transmitting filter layer provided in a
region partitioned by the partition wall , that shields visible
1. Field of the Invention light and transmits at least a portion of near - infrared light,
20 in which the refractive index of the partition wall is
The present invention relates to a structure, a composition smaller than the refractive index of the near - infrared trans
for forming a near - infrared transmitting filter layer, and an mitting filter layer structure at at least a portion of the
optical sensor . wavelengths of the near -infrared light transmitted by the
near - infrared transmitting filter layer.
2. Description of the Related Art 25 <2 > The structure as described in < 1 > ,
in which the refractive index of the partition wall is
From the related art, attempts have been made to perform smaller than the refractive index of the near - infrared trans
coloration of images and the like using color filters have mitting filter layer by 0.2 or more at at least a portion of the
hitherto been made in a solid - state imaging element such as wavelengths of the near - infrared light transmitted by the
a charge coupled device (CCD) image sensor. For example, 30 near-infrared transmitting filter layer.
JP2009-111225A describes a solid - state imaging element <3 > The structure as described in < 1 > or <2 > ,
comprising a semiconductor substrate ; a color filter array in which the refractive index of the partition wall is
having color filter layers having two or more colors and a smaller than the refractive index of the near - infrared trans
separation wall that separates color filter layers having at mitting filter layer at an entire wavelength in a wavelength
least different colors from each other, and a light collecting 35
range of 700 to 1,000 nm .
means arranged between the semiconductor substrate and <4 > The structure as described in any one of < 1 > to <3 > ,
the color filter array. in which the maximum value of the refractive index with
Moreover, in recent years, an optical sensor that senses respect to light in a wavelength range of 700 to 1,000 nm of
near - infrared light have been studied . The optical sensor can
also be utilized for distance measurement, three -dimensional 40 the partition wall is 1.4 or less .
measurement, or the like since the near - infrared light is < 5 > The structure as described in any one of < 1 > to <4 > ,
hardly scattered due to their longer wavelength than that of in which the maximum value of the refractive index with
visible light. In addition , since the near - infrared light is not respect to light in a wavelength range of 400 to 1,000 nm of
visible to the eyes of humans, animals, or the like , it is the partition wall is 1.4 or less .
impossible for a subject to recognize near - infrared light even 45 < b > The structure as described in any one of < 1 > to < 5 > ,
in a case where the subject is irradiated with the near- in which the partition wall includes at least one selected
infrared light at night, and accordingly, the optical sensor from silica particles , a siloxane resin , a fluorine resin , or
can also be used to photograph nocturnal wild animals or to silicon dioxide .
photograph an opponent while not stimulating the opponent <7 > The structure as described in any one of < b > to < 6 ) ,
in security applications . In this regard , the optical sensor that 50 further comprising a protective layer on a surface of the
senses near - infrared light can be developed in a variety of partition wall .
applications. For such an optical sensor, filters having a < 8 > The structure as described in any one of < b > to <7 > ,
transmission band in a near - infrared region , such as a in which the structure has a plurality of regions parti
near -infrared transmitting filter, have been used ( see , for tioned by partition walls on the support, a near - infrared
example , WO2016 / 117596A and WO2016 / 117597A) . 55 transmitting filter layer is provided in at least one region of
the regions partitioned by the partition walls , and at least one
SUMMARY OF THE INVENTION layer selected from a color filter layer or a near - infrared
shielding filter layer is provided in at least one region of the
Optical sensors in the related art cannot be said to have remaining regions partitioned by the partition walls .
sufficient sensitivity to near -infrared light, and thus, there is 60 < 9 > The structure as described in any one of < b > to < 8 > ,
a demand for further improvement in their sensitivity to the in which a content of the color material included in the
near - infrared light. In addition , also in the inventions near - infrared transmitting filter layer is 50 % to 75 % by
described in WO2016 / 117596A and WO2016 / 117597A , it mass .
cannot be said that the sensitivity to the near - infrared light < 10 > A composition for forming a near - infrared trans
is sufficient. 65 mitting filter layer, comprising:
Therefore , an object of the present invention is to provide a color material; and
a structure capable of detecting near - infrared light with good a curable compound ,
 US 10,991,749 B2
3 4
in which the composition is used for the formation of the group ” includes not only an alkyl group having no substitu
near - infrared transmitting filter layer in the structure as ent ( unsubstituted alkyl group ), but also an alkyl group
described in any one of < 1 > to < 9 > . having a substituent ( substituted alkyl group ).
< 11 > An optical sensor comprising the structure as In the present specification , " exposure” includes, unless
described in any one of < b > to < 9 > . 5 otherwise specified, not only exposure using light but also
According to the present invention , it is possible to lithography using particle rays such as electron beams and
provide a structure capable of detecting near - infrared light ion beams . In addition , examples of light used for the
with good sensitivity . Further, it is also possible to provide exposure generally include actinic rays or radiation such as
a composition for forming a near -infrared transmitting filter a bright line spectrum of a mercury lamp, far ultraviolet rays
layer which can be used in the above -mentioned structure, 10 typified by an excimer laser, extreme ultraviolet rays ( EUV
and an optical sensor capable of detecting near -infrared light light), X - rays, and electron beams .
with good sensitivity . In the present specification, " a (meth )allyl group ” repre
sents either or both of allyl and methallyl, “ (meth )acrylate”
BRIEF DESCRIPTION OF THE DRAWING represents either or both of acrylate and methacrylate,
15 “ (meth )acryl” represents either or both of acryl and meth
FIG . 1 is a schematic view showing an embodiment of the acryl, and “ (meth )acryloyl” represents either or both of
structure of the present invention . acryloyl and methacryloyl.
FIG . 2 is a schematic view showing an embodiment of the In the present specification, a weight -average molecular
structure of the present invention . weight and a number -average molecular weight are each
FIG . 3 is a schematic view showing an embodiment of the 20 defined as a value in terms of polystyrene, as measured by
structure of the present invention . means of gel permeation chromatography (GPC ) . In the
FIG . 4 is a schematic view showing an embodiment of the present specification, the weight -average molecular weight
structure of the present invention . (Mw ) and the number -average molecular weight ( Mn ) can
FIG . 5 is a schematic view showing an embodiment of the be determined , for example, by using HLC - 8220 (manufac
structure of the present invention . 25 tured by Tosoh Corporation ), TSKgel Super AWM - H
FIG . 6 is a schematic view showing an embodiment of the (manufactured by Tosoh Corporation , 6.0 mm ID ( inner
structure of the present invention . diameter )x15.0 cm) as columns, and a 10 -mmol/ L lithium
FIG . 7 is a schematic view showing an embodiment of the bromide N -methylpyrrolidinone (NMP) solution as an elu
structure of the present invention . ent.
FIG . 8 is a schematic view showing an embodiment of the 30 In the present specification, near - infrared light refers to
structure of the present invention . light at a wavelength of 700 to 2,500 nm .
FIG.9 is a schematic view showing an embodiment of the In the present specification, the total solid content refers
structure of the present invention . to a total mass of the components excluding a solvent from
FIG . 10 is a schematic view showing an embodiment of all the components of a composition .
the structure of the present invention. 35 In the present specification , a term “ step ” not only means
FIG . 11 is a schematic view showing an embodiment of an independent step but also includes a step which is not
the structure of the present invention. clearly distinguished from other steps in a case where an
FIG . 12 is a schematic view showing an embodiment of intended action of the step is accomplished .
the structure of the present invention . < Structure >
FIG . 13 is a schematic view showing an embodiment of 40 The structure of an embodiment of the present invention
the structure of the present invention . includes:
FIG . 14 is a schematic view showing an embodiment of a support,
the structure of the present invention. a partition wall provided on the support, and
FIG . 15 is a schematic view showing an embodiment of a near - infrared transmitting filter layer provided in a
the structure of the present invention. 45 region partitioned by the partition wall , that shields visible
FIG . 16 is a schematic view showing an embodiment of light and transmits at least a portion of near - infrared light,
the structure of the present invention . in which the refractive index of the partition wall is
FIG . 17 is a schematic view showing an embodiment of smaller than the refractive index of the near - infrared trans
the structure of the present invention. mitting filter layer structure at at least a portion of the
FIG . 18 is a schematic view showing an embodiment of 50 wavelengths of the near -infrared light transmitted by the
the structure of the present invention . near - infrared transmitting filter layer.
According to the structure of the embodiment of the
DESCRIPTION OF THE PREFERRED present invention, it is possible to enhance light collecting
EMBODIMENTS properties for near - infrared light, and thus further improve
55 the sensitivity to the near - infrared light by providing a
Hereinafter, the contents of the present invention will be near- infrared transmitting filter layer in a region partitioned
described in detail . by the partition wall having the above -mentioned refractive
In the present specification , a numerical range expressed index characteristics. In this regard , for example , by incor
using “ to ” means a range that includes the preceding and porating the structure of the embodiment of the present
succeeding numerical values of “ to ” as the lower limit value 60 invention into an optical sensor, it is possible to perform
sensing with higher accuracy using near - infrared light, or the
and the upper limit value, respectively .
In citations for a group ( atomic group ) in the present like . Further, since the near -infrared transmitting filter layer
specification, in a case where the group ( atomic group ) is has low transmission of i-rays, it tends to have low curabil
denoted without specifying whether it is substituted or ity. Therefore , in the related art, there have been some cases
unsubstituted, the group (atomic group) includes both a 65 where it is difficult to form pixels of a near - infrared trans
group (atomic group) having no substituent and a group mitting filter layer with good rectangularity or a color
( atomic group ) having a substituent. For example, an " alkyl material is eluted from the near - infrared transmitting filter
 US 10,991,749 B2
5 6
layer to cause mixed color with other adjacent filter layers enhance the light collecting properties for near - infrared
and the like . However, the structure of the embodiment of light, and thus, further improve the sensitivity to near
the present invention has a partition wall provided around a infrared light. This is particularly effective in a case where
near - infrared transmitting filter layer, the rectangularity of the near- infrared transmitting filter layer in the structure of
the near - infrared transmitting filter layer is good, and fur- 5 the embodiment of the present invention is a filter layer that
ther, even in a case where other filter layers other than the transmits light at at least a portion of the wavelengths in a
near-infrared transmitting filter layer are provided, it is wavelength range of 700 to 1,000 nm .
possible to effectively suppress the color material in the Moreover, the maximum value of the refractive index
near - infrared transmitting filter layer from causing mixed with respect to light in a wavelength range of 700 to 1,000
color with the other filter layers. 10 nm of the partition wall is preferably 1.4 or less , more
In the structure of the embodiment of the present inven- preferably 1.37 or less , and still more preferably 1.34 or less .
tion, the support is not particularly limited . The support can The refractive index with respect to light in a wavelength
be appropriately selected depending on its applications. range of 700 to 1,000 nm of the near - infrared transmitting
Examples of the support include substrates formed of mate- filter layer is more than 1.4 in many cases , and accordingly ,
rials such as silicone , alkali- free glass , soda glass , Pyrex 15 in a case where the maximum value of the above mentioned
-
(registered trademark ) glass , and quartz glass . It is also refractive index of the partition wall is 1.4 or less , it is
preferable to use an InGaAs substrate . Since the InGaAs possible to further enhance the light collecting properties for
substrate has good sensitivity to light at a wavelength of near -infrared light, and thus further improve the sensitivity
more than 1,000 nm , it is easy to obtain an optical sensor to near - infrared light.
having good sensitivity to light at a wavelength of more than 20 Furthermore, the maximum value of the refractive index
1,000 nm by forming each near - infrared transmitting filter with respect to light in a wavelength range of 400 to 1,000
layer on the InGaAs substrate . Further, a charge coupled nm of the partition wall is preferably 1.4 or less , more
device (CCD ) , a complementary metal oxide semiconductor preferably 1.37 or less , and still more preferably 1.34 or less .
( CMOS ) , a transparent conductive film , or the like may be Also , according to this aspect , it is possible to further
formed . Further, there are some cases where a black matrix 25 enhance the light collecting properties for near - infrared
made of a light shielding material such as tungsten is formed light, and thus further improve the sensitivity to near
on a support. In addition , an underlayer may be provided on infrared light. Further, the refractive index with respect to
the support , as desired , in order to improve the adhesiveness light in a wavelength range of 400 to 1,000 nm ofwhich will
to the upper layer, to prevent the diffusion of materials, or to be described later color filter layer is more than 1.4 in many
smoothen a surface of a substrate . 30 cases . In this regard , in a case where a near - infrared trans
The structure of the embodiment of the present invention mitting filter layer is provided in at least one region of the
may have a partition wall provided on the support. The regions partitioned by the partition wall and a color filter
partition wall may be provided in direct contact with the layer is provided in at least one region of the remaining
support. Further, in a case where an underlayer is provided regions partitioned by the partition walls , it is possible to
on the support, the partition wall may be provided on the 35 enhance the light collecting properties for each of visible
underlayer. In addition , in a case of using a support having light and near - infrared light, and thus further improve the
a black matrix on the support, the partition wall may also be sensitivity to near- infrared light.
provided on the black matrix . The shape of a region parti- With regard to a material of the partition wall , the
tioned by the partition wall on the support region (herein- partition wall may be formed of a material satisfying the
after also referred to as a shape of the opening of the 40 conditions for the above -mentioned refractive index, and is
partition wall ) is not particularly limited , and it may be , for not particularly limited . Various inorganic materials or
example , any one of a square shape, a rectangular shape, a organic materials can be used . A maximum value of the
circular shape, an elliptical shape , a polygonal shape , and the refractive index with respect to light in a wavelength range
like. of 700 to 1,000 nm in the material constituting the partition
In the structure of the embodiment of the present inven- 45 wall is preferably 1.4 or less , more preferably 1.37 or less ,
tion, the refractive index of the partition wall is smaller than and still more preferably 1.34 or less . Preferred examples of
the refractive index of the near- infrared transmitting filter the material of the partition wall include organic materials
layer at at least a portion of the wavelengths of the near- such as a siloxane resin and a fluorine resin , and inorganic
infrared light transmitted by the near - infrared transmitting materials such as silica particles and silicon dioxide . Among
filter layer, and the refractive index of the partition wall is 50 those, it is preferable that the partition wall does not sub
preferably smaller by 0.2 or more, more preferably smaller stantially include particles for a reason that the processabil
by 0.25 or more , and still more preferably smaller by 0.30 ity of the partition wall is good and it is easy to form a
or more . The upper limit is not particularly limited, and is partition wall having small variations in a width dimension ,
preferably 1.00 or less . According to this aspect , it is fewer defects, or the like . In addition, it is preferable that the
possible to further enhance the light collecting properties for
55 material of the partition wall is a siloxane resin and / or a
near - infrared light, and thus, further improve the sensitivity fluorine resin . A case where the partition wall does not
to near - infrared light. substantially include particles means that the content of the
Furthermore, in the structure of the embodiment of the particles in the partition wall is 1 % by mass or less , and the
present invention , the refractive index of the partition wall content is preferably 0.5 % by mass or less , and more
is preferably smaller than the refractive index of the near- 60 preferably 0.1 % by mass or less , and still more preferably,
infrared transmitting filter layer at an entire wavelength in a the particles are not contained .
wavelength range of 700 to 1,000 nm , and the refractive Examples of the siloxane resin include a resin obtained
index of the partition wall is more preferably smaller by 0.2 through a hydrolyzation reaction and a fusion reaction using
or more , still more preferably smaller by 0.25 or more , and an alkoxysilane raw material. The siloxane resin may be a
particularly preferably smaller by 0.30 or more . The upper 65 siloxane resin which has a silsesquioxane structure of any of
limit is not particularly limited, and is preferably 1.00 or a cage type, a ladder type, a random type, or the like . Further,
less . According to this aspect , it is possible to further with regard to the “ cage type ” , the “ ladder type ” , and the
 US 10,991,749 B2
7 8
" random type ” , it is possible to refer to the structures which
present specification, a resin including a siloxane bond and
are described in , for example , Chemistry and Application a fluorine atom in a molecule thereof is intended to corre
Development of Silsesquioxane Material (CMC Publishing) spond to the siloxane resin .
or the like. The width of the partition wall is preferably 20 to 500 nm .
The siloxane resin preferably has a silsesquioxane struc- 5 The lower limit is preferably 30 nm or more , more prefer
ture represented by Formula ( S1 ) . ably 40 nm or more, and still more preferably 50 nm or
more . The upper limit is preferably 300 nm or less , more
— (R'SiO32)n Formula ( S1 ) preferably 200 nm or less , and still more preferably 100 nm
(In Formula ( S1 ) , R ' represents an alkyl group having 1 or less .
to 3 carbon atoms. n represents an integer from 20 to 1,000 . ) 10 In addition , the height of the partition wall is preferably
The alkyl group represented by R ! mayhave a substituent. 200 nm or more , more preferably 300 nm or more , and still
Examples of the substituent include a fluorine atom , an more preferably 400 nm or more . The upper limit is pref
amino group , a sulfonamido group , an acyloxy group , a erably the thickness of the near - infrared transmitting filter
carbamoyl group , and an acylamino group . layerx200 % or less , more preferably the thickness of the
Examples of the alkoxysilane raw material include tri- 15 near-infrared transmitting filter layerx150 % or less , and still
alkoxysilane and tetraalkoxysilane. The alkoxysilane raw more preferably substantially the same as the thickness of
material preferably includes at least trialkoxysilane, and the near - infrared transmitting filter layer.
more preferably includes trialkoxysilane and tetraalkoxysi The ratio of the width to the height (height /width ) of the
lane . The trialkoxysilane is preferably a compound repre partition wall is preferably 1 to 100 , more preferably 5 to 50 ,
sented by Formula (52 ) . The tetraalkoxysilane is preferably 20 and still more preferably 5 to 30. A partition wall having the
ratio in the above -mentioned range can be easily formed ,
a compound represented by Formula ( S3 ) .
and thus, the productivity is excellent. In addition , a struc
R’Si ( OR ) ; Formula ( S2) ture having a good near - infrared recognition ability can be
obtained .
Si(OR ) Formula (S3)
25 It is also preferable that a protective layer is provided on
a surface of the partition wall in the structure of the
(R2 and R3 each independently represent an alkyl group .) embodiment of the present invention . The protective layer is
The number of carbon atoms of the alkyl group repre- provided on the side of the partition wall , and it is preferable
sented by each of R2 and R3 is preferably 1 to 10 , more that the partition wall and the near - infrared transmitting
preferably 1 to 4 , and still more preferably 1 to 3. The alkyl 30 filter layer are into contact with each other through the
group represented by each of R2 and R3 is preferably a linear protective layer. By providing the protective layer on a
alkyl group . The alkyl group represented by each of R2 and surface of the partition wall , it is possible to suppress for the
R3 may have a substituent. Examples of the substituent color material or the like included in the near - infrared
include the above -mentioned substituents which the alkyl transmitting filter layer from being diffused into the partition
group represented by R1 may have. 35 wall or to improve the adhesiveness between the partition
With regard to the details of the siloxane resin , reference wall and the near - infrared transmitting filter layer. As a
may be made to the descriptions in paragraph Nos . 0014 to material of the protective layer, various inorganic materials
0039 of JP2014-063125A , JP2004-021036A , and JP2011- or organic materials can be used . Examples of the organic
084672A , the contents of which are incorporated herein by materials include an acrylic resin , a polystyrene resin , a
reference . 40 polyimide resin , and an organic spin -on - glass ( SOG ) resin .
Examples of the fluorine resin include a resin which Further, the protective layer can also be formed using a
contains fluorine in the molecule . Specific examples thereof composition including a compound having a group having
include polytetrafluoroethylene, polyhexafluoropropylene, a an ethylenically unsaturated bond . Examples of the group
tetrafluoroethylene/hexafluoropropylene copolymer, a tet- having an ethylenically unsaturated bond include a vinyl
rafluoroethylene /perfluoroalkylvinyl ether copolymer, a tet- 45 group, a (meth ) allyl group , a (methacryloyl group , a styryl
rafluoroethylene/ ethylene copolymer, a hexafluoropropyl- group , with the (meth )allyl group or the (methacryloyl
ene /propylene copolymer, polyvinylidene fluoride, and a group being preferable . The compound having a group
vinylidene fluoride / ethylene copolymer. Further, an amor- having an ethylenically unsaturated bond may be either a
phous fluorine resin is also preferably used , and examples of monomer or a resin such as a polymer. Examples of the
a commercially available product thereof include CYTOP 50 compound having a group having an ethylenically unsatu
(manufactured by Asahi Glass Co. , Ltd. ) . The molecular rated bond include the polymerizable compounds described
weight of a fluorine resin such as polytetrafluoroethylene is for a composition for a near- infrared transmitting filter
preferably in the range of 100,000 to 10,000,000 , and more which will be described later, and resins having a polymer
preferably in the range of 100,000 to 1,000,000 . Examples izable group . Examples of the inorganic materials include
of commercial products of the polytetrafluoro ethylene 55 silicon dioxide . In a case where a protective layer formed of
include TEFLON (registered trademark ) 6 - J , TEFLON (reg- an organic material is provided on a surface of the partition
istered trademark ) 6C - J , and TEFLON ( registered trade- wall , it is possible to improve the adhesiveness between the
mark ) 62 - J , each manufactured by Du Pont -Mitsui Fluoro- near -infrared transmitting filter layer and the partition wall .
chemicals Co. , Ltd. , and FLUON CD1 or CD076 Further, in a case where a protective layer formed of an
manufactured by Asahi Glass Co. , Ltd. In addition, as a 60 inorganic material is provided on a surface of the partition
commercial product of polytetrafluoroethylene - containing wall , it is possible to effectively suppress for the color
mixed powder formed of polytetrafluoroethylene particles material or the like included in the near - infrared transmitting
and an organic polymer, “ METABLEN ( registered trade- filter layer from being diffused into the partition wall , and
mark )” A series are commercially available from Mitsubishi thus, to suppress contamination of the partition wall or
Rayon Co. , Ltd., and “ METABLEN ( registered trademark ) ” 65 variations in the refractive index of the partition wall . The
A - 3000 , “ METABLEN ( registered trademark ) ” A - 3800 , and material of the protective layer can be appropriately selected
the like are commercially available . In addition , in the depending on the material of the partition wall , and it is
 US 10,991,749 B2
9 10
preferable that the material of the protective layer is the in a wavelength range of 400 to 640 nm and transmit
same material as that of the partition wall from the viewpoint near - infrared light at a wavelength of 720 nm .
of the adhesiveness to the partition wall of the protective ( 2 ) : A filter layer in which the maximum value in a
layer or the film forming properties of the protective layer. wavelength range of 400 to 750 nm of the transmittance of
Specifically, in a case where the material of the partition wall 5 light in the thickness direction is 20 % or less ( preferably
includes silica particles or a siloxane resin , the material of 15 % or less , and more preferably 10% or less ) and the
the protective layer is preferably silicon dioxide from the minimum value in a wavelength range of 900 to 1,300 nm
viewpoint of the adhesiveness to the partition wall of the of the transmittance of light in the thickness direction is 70 %
tective layerlayer
protective . or the film forming properties of the pro- 10 oror more
more)(.preferably
With this 75filter% orlayermore
, it
, and more preferably 80 %
is possible to shield light
In the structure of the embodiment of the present inven in a wavelength range of 400 to 750 nm and transmit
tion, a near - infrared transmitting filter layer that shields near - infrared light at a wavelength of 850 nm .
visible light and transmits at least a portion of near - infrared ( 3 ) : A filter layer in which the maximum value in a
wavelength range of 400 to 850 nm of the transmittance of
light is provided in a region partitioned by the partition wall . 15 light in the thickness direction is 20 % or less ( preferably
The near -infrared transmitting filter layer may be any of 15 % or less , and more preferably 10% or less ) and the
filter layers having spectral characteristics of shielding vis minimum value in a wavelength range of 1,000 to 1,300 nm
ible light and transmitting at least a portion of near - infrared of the transmittance of light in the thickness direction is 70 %
light. The near -infrared transmitting filter layer is , for or more (preferably 75 % or more, and more preferably 80 %
example, preferably a filter layer having spectral character- 20 or more ). With this filter layer, it is possible to shield light
istics of transmitting at least a portion of light at a wave- in a wavelength range of 400 to 850 nm and transmit
length in a wavelength range of 700 to 2,500 nm , more near - infrared light at a wavelength of 940 nm .
preferably a filter layer having spectral characteristics of ( 4 ) : A filter layer in which the maximum value in a
transmitting at least a portion of light at a wavelength in a wavelength range of 400 to 950 nm of the transmittance of
wavelength range of 700 to 2,000 nm , still more preferably 25 light in the thickness direction is 20% or less (preferably
a filter layer having spectral characteristics of transmitting at 15 % or less , and more preferably 10% or less ) and the
least a portion of light at a wavelength in a wavelength range minimum value in a wavelength range of 1,100 to 1,300 nm
of 700 to 1,500 nm , even still more preferably a filter layer of the transmittance of light in the thickness direction is 70 %
having spectral characteristics of transmitting at least a or more ( preferably 75 % or more, and more preferably 80 %
portion of light at a wavelength in a wavelength range of 700 30 or more ). With this filter layer, it is possible to shield light
to 1,300 nm , and particularly preferably a filter layer having in a wavelength range of 400 to 950 nm and transmit
spectral characteristics of transmitting at least a portion of near - infrared light at a wavelength of 1,040 nm .
light at a wavelength in a wavelength range of 700 to 1,000 In the structure of the embodiment of the present inven
nm . Further, the near - infrared transmitting filter layer may tion , a transparent layer may be provided on a surface of the
be formed of a film in the form of one layer (monolayered 35 near - infrared transmitting filter layer and / or between the
film ) or may be formed of a film in the form of two or more near - infrared transmitting filter layer and the support. In a
layers (multilayered film ). Further, in a case where the case where the thickness of the near - infrared transmitting
near - infrared transmitting filter layer is formed of the mul- filter layer is smaller than the height of the partition wall , or
tilayered film , a whole volume of the layers only needs to other cases , it is preferable that by providing the transparent
have the above-mentioned spectral characteristics, but it is 40 layer, the thickness of a laminate of the near - infrared trans
not necessary that the film in the form of one layer itself has mitting filter layer and the transparent layer is set to be
the above -mentioned spectral characteristics, respectively . equivalent to the height of the partition wall . By setting the
The thickness of the near -infrared transmitting filter layer thickness in this manner, it is possible to improve processing
is not particularly limited . The thickness is , for example, accuracy of a lens, for example, in the formation of the lens
preferably 100 um or less , more preferably 15 um or less , 45 on the near - infrared transmitting filter layer, and also
still more preferably 5 um or less , and particularly preferably improve the adhesiveness to the lens . In addition, it is
1 um or less . The lower limit value is preferably 0.1 um or possible to expect a higher resolution by the control of
more , more preferably 0.2 um or more, and still more incident angles. The transparent layer can be formed by, for
preferably 0.3 um or more . Further, from the viewpoint of example , using a composition including a resin . Examples of
the light collecting properties for near - infrared light, the 50 the resin include the resins for the composition for a near
thickness of the near - infrared transmitting filter layer is infrared transmitting filter which will be described later.
preferably the height of the partition wallx50 % to the height Further, for the transparent layer, the radiation - sensitive
of the partition wallx150 % , more preferably the height of composition described in JP2013-254047A , the contents of
the partition wallx75 % to the height of the partition wallx which are incorporated herein by reference, can be also
125 % , and still more preferably the height of the partition 55 used .
wallx90% to the height of the partition wallx110 % . The near - infrared transmitting filter layer can be formed
Preferred examples of the near - infrared transmitting filter using a composition ( composition for forming a near- infra
layer include a filter layer having spectral characteristics of red transmitting filter layer ) including a color material and a
any one of ( 1 ) to (4) below . curable compound. The content of the color material in the
( 1 ): A filter layer in which the maximum value in a 60 near -infrared transmitting filter layer is preferably 50% to
wavelength range of 400 to 640 nm of the transmittance of 75 % by mass . The lower limit is preferably 35 % by mass or
light in the thickness direction is 20% or less (preferably more , more preferably 45 % by mass or more, and still more
15 % or less , and more preferably 10 % or less ) and the preferably 55 % by mass or more . The upper limit is pref
minimum value in a wavelength range of 800 to 1,300 nm erably 80% by mass or less , more preferably 75 % by mass
of the transmittance of light in the thickness direction is 70 % 65 or less , and still more preferably 70% by mass or less . Since
or more ( preferably 75 % or more, and more preferably 80 % the structure of the embodiment of the present invention has
or more) . With this filter layer, it is possible to shield light the partition wall around the near - infrared transmitting filter
 US 10,991,749 B2
11 12
layer, it is possible to suppress the color material in the ( 3 ) A transmittance of light in a wavelength range of 600
near - infrared transmitting filter layer from being eluted into nm is preferably 70% or more , more preferably 80% or more
the other filter layers adjacent thereto and thus causing still more preferably 90 % or more, and particularly prefer
mixed color even with an increase in the concentration of the ably 95 % or more .
color material in the near - infrared transmitting filter layer. In 5 ( 4 ) A transmittance of light in a wavelength range of 650
addition , it is possible to increase the concentration of the nm is preferably 70% or more , more preferably 80% or more
color material in the near - infrared transmitting filter layer, still more preferably 90 % or more, and particularly prefer
and therefore , it is possible to detect desired light having ably 95 % or more .
reduced noise caused by visible light. A transmittance at any in a wavelength range of 400 to
Preferred aspects of the structure of the embodiment of 10 650
ably nm 70 %oforthemore
near, more
-infraredpreferably
shielding80filter
% or layer
more ,isand
prefer
still
the present invention include an aspect , in which more preferably 90% or more . Further, a transmittance at at
in which the structure has a plurality of regions parti least one point in a wavelength range of 700 to 1,000 nm is
tioned by the above -mentioned partition walls on a support, preferably 20% or less .
a near- infrared transmitting filter layer is provided in at 15 A thickness of the near - infrared shielding filter layer is not
least one region of the above -mentioned regions partitioned particularly limited . The thickness is , for example , prefer
by the partition walls , and ably 100 um or less , more preferably 15 um or less , still
at least one layer selected from a color filter layer or a more preferably 5 um or less , and particularly preferably 1
near -infrared shielding filter layer is provided in at least one um or less . The lower limit value is preferably 0.1 um or
region of the remaining regions partitioned by the above- 20 more, more preferably 0.2 um or more, and still more
mentioned other partition walls . preferably 0.3 um or more .
In a case where the structure of the embodiment of the In a case where the structure of the embodiment of the
present invention further has a color filter layer, it is possible present invention has a near - infrared shielding filter layer, a
to further perform image recognition at the same time with transparent layer may be provided on a surface of the
sensing through near - infrared light. Further, in a case where 25 near - infrared shielding filter layer and / or between the near
the structure of the embodiment of the present invention infrared shielding filter layer and the support. In a case
further has a near - infrared shielding filter layer, it is possible where the thickness of the near - infrared transmitting filter
to further reduce noise by reducing the amount of near- layer is smaller than the height of the partition wall , or other
infrared light incorporated into the color filter pixel . Further, cases , it is preferable that the thickness of a laminate of the
in the present invention , the near -infrared shielding filter 30 near - infrared shielding filter layer and the transparent layer
layer means a filter layer that transmits visible light and is set to be equivalent to the height of the partition wall by
shields at least a portion of near - infrared light. The near- providing the transparent layer. By setting the thickness in
infrared shielding filter layer may transmit all of visible this manner, it is possible to improve the processing accu
lights, or may only transmit light in a specific wavelength racy of a lens , for example, in the formation of the lens on
region among the visible lights. The near- infrared shielding 35 the near -infrared shielding filter layer, and it is also possible
filter layer can be formed using a composition including a to improve the adhesiveness to the lens . In addition , it is
near - infrared absorbing dye and the like. Incidentally, in the possible to expect a higher resolution by the control of
present invention , the color filter layer means a filter layer incident angles.
that transmits light in a specific wavelength range and Examples of the color filter layer include filter layers
shields light in a specific wavelength range among the 40 including colored layers in one or more colors selected from
visible lights. The color filter layer may have spectral red, blue , green , cyan, magenta, and yellow. The color filter
characteristics of shielding at least a portion of near - infrared layer may be formed of a single colored layer or may include
light. The color filter layer having spectral characteristics of colored layers in two or more colors . Further, in a case where
shielding at least a portion of near - infrared light can be the structure of the embodiment of the present invention has
formed using a composition including a chromatic coloring 45 colored layers in two or more colors , the colored layers in
agent and a near - infrared absorbing dye. the respective colors may be provided by one color in each
The near - infrared shielding filter layer has the maximum of different regions partitioned by partition walls or the
absorption wavelength in a wavelength range of preferably colored layers in a plurality of colors may be provided in one
700 to 2,000 nm , more preferably 700 to 1,300 nm , and still region partitioned by the partition wall .
more preferably 700 to 1,000 nm . Further, absorbance 50 The thickness of the color filter layer ( the thickness of the
Amax / absorbance A550 which is a ratio of an absorbance colored layer) is not particularly limited . The thickness is ,
Amax at the maximum absorption wavelength and an absor- for example, preferably 100 um or less , more preferably 15
bance A550 at a wavelength of 550 nm is preferably 50 to um or less , and still more preferably 5 um or less , and
500 , more preferably 70 to 450 , and still more preferably particularly preferably 1 um or less . The lower limit value is
100 to 400 . 55 preferably 0.1 um or more , more preferably 0.2 um or more ,
It is preferable that the near -infrared shielding filter layer and still more preferably 0.3 um or more .
satisfies at least one condition of ( 1 ) to (4 ) below , and it is In a case where the structure of the embodiment of the
more preferable that the near - infrared shielding filter layer present invention has a color filter layer, it is preferable that
satisfies all of the condition of ( 1 ) to (4 ) . the structure further has a near - infrared shielding filter layer
( 1 ) A transmittance of light in a wavelength range of 400 60 on an optical path of the color filter layer. According to this
nm is preferably 70 % or more , more preferably 80% or more aspect , it is possible to detect visible light having less noise .
still more preferably 85 % or more , and particularly prefer- In this case , the near - infrared shielding filter layer may be
ably 90% or more . provided on the color filter layer or between the color filter
(2 ) A transmittance of light in a wavelength range of 500 layer and the support.
nm is preferably 70 % or more , more preferably 80% or more 65 Moreover, in a case where the structure of the embodi
still more preferably 90 % or more , and particularly prefer- ment of the present invention has a color filter layer, a
ably 95 % or more . transparent layer may be provided on a surface of the color
 US 10,991,749 B2
13 14
filter layer and / or between the color filter layer and the display device and an organic electroluminescence ( organic
support. In a case where the thickness of the color filter layer EL ) display device ). For example , an optical sensor into
is smaller than the height of the partition wall , the thickness which the structure of the embodiment of the present inven
of the color filter layer is smaller than that of the other filter tion is introduced can be preferably used in applications for
layers, or other cases , it is preferable that the thickness of a 5 surveillance, security applications, mobile applications ,
laminate of the color filter layer and the transparent layer is automotive applications , agricultural applications , medical
set to be equivalent to the height of the partition wall by applications , distance measuring applications , gesture rec
providing the transparent layer. By setting the thickness in ognition applications , vital recognition applications, or the
this manner , it is possible to improve the processing accu- like.
racy of a lens, for example, in the formation of the lens on 10 Hereinafter, the structure of the embodiment of the pres
the color filter layer, such as the formation of the lens on the ent invention will be described in detail with reference to the
near -infrared transmitting filter layer , and it is also possible drawings. FIG . 1 is a schematic view showing an embodi
to improve the adhesiveness to the lens . In addition , it is ment of the structure of the present invention . A structure
possible to expect a higher resolution by the control of 101 includes a support 1 , a partition wall 2 provided on the
incident angles. 15 support, and a near -infrared transmitting filter layer 11
In the structure of the embodiment of the present inven- provided in a region partitioned by the partition wall 2 .
tion, a transparent layer may be provided at a position Further, a lens 50 is provided on the near - infrared transmit
different from the region in which the near - infrared trans- ting filter layer 11. The partition wall 2 is a partition wall
mitting filter layer and the color filter layer are provided. In having the above -mentioned refractive index characteristics.
this case , the color filter layer and the transparent layer may 20 Furthermore, in FIG . 1 , the height H1 of the partition wall
be provided at a position in the same region partitioned by 2 is the same as the height ( thickness ) H2 of the near
the partition wall , and the color filter layer and the trans- infrared transmitting filter layer 11 , but the height H1 of the
parent layer may be each provided in different regions partition wall 2 may be smaller or larger than the height
partitioned by the partition walls . (thickness ) H2 of the near - infrared transmitting filter layer
In a case where the structure of the embodiment of the 25 11. Further, in a case where the height H1 of the partition
present invention has another filter layer, in addition to the wall 2 is larger or smaller than the height ( thickness ) H2 of
near - infrared transmitting filter layer, it is preferable that the the near - infrared transmitting filter layer 11 , it is preferable
height difference between the top surfaces of the respective that the height difference between the partition wall 2 and
filter layers is substantially equal to each other. According to the near - infrared transmitting filter layer 11 is filled with the
this aspect , it is possible to expect effects such as flatness , 30 transparent layer or the lens 50. Further, in FIG . 1 , the
adhesiveness , and a higher resolution by the control of partition wall 2 is directly provided on the support 1 , but by
incident angles. providing an underlayer or a black matrix on the support 1 ,
It is also preferable that the structure of the embodiment the partition wall 2 may be formed on the underlayer or the
of the present invention further has a band- pass filter that black matrix . Further, in FIG . 1 , the near - infrared transmit
transmits a portion of near - infrared light on the optical path 35 ting filter layer 11 and the partition wall 2 are directly in
of the near - infrared transmitting filter layer. According to contact with each other, but a protective layer may be
this aspect , it is possible to detect light having less noise with formed on a surface of the partition wall 2 , and the near
high sensitivity. Examples of the band -pass filter include a infrared transmitting filter layer 11 and the partition wall 2
laminate forming by alternately laminating a high -refrac- may be in contact with the protective layer. Further, an
tive - index layer and a low - refractive - index layer. 40 intermediate layer may be provided between the near - infra
The band - pass filter may be a band -pass filter that shields red transmitting filter layer 11 and the lens 50. The inter
visible light or may be a band -pass filter that transmits mediate layer can be formed using a composition for form
visible light. The spectral characteristics of the visible region ing a transparent layer or the like .
of the band -pass filter can be appropriately selected depend- FIG . 2 is a schematic view showing an embodiment of the
ing on the application . For example, in a case where the 45 structure of the present invention , in which the structure
structure of the embodiment of the present invention does further has a near - infrared shielding filter layer, in addition
not have a color filter layer or a case where the structure has to the near - infrared transmitting filter layer 11. This structure
a color filter layer but the band -pass filter is not provided on 102 has a support 1 , a partition wall 2 provided on the
the optical path of the color filter layer, it is preferable that support 1 , a near -infrared transmitting filter layer 11 pro
the band -pass filter shields visible light. By using such a 50 vided in a region partitioned by the partition wall 2 , and a
band -pass filter in combination , it is possible to detect near - infrared shielding filter layer 21 provided in a region
desired light such as near - infrared light having less noise partitioned by the partition wall 2 , different from the region
caused by visible light. Further, in a case where the structure in which the near - infrared transmitting filter layer 11 is
of the embodiment of the present invention has a color filter provided . In addition, a lens 50 is provided on the near
layer and a band -pass filter provided on an optical path ofthe 55
color filter layer, it is preferable that such a band -pass filter
infrared transmitting filter layer 11 and the near -infrared
shielding filter layer 21. The partition wall 2 is a partition
is a filter that transmits visible light. According to this wall having the above -mentioned refractive index charac
aspect , it is possible to simultaneously detect visible light teristics .
and near - infrared light having less noise with good sensi- The height of the partition wall 2 may be larger or smaller
tivity . 60 than the height ( thickness) of the near - infrared transmitting
The structure of the embodiment of the present invention filter layer 11. Further, the height of the partition wall 2 may
may have an anti - reflection film , a flattened film , a lens , or be smaller or larger than the height ( thickness ) of the
the like , which is provided on each of the filter layers . near -infrared shielding filter layer 21. Further, in FIG . 2 , the
The structure of the embodiment of the present invention height ( thickness ) of the near- infrared transmitting filter
can be preferably used after being introduced into various 65 layer 11 and the height (thickness) of the near -infrared
optical sensors such as a solid - state imaging element, or into shielding filter layer 21 are the same as each other, but the
an image display device ( for example, a liquid crystal heights of the filter layers of the both may be different from
 US 10,991,749 B2
15 16
each other. From the viewpoint of flatness, adhesiveness, a a color filter layer 30. A structure 106 shown in FIG . 6 has
higher resolution by the control of incident angles, or the the same configuration as in FIG . 3 , except that it does not
like , it is preferable that the heights ( thicknesses ) of the filter have the near - infrared shielding filter layer 22. A structure
layers of the both are almost same as each other. Inciden- 107 shown in FIG . 7 has the same configuration as in FIG .
tally, it is preferable that the height differences of the filter 5 3 , except that it has a protective layer 3 on a surface of the
layers of the both are almost same as each other. Further, in
FIG . 2 , the partition wall 2 is directly provided on the partition wall 2. A structure 108 shown in FIG . 8 has the
support 1 , but by providing a black matrix on the support 1 , which the color filteraslayer
same configuration in FIG . 3 , except that in a region in
30 is provided, a partition wall 2a
a partition wall 2 may be formed on the underlayer or black is provided between the near -infrared shielding filter layers
matrix
filter layer 11 , the partition wall 2 , the near - infrared shield partitioned by the partition wallshielding
. Further , in FIG . 2 , the near -infrared transmitting 10 22, each of the near -infrared filter layers 22 is
2a ,
ing filter layer 21 , and the partition wall 2 are each directly 2 and the partition wall 2a , but the partition or by the partition wall
in contact with each other, but a protective layer may be wall is not
formed on a surface of the partition wall 2 and the near provided between the respective colored layers of the
infrared transmitting filter layer 11 or the near-infrared 15 respective near-infrared shielding filter layers. A structure
shielding filter layer 21 and the partition wall 2 may be in 109 shown in FIG . 9 has the same configuration as in FIG .
contact through the protective layer. In addition , an inter 3 , except that in a region in which the color filter layer 30
mediate layer may be provided between the near - infrared is provided, a partition wall 2b is provided on the near
transmitting filter layer 11 and the lens 50 , and between the infrared shielding filter layers 22 , each of the colored layers
near - infrared shielding filter layer 21 and the lens 50 . 20 is partitioned by the partition wall 2b , or by the partition wall
FIGS . 3 to 18 are schematic views showing the structure 2 and the partition wall 2b . A structure 110 shown in FIG . 10
of the embodiment of the present invention , which are has the same configuration as in FIG . 3 , except that in a
schematic views of a structure further having a color filter region in which the color filter layer 30 is provided, there is
layer, in addition to the near- infrared transmitting filter layer no partition wall between the colored layers , and colored
11 . 25 layers 31 to 33 are formed in one region partitioned by
A structure 103 shown in FIG . 3 has a support 1 , a partition wall 2. A structure 111 shown in FIG . 11 has the
partition wall 2 provided on the support 1 , a near - infrared same configuration as in FIG . 3 , except that the top surface
transmitting filter layer 11 provided in a region partitioned of each of the colored layers is higher than the near - infrared
by the partition wall 2 , and a color filter layer 30 provided transmitting filter layer 11 and the height difference between
in a region partitioned by the partition wall 2 , different from 30 the both is filled with the lens 50. A structure 112 shown in
the region in which the near -infrared transmitting filter layer FIG . 12 has the same configuration as in FIG . 3 , except that
11 is provided . In FIG . 3 , the color filter layer 30 is formed the top surface of each of the colored layers is lower than the
of colored layers 82 , and 33. The colored layers 31 to 33 near - infrared transmitting filter layer 11 and the height
may be colored layers which are the same as or different difference between the both is filled with the lens 50. A
from each other. Further, a near -infrared shielding filter layer 35 structure 113 shown in FIG . 13 has the same configuration
22 is provided between the colored layer and the support 1 . as in FIG . 3 , except that in a region in which the color filter
That is , a laminate of the near - infrared shielding filter layer layer 30 is provided , a transparent layer 41 is provided on
22 and the colored layer 31 , a laminate of the near - infrared each of the colored layers. A structure 114 shown in FIG . 14
shielding filter layer 22 and the colored layer 32 , and a has the same configuration as in FIG . 3 , except that a
laminate of the near - infrared shielding filter layer 22 and the 40 laminate of a near - infrared shielding filter layer 22 and a
colored layer 33 are each formed on a region partitioned by transparent layer 42 is provided in a region partitioned by the
the partition wall . Further, a lens 50 is provided on the partition wall 2 on the support 1 , different from the region
near- infrared transmitting filter layer 11 and the color filter in which the near- infrared transmitting filter layer 11 and the
layer 30. In addition , in FIG . 3 , the thicknesses of the color filter layer 30 are provided . Further, in FIG . 14 , only
laminate of the near - infrared shielding filter layer 22 and the 45 the transparent layer 42 may be provided , instead of the
colored layer 31 , the laminate of the near - infrared shielding laminate of the near- infrared shielding filter layer 22 and the
filter layer 22 and the colored layer 32 , and the laminate of transparent layer 42. A structure 115 shown in FIG . 15 has
the near - infrared shielding filter layer 22 and the colored the same configuration as in FIG . 3 , except that the top
layer 33 are same as each other, but may be different from surface of the near - infrared transmitting filter layer 11 is
each other. From the viewpoint of flatness, adhesiveness, a 50 higher than the top surface of each of the colored layers, and
higher resolution by the control of incident angles, or the the height difference of the both is filled with a lens 50. A
like , it is preferable that the heights (thicknesses ) of the structure 116 shown in FIG . 16 has the same configuration
respective laminates are almost same as each other. Inci- as in FIG . 3 , except that the top surface of the near -infrared
dentally, it is preferable that the height differences of the transmitting filter layer 11 is lower than the top surface of
colored layer and the top surface of the near - infrared trans- 55 each of the colored layers , and the height difference of the
mitting filter layer 11 are almost same as each other. In both is filled with the lens 50. A structure 117 shown in FIG .
addition, an intermediate layer may be provided between the 17 has the same configuration as in FIG . 3 , except that a
near -infrared transmitting filter layer 11 and the lens 50 , transparent layer 41 is provided on the near - infrared trans
between the color filter layer 30 and the lens 50 , and between mitting filter layer 11. A structure 118 shown in FIG . 18 has
the color filter layer 30 and the near -infrared shielding filter 60 the same configuration as in FIG . 3 , except that a black
layer 22 . matrix 5 is provided on the support 1 and the partition wall
A structure 104 shown in FIG . 4 has the same configu- 2 are provided on the black matrix 5. In FIGS . 5 to 18 , an
ration as in FIG . 3 , except that an underlayer 4 is provided underlayer may further be formed on the support 10. Further,
on the support 1 and the partition wall 2 is provided on the in FIGS . 4 to 18 , an intermediate layer may be provided
underlayer 4. A structure 105 shown in FIG . 5 has the same 65 between the members of the upper layer and the lower layer.
configuration as in FIG . 3 , except that a near - infrared In addition, in FIGS . 4 to 6 , and 8 to 18 , a protective layer
shielding filter layer 22 is provided on each colored layer of may further be provided on a surface of the partition wall .
 US 10,991,749 B2
17 18
<Optical Sensor > case where the absorbance is measured in the state of a film ,
Next, the optical sensor of an embodiment of the present for example, a method of adjusting the thickness of the film
invention will be described . The optical sensor of the may be mentioned .
embodiment of the present invention includes the above- It is more preferable that the composition for a near
mentioned structure of the embodiment of the present inven- 5 infrared transmitting filter layer satisfies spectral character
tion . The optical sensor of the embodiment of the present istics of any one of ( 1 ) to ( 4 ) below.
invention can be preferably used in applications such as ( 1 ) : A ratio of the minimum value Amin 1 in an absor
surveillance applications, security applications, mobile bance in a wavelength range of 400 to 640 nm to the
applications, automotive applications, agricultural applica- maximum value Bmax 1 in an absorbance in a wavelength
tions , medical applications, distance measuring applications, 10 range of 800 to 1,300 nm , Amin 1 / Bmax 1 , is preferably 5
gesture recognition applications, and vital recognition appli- or more, more preferably 7.5 or more , still more preferably
cations. 15 or more , and even still more preferably 30 or more .
Composition for Forming Near -Infrared Transmitting According to this aspect , it is possible to form a film capable
Filter Layer > of shielding light in a wavelength range of 400 to 640 nm
Next, the composition for forming a near-infrared trans- 15 nmand. transmitting near -infrared light at a wavelength of 720
mitting filter layer of an embodiment of the present inven
tion will be described . The composition for forming a ( 2 ) : A ratio of the minimum value Amin 2 in an absor
near - infrared transmitting filter layer of the embodiment of bance in a wavelength range of 400 to 750 nm to the
the present invention is a composition used for the formation maximum value Bmax 2 in an absorbance in a wavelength
of the above-mentioned near -infrared transmitting filter 20 range of 900 to 1,300 nm , Amin 2/Bmax 2 , is preferably 5
layer of the structure of the embodiment of the present or more, more preferably 7.5 or more , still more preferably
invention , in which the composition includes a color mate- 15 or more , and even still more preferably 30 or more.
rial and a curable compound . Hereinafter, the composition According to this aspect , it is possible to form a film capable
for forming a near - infrared transmitting filter layer is also of shielding light in a wavelength range of 400 to 750 nm
referred to as a composition for a near - infrared transmitting 25 and transmitting near - infrared light at a wavelength of 850
filter. nm .
Next, the composition for a near - infrared transmitting ( 3 ) : A ratio of the minimum value Amin 3 in an absor
filter has a ratio of the minimum value Amin in an absor- bance in a wavelength range of 400 to 850 nm to the
bance in a wavelength range of 400 to 640 nm to the maximum value Bmax 3 in an absorbance in a wavelength
maximum value Bmax in an absorbance in a wavelength 30 range of 1,000 to 1,300 nm , Amin 3 /Bmax 3 , is preferably
range of 1,100 to 1,300 nm , Amin /Bmax , of preferably 5 or 5 or more, more preferably 7.5 or more, still more preferably
more, more preferably 7.5 or more , still more preferably 15 15 or more , and even still more preferably 30 or more .
or more, and particularly preferably 30 or more . According to this aspect, it is possible to form a film capable
An absorbance Al , at a certain wavelength à is defined by of shielding light in a wavelength range of 400 to 830 nm
Expression ( 1 ) . 35 and transmitting near - infrared light at a wavelength of 940
nm .
AN = -log ( IN100 ) (1) ( 4 ) : A ratio of the minimum value Amin 4 in an absor
A? is an absorbance at a wavelength 2 , and Tì , represents bance in a wavelength range of 400 to 950 nm to the
a transmittance ( % ) at the wavelength à . maximum value Bmax 4 in an absorbance in a wavelength
In the present invention , a value of the absorbance may be 40 range of 1,100 to 1,300 nm , Amin 4 /Bmax 4 , is preferably
a value measured in the form of a solution or a value of a 5 or more , more preferably 7.5 or more , still more preferably
film which is formed using the composition for a near- 15 or more , and even still more preferably 30 or more .
infrared transmitting filter. In a case where the absorbance is According to this aspect, it is possible to form a film capable
measured in the state of the film , it is preferable that the of shielding light in a wavelength range of 400 to 950 nm
absorbance is measured using a film prepared by applying 45 and transmitting near - infrared light at a wavelength of 1,040
the composition for a near - infrared transmitting filter onto a nm .
glass substrate using a method such as spin coating such that In a case where a film having a thickness of 1 um , 2 um ,
the thickness of the dried film is a predetermined value , and 3 um , 4 um , or 5 um is formed using the composition for a
drying the applied composition using a hot plate at 100 ° C. near -infrared transmitting filter, it is preferable to satisfy the
for 120 seconds. The thickness of the film can be measured 50 spectral characteristics that the maximum value in a wave
using a stylus surface profilometer (DEKTAK 150 , manu- length range of 400 to 640 nm of the transmittance of light
factured by ULVAC Inc. ) onto a substrate including the film . in the thickness direction of the film is 20% or less and the
Moreover, the absorbance can be measured using a spec- minimum value in a wavelength range of 1,100 to 1,300 nm
trophotometer known in the related art. A measurement of the transmittance of light in the thickness direction is 70 %
condition for the absorbance is not particularly limited, but 55 or more. The maximum value in a wavelength range of 400
it is preferable that the maximum value B in the absorbance to 640 nm is preferably 15 % or less , and more preferably
in a wavelength range of 1,100 to 1,300 nm is measured 10% or less . The minimum value in a wavelength range of
under conditions which are adjusted such that the minimum 1,100 to 1,300 nm is preferably 75 % or more , and more
value A in the absorbance in a wavelength range of 400 to preferably 80 % or more .
640 nm is 0.1 to 3.0 . By measuring the absorbance under 60 The composition for a near - infrared transmitting filter
such conditions, a measurement error can be further layer preferably satisfies spectral characteristics of any one
reduced . A method of adjusting the minimum value Amin in of ( 11 ) to ( 14 ) below.
the absorbance in a wavelength range of 400 to 640 nm to ( 11 ) : An aspect in which in a case where a film having a
be 0.1 to 3.0 is not particularly limited . For example, in a thickness of 1 um , 2 um , 3 um , 4um , or 5 um is formed using
case where the absorbance is measured in the state of a 65 the composition for a near - infrared transmitting filter, the
solution , for example, a method of adjusting the optical path maximum value in a wavelength range of 400 to 640 nm of
length of a sample cell may be mentioned . In addition, in a the transmittance of light in the thickness direction of the
 US 10,991,749 B2
19 20
film is 20 % or less ( preferably 15 % or less , and more shields light in a wavelength range of 400 to 640 nm . In
preferably 10 % or less ) , and the minimum value in a addition , the light shielding material is preferably a color
wavelength range of 800 to 1,300 nm of the transmittance of material that transmits light at a wavelength of 1,100 to
light in the thickness direction of the film is 70 % or more 1,300 nm . In the present invention , the light shielding
( preferably 75 % or more , and more preferably 80 % or 5 material preferably satisfies at least one requirement of ( 1 )
more ). or ( 2 ) below.
( 12 ) : An aspect in which in a case where a film having a ( 1 ) : Two or more chromatic coloring agents are included
thickness of 1 um , 2 um , 3 um , 4 um , or 5 um is formed using and a combination of the two or more chromatic coloring
the composition for a near - infrared transmitting filter, the agents forms black .
maximum value in a wavelength range of 400 to 750 nm of 10 ( 2 ) : An organic black coloring agent is included . In the
the transmittance of light in the thickness direction of the aspect of (2 ) , it is preferable that a chromatic coloring agent
film is 20 % or less ( preferably 15 % or less , and more is further contained .
preferably 10 % or less ) , and the minimum value in a Moreover, in the present invention , the chromatic color
wavelength range of 900 to 1,300 nm of the transmittance of ing agent means a coloring agent other than a white coloring
light in the thickness direction of the film is 70% or more 15 agent and a black coloring agent. Further, in the present
( preferably 75 % or more , and more preferably 80 % or invention , the organic black coloring agent used for the light
more ) shielding material means a material that absorbs visible light
( 13 ) : An aspect in which in a case where a film having a but transmits at least a portion of near - infrared light. Accord
thickness of 1 um , 2 um , 3 um , 4 um , or 5um is formed using ingly, in the present invention, the organic black coloring
the composition for a near -infrared transmitting filter, the 20 agent used for the light shielding material does not include
maximum value in a wavelength range of 400 to 830 nm of a black coloring agent that absorbs both visible light and
the transmittance of light in the thickness direction of the near - infrared light, for example, carbon black and titanium
film is 20 % or less ( preferably 15 % or less , and more black . The organic black coloring agent is preferably a
preferably 10 % or less ) , and the minimum value in a coloring agent having the maximum absorption wavelength
wavelength range of 1,000 to 1,300 nm of the transmittance 25 in a wavelength range from 400 nm to 700 nm .
of light in the thickness direction of the film is 70% or more In the present invention , it is preferable that the light
(preferably 75 % or more , and more preferably 80 % or shielding material is a material in which a ratio A / B of the
more ). minimum value A of an absorbance in a wavelength range of
( 14 ) : An aspect in which in a case where a film having a 400 to 640 nm to the maximum value B of an absorbance in
thickness of 1 um , 2 um , 3 um , 4 um , or 5 um is formed using 30 a wavelength range of 1,100 to 1,300 nm is 4.5 or more .
the composition for a near - infrared transmitting filter, the The above - described characteristics may be satisfied
maximum value in a wavelength range of 400 to 950 nm of using one material singly or using a combination of a
the transmittance of light in the thickness direction of the plurality of materials. For example, in a case of the aspect
film is 20 % or less ( preferably 15 % or less , and more ( 1 ) , it is preferable that the spectral characteristics are
preferably 10 % or less ) , and the minimum value in a 35 satisfied using a combination of a plurality of chromatic
wavelength range of 1,100 to 1,300 nm of the transmittance coloring agents. In addition , in a case of the aspect of (2 ) , the
of light in the thickness direction of the film is 70% or more spectral characteristics may be satisfied using an organic
( preferably 75 % or more , and more preferably 80 % or black coloring agent. In addition , the spectral characteristics
more ). may be satisfied using a combination of an organic black
Hereinafter, the respective components that can constitute 40 coloring agent and a chromatic coloring agent.
the composition for a near - infrared transmitting filter will be ( Chromatic Coloring Agent)
described . In the present invention , the chromatic coloring agent is
<<Color Material>> preferably a coloring agent selected from a red coloring
The composition for a near -infrared transmitting filter agent, a green coloring agent, a blue coloring agent, a yellow
includes a color material. The content of the color material 45 coloring agent, a violet coloring agent, and an orange
is preferably 35 % to 80 % by mass with respect to the total coloring agent. In the present invention , the chromatic
solid content of the composition for a near - infrared trans- coloring agent may be either a pigment or a dye, and is
mitting filter. The lower limit is preferably 40% by mass or preferably the pigment. It is preferable that an average
more , more preferably 45 % by mass or more , still more particle diameter (r) of the pigment satisfies preferably 20
preferably 50 % by mass or more , and particularly preferably 50 nmsrs300 nm , more preferably 25 nmsrs250 nm , and still
55 % by mass or more . The upper limit is preferably 75 % by more preferably 30 nmsrs200 nm . An “ average particle
mass or less , and more preferably 70% by mass or less . diameter ” as mentioned herein means the average particle
Examples of the color material include a color material that diameter for secondary particles to which primary particles
shields visible light which will be described later, and a of the pigment are aggregated . In addition , with regard to a
near - infrared absorbing dye. The content of the color mate- 55 particle size distribution of the secondary particles of the
rial is preferably 50% to 75 % by mass with respect to the pigment (hereinafter simply referred to as “ particle size
total solid content of the composition for a near - infrared distribution ") which can be used, secondary particles having
transmitting filter a particle diameter in the range of an average particle
<< Color Material that Shields Visible Light >> diameter : 100 nm account for preferably 70 % by mass or
It is preferable that the composition for a near - infrared 60 more, and more preferably 80% by mass or more in the
transmitting filter contains a color material that shields entire pigment. In addition, the particle size distribution of
visible light ( hereinafter also referred to as a light shielding the secondary particles can be measured using a scattering
material. In the present invention , the light shielding mate- intensity distribution .
rial is preferably a color material that absorbs light in a The pigment is preferably an organic pigment. Examples
wavelength range from violet to red . Further, in the present 65 of the organic pigment include the following pigments.
invention , the light shielding material is preferably a color Color Index (C.I. ) Pigment Yellow 1 , 2 , 3 , 4 , 5 , 6 , 10 , 11 ,
material that shields visible light is a color material that 12 , 13 , 14 , 15 , 16 , 17 , 18 , 20 , 24 , 31 , 32 , 34 , 35 , 35 : 1 , 36 ,
 US 10,991,749 B2
21 22
36 : 1 , 37 , 37 : 1 , 40 , 42 , 43 , 53 , 55 , 60 , 61 , 62 , 63 , 65 , 73 , 74 , ( 6 ) An aspect in which the light shielding material con
77 , 81 , 83 , 86 , 93 , 94 , 95 , 97 , 98 , 100 , 101 , 104 , 106 , 108 , tains a red coloring agent, a blue coloring agent, and a green
109 , 110 , 113 , 114 , 115 , 116 , 117 , 118 , 119 , 120 , 123 , 125 , coloring agent.
126 , 127 , 128 , 129 , 137 , 138 , 139 , 147 , 148 , 150 , 151 , 152 , ( 7 ) An aspect in which the light shielding material con
153 , 154, 155 , 156 , 161 , 162 , 164 , 166 , 167 , 168 , 169 , 170 , 5 tains a yellow coloring agent and a violet coloring agent.
171 , 172 , 173 , 174 , 175 , 176 , 177 , 179 , 180 , 181 , 182 , 185 , In the above aspect of ( 1 ) , the mass ratio of the red
coloring
187 , 188 , 193 , 194 , 199 , 213 , 214 , and the like ( all of which coloring agent agent to the blue coloring agent in terms of red
are yellow pigments ), : blue coloring agent is preferably 20 to 80:20
C. I. Pigment Orange 2 , 5 , 13 , 16 , 17 : 1 , 31 , 34 , 36 , 38 , 43 , to 80 , more preferably 20 to 60:40 to 80 , and still more
46 , 48, 49 , 51 , 52 , 55 , 59 , 60, 61 , 62 , 64 , 71 , 73 , and the like 10 preferably
In the above aspect of80(2. ) , the mass ratio of the red
20 to 50:50 to
( all of which are orange pigments ), coloring agent to the blue coloring agent to the yellow
C. I. Pigment Red 1 , 2 , 3 , 4 , 5 , 6 , 7 , 9 , 10 , 14 , 17 , 22 , 23 , coloring agent in terms of red coloring agent:blue coloring
31,38 , 41 , 48 : 1 , 48 : 2 , 48 : 3 , 48 : 4 , 49 , 49 : 1 , 49 : 2 , 52 : 1 , 52 : 2 , agent :yellow coloring agent is preferably 10 to 80:20 to
53105: 1, , 112
57 :,1 119
, 60, : 1122
, 63, :123
1 , 66, 144
, 67, ,146
81 :, 1149
, 81, : 2150
, 81, :155
3 , ,83166
,88, ,168
90,, 15 80:10 to 40, more preferably 10 to 60:30 to 80:10 to 30, and
still more preferably 10 to 40:40 to 80:10 to 20 .
169 , 170 , 171 , 172 , 175 , 176 , 177 , 178 , 179 , 184 , 185 , 187 , In the above aspect of (3 ) , the mass ratio of the red
188 , 190 , 200 , 202 , 206 , 207 , 208 , 209 , 210 , 216 , 220 , 224 , coloring agent to the blue coloring agent to the yellow
226 , 242 , 246 , 254 , 255 , 264 , 270 , 272 , 279 , and the like ( all coloring agent to the violet coloring agent in terms of red
of which are red pigments ), 20 coloring agent : blue coloring agent:yellow coloring agent:
C. I. Pigment Green 7 , 10 , 36 , 37 , 58 , 59 , and the like ( all violet coloring agent is preferably 10 to 80:20 to 80 : 5 to 40 : 5
of which are green pigments ), to 40 , more preferably 10 to 60:30 to 80 : 5 to 30 : 5 to 30 , and
C. I. Pigment Violet 1 , 19 , 23 , 27 , 32 , 37 , 42 , and the like still more preferably 10 to 40:40 to 80 : 5 to 20 : 5 to 20 .
( all of which are violet pigments ), In the above aspect of (4 ) , the mass ratio of the red
C. I. Pigment Blue 1 , 2 , 15 , 15 : 1 , 15 : 2 , 15 : 3 , 15 : 4 , 15 : 6 , 25 coloring agent to the blue coloring agent to the yellow
16 , 22 , 60 , 64 , 66 , 79 , 80 , and the like (all of which are blue coloring agent to the violet coloring agent to the green
pigments ). coloring agent in terms of red coloring agent:blue coloring
These organic pigments can be used singly or in combi agent : yellow coloring agent : violet coloring agent:green col
nation of two or more kinds thereof. oring agent is preferably 10 to 80:20 to 80 : 5 to 40 : 5 to 40 : 5
The dye is not particularly limited and known dyes can be 30 to30,40and
, more preferably 10 to 60:30 to 80: 5 to 30: 5 to 30: 5 to
still more preferably 10 to 40:40 to 80 : 5 to 20 : 5 to
used . In terms of the chemical structures, a dye such as a 20 : 5 to 20 .
pyrazole azo - based dye, an anilino azo - based dye, a triaryl In the above aspect of ( 5 ) , the mass ratio of the red
methane -based dye, an anthraquinone -based dye, an coloring agent to the blue coloring agent to the yellow
anthrapyridone
nol -based dye, a-based dye, a benzylidene
pyrazolotriazole -based
azo -based dyedye , an oxo- 35
, a pyridone coloring agent to the green coloring agent in terms of red
azo -based dye, a cyanine -based dye, a phenothiazine -based coloring agent:blue coloring agent: yellow coloring agent:
green coloring agent is preferably 10 to 80:20 to 80 : 5 to 40 :5
dye , a pyrrolopyrazole azomethine- based dye, a xanthene to 40 , more preferably 10 to 60:30 to 80 : 5 to 30 : 5 to 30 , and
based dye, a phthalocyanine -based dye, a benzopyran - based still more preferably 10 to 40:40 to 80 : 5 to 20 : 5 to 20 .
dye, an indigo - based dye, or a pyrromethene-based dye can 40 In the above aspect of ( 6 ) , the mass ratio of the red
be used . In addition , a dimer of such a dye may be used . In coloring agent to the blue coloring agent to the green
addition , dyes described in JP2015-028144A and JP2015- coloring agent in terms of red coloring agent:blue coloring
034966A can also be used . agent : green coloring agent is preferably 10 to 80:20 to 80:10
It is preferable that the light shielding material includes at to 40 , more preferably 10 to 60:30 to 80:10 to 30 , and still
least two or more selected from a red coloring agent, a blue 45 more preferably 10 to 40:40 to 80:10 to 20 .
coloring agent, a yellow coloring agent, a violet coloring In the above aspect of (7 ) , the mass ratio of the yellow
agent, or a green coloring agent. That is , it is preferable that coloring agent to the violet coloring agent in terms of yellow
the light shielding material forms black by combination of at coloring agent:violet coloring agent is preferably 10 to 50:40
least two or more selected from a red coloring agent, a blue to 80 , more preferably 20 to 40:50 to 70 , and still more
coloring agent, a yellow coloring agent, a violet coloring 50 preferably 30 to 40:60 to 70 .
agent, or a green coloring agent. Preferred examples of the As the yellow coloring agent, C. I. Pigment Yellow 139 ,
combination include the following aspects . 150 , or 185 is preferable , C. I. Pigment Yellow 139 or 150
( 1 ) An aspect in which the light shielding material con- is more preferable, and C. I. Pigment Yellow 139 is still
tains a red coloring agent and a blue coloring agent. more preferable. As the blue coloring agent, C. I. Pigment
( 2) An aspect in which the light shielding material con- 55 Blue 15 : 6 is preferable. As the violet coloring agent, C. I.
tains red coloring agent, a blue coloring agent, and a yellow Pigment Violet 23 is preferable. As the red coloring agent,
coloring agent. Pigment Red 122 , 177 , 224 , or 254 is preferable, Pigment
(3 ) An aspect in which the light shielding material con- Red 122 , 177 , or 254 is more preferable, and Pigment Red
tains a red coloring agent, a blue coloring agent, a yellow 254 is still more preferable. As the green coloring agent , C.
coloring agent, and a violet coloring agent. 60 I. Pigment Green 7 ; 36 , 58 , or 59 is preferable .
(4 ) An aspect in which the light shielding material con- ( Organic Black Coloring Agent)
tains a red coloring agent, a blue coloring agent, a yellow In the present invention , examples of the organic black
coloring agent, a violet coloring agent, and a green coloring coloring agent include a bisbenzofuranone compound, an
agent. azomethine compound, a perylene compound, and an azo
( 5 ) An aspect in which the light shielding material con- 65 based compound , and the bisbenzofuranone compound or
tains a red coloring agent, a blue coloring agent, a yellow the perylene compound is preferable . Examples of the
coloring agent, and a green coloring agent. bisbenzofuranone compound include those described in
 US 10,991,749 B2
23 24
JP2010-534726A , JP2012-515233A , and JP2012-515234A , an alkenyl group , alkynyl group , an aralkyl group , an aryl
and are available as , for example, " Irgaphor Black ” manu- group , 303
a heteroaryl group , OR301, COR 302
factured by BASF Corporation . Examples of the perylene COOR OCOR304 NR305R306 NHCOR 307
compound include C. I. Pigment Black 31 and 32. Examples CONR308R309 NHCONR310R311 NHCOOR312
2

of the azomethine compound include those described in 5 SR313, SO , R314, SO , OR315, NHSO , R316 , or
JP1989-170601A (JP - H01-170601A) , JP1990-034664A SO , NR317R315 , and R301 to R318 each independently
( JP - H02-034664A) , and the like , and are available as , for represent a hydrogen atom , an alkyl group , an alkenyl group ,
example , " CHROMOFINE BLACK A1103” manufactured an alkynyl group , an aryl group , or a heteroaryl group .
by Dainichiseika Color & Chemicals Mfg. Co. , Ltd. With regard to the details of the bisbenzofuranone com
In the present invention , the bisbenzofuranone com- 10 pounds , reference can be made to the descriptions in para
pounds are preferably compounds represented by the fol- graph Nos . 0014 to 0037 of JP2010-534726A , the contents
lowing formulae or a mixture thereof. of which are incorporated herein by reference .
In the present invention , in a case where an organic black
coloring agent is used as the light shielding material, it is
15 preferable that the organic black coloring agent is used in
R2 combination of a chromatic coloring agent. By using the
(R3)
organic black coloring agent in combination of the chro
matic coloring agent, excellent spectral characteristics are
likely to be obtained . Examples of the chromatic coloring
20 agent which is used in combination with the organic black
coloring agent include a red coloring agent, a blue coloring
b(R4) agent, and a violet coloring agent, and the red coloring agent
or the blue coloring agent is preferable. These may be used
Rl and /or singly or in combination of two or more kinds thereof.
25 In addition , with regard to a mixing ratio of the chromatic
coloring agent to the organic black coloring agent, the
R2 amount of the organic black coloring agent is preferably 10
to 200 parts by mass , and more preferably 15 to 150 parts by
mass , with respect to 100 parts by mass of the organic black
30 coloring agent.
In the present invention , the content of the pigment in the
R and /or light shielding material is preferably 95 % by mass or more ,
ö(R4) more preferably 97 % by mass or more , and still more
preferably 99 % by mass or more, with respect to the total
35 mass of the light shielding material.
The content of the light shielding material in the compo
sition for a near - infrared transmitting filter is preferably 10 %
(R)a to 80 % by mass with respect to the total solid content of the
b(R ) composition for forming a near - infrared transmitting filter.
40 The lower limit is preferably 30% by mass or more, more
preferably 35 % by mass or more , still more preferably 40 %
by mass or more , even still more preferably 45 % by mass or
more, and particularly preferably 50 % by mass or more . The
upper limit is preferably 75 % by mass or less , and more
N 45 preferably 70 % by mass or less .
R2 (Near- Infrared Absorbing Dye )
R? The composition for a near - infrared transmitting filter can
contain a near - infrared absorbing dye as the color material.
In the near -infrared transmitting filter, the near - infrared
50 absorbing dye plays a role in limiting transmissive light
(near - infrared light) to a longer wavelength side .
In the present invention , a compound having the maxi
(R3) mum absorption wavelength in a wavelength range of the
near - infrared region ( preferably in a wavelength range of
55 more than 700 nm and 1,300 nm or less ) can be preferably
In the formula, R and R each independently represent a used as the near -infrared absorbing dye. The near - infrared
hydrogen atom or a substituent, R3 and R * each indepen- absorbing dye may be either a pigment or a dye.
dently represent a substituent, and a and b each indepen- In the present invention , as the near- infrared absorbing
dently represent an integer of 0 to 4 ; in a case where a is 2 dye, a near - infrared absorbing compound having a i -con
or more, a plurality of Rº's may be the same as or different 60 jugated plane including a monocyclic or fused aromatic ring
from each other and the plurality of Rº’s may be bonded to can be preferably used . The number of atoms other than
each other to form a ring, in a case where b is 2 or more , a hydrogen constituting a h -conjugated plane contained in the
plurality of Rº's may be the same as or different from each near - infrared absorbing compound is preferably 14 or more ,
other and the plurality of Rº's may be bonded to each other more preferably 20 or more , still more preferably 25 or
to form a ring. 65 more, and particularly preferably 30 or more . The upper
The substituent represented by each of R ' to R + represents limit is , for example, preferably 80 or less , and more
a halogen atom , a cyano group , a nitro group , an alkyl group , preferably 50 or less .
 US 10,991,749 B2
25 26
The -conjugated plane contained in the near - infrared include the compounds described in paragraph No. 0093 of
absorbing compound preferably includes two or more mono- JP2012-077153A , the contents of which are incorporated
cyclic or fused aromatic rings, more preferably includes herein by reference . Further, as the cyanine compound, the
three or more monocyclic or fused aromatic rings , still more phthalocyanine compound, the naphthalocyanine com
preferably includes four or more monocyclic or fused aro- 5 pound, the diimmonium compound, and the squarylium
matic rings, and particularly preferably includes five or more compound, the compounds described in paragraph Nos .
monocyclic or fused aromatic rings . The upper limit is 0010 to 0081 of JP2010-111750A , the contents of which are
preferably 100 or less , more preferably 50 or less , and still incorporated herein by reference , may be used . Incidentally,
more preferably 30 or less . Examples of the above -men- with reference to the cyanine compound, reference can be
tioned aromatic ring include a benzene ring, a naphthalene 10 made to , for example, “ Functional Colorants, edited by
ring , a pentalene ring , an indene ring , an azulene ring , a Makoto Okawara /Masaru Matsuoka / Teijiro Kitao /Tsuneoka
heptalene ring, an indacene ring, a perylene ring , a penta- Hirashima , published by Kodansha Scientific Ltd.” , the
cene ring , a quarterylene group , an acenaphthene ring , a contents of which are incorporated herein by reference . In
phenanthrene ring, an anthracene ring, a naphthacene ring, addition , as the near -infrared absorbing compound, the
a chrysene ring , a triphenylene ring , a fluorene ring, a 15 compounds described in JP2016-146619A , the contents of
pyridine ring , a quinoline ring , an isoquinoline ring, an which are incorporated herein by reference, can also be
imidazole ring, a benzimidazole ring, a pyrazole ring, a used .
thiazole ring, a benzothiazole ring, a triazole ring , a benzo- As the pyrrolopyrrole compound, a compound repre
triazole ring , an oxazole ring, a benzoxazole ring , an imi- sented by Formula ( PP ) is preferable.
dazoline ring, a pyrazine ring, an a quinoxaline ring , an a 20
pyrimidine ring, an a quinazoline ring, a pyridazine ring, a
triazine ring , a pyrrole ring , an indole ring , an isoindole ring, Rla
( PP )
a carbazole ring, and a fused ring having such the ring . R2
The near - infrared absorbing compound is preferably a N -R4
compound having the maximum absorption wavelength in a 25 R3
wavelength range of700 to 1,000 nm . Further, in the present
specification, an expression, “ having the maximum absorp N R3
tion wavelength in a wavelength range of 700 to 1,000 nm ” R47
means having a wavelength exhibiting the maximum absor RID
R2
bance in a wavelength range of 700 to 1,000 nm in an 30
absorption spectrum in a solution of the near - infrared
absorbing compound. Examples of a measuring solvent used In the formula, Rla and Rib each independently represent
for the measurement of the absorption spectrum of the an alkyl group , an aryl group , or a heteroaryl group , R² and
solution of the near -infrared absorbing compound include Reach independently represent a hydrogen atom or a
chloroform , methanol, dimethyl sulfoxide, ethyl acetate , and 35 substituent, R2 and R3 may be bonded to each other to form
tetrahydrofuran . In a case of the compound which is dis- a ring , R * 's each independently represent a hydrogen atom ,
solved in chloroform , chloroform is used as the measure- an alkyl group , an aryl group , a heteroaryl group ,
ment solvent. In a case of the compound which is not BR44R4B , or a metal atom , R * may be bonded to at least
dissolved in chloroform , methanol is used . In addition, in a one selected from Rla , Rlb , or R3 through a covalent bond
case where the compound is not dissolved in any of chlo- 40 or a coordination bond, and R44 and R4B each independently
roform and methanol, dimethyl sulfoxide is used . represent a substituent. With reference to the details of
In the present invention , as the near - infrared absorbing Formula ( PP ) , reference can be made to the descriptions in
compound, at least one compound selected from a pyrrolo- paragraph Nos . 0017 to 0047 of JP2009-263614A , para
pyrrole compound, a cyanine compound, a squarylium com- graph Nos. 0011 to 0036 of JP2011-068731A , and paragraph
pound, a phthalocyanine compound, a naphthalocyanine 45 Nos . 0010 to 0024 of WO2015 / 166873A , the contents of
compound , a quaterrylene compound, a merocyanine com- which are incorporated herein by reference .
pound, a croconium compound, an oxonol compound, a Rla and R16 are each independently preferably an aryl
diimmonium compound, a dithiol compound, a triarylmeth- group or a heteroaryl group , and more preferably an aryl
ane compound, a pyrromethene compound, an azomethine group . Further, the alkyl group , the aryl group , and the
compound, an anthraquinone compound, or a dibenzofura- 50 heteroaryl group, represented by each of Rla and R16 , may
none compound is preferable ; at least one compound have a substituent or may be unsubstituted . Examples of the
selected from a pyrrolopyrrole compound, a cyanine com substituent include an alkoxy group , a hydroxy group , a
pound, a squarylium compound, a phthalocyanine com- halogen atom , a cyano group, a nitro group , OCOR11
pound, a naphthalocyanine compound , or a diimmonium SOR ! ?, and SO_R13. Ril to R13 each independently
compound is more preferable; at least one selected from a 55 represent a hydrocarbon group or a heterocyclic group .
pyrrolopyrrole compound, a cyanine compound, or a squary- Further, examples of the substituent include the substituents
lium compound is more preferable; and a pyrrolopyrrole described in paragraph Nos . 0020 to 0022 of JP2009
compound is particularly preferable. Examples of the diim- 263614A . Among those, as the substituent, an alkoxy group ,
monium compound include the compounds described in a hydroxy group , a cyano group , a nitro group , -OCOR11
JP2008-528706A , the contents of which are incorporated 60 SOR12,or SO_R13 is preferable .As the group repre
herein by reference . Examples of the phthalocyanine com- sented by each of Rla or Rlb , an aryl group having an alkoxy
pound include the compounds described in paragraph No. group having a branched alkyl group as a substituent, an aryl
0093 of JP2012-077153A , the oxytitanium phthalocyanine group having a hydroxy group as a substituent, or an aryl
described in JP2006-343631A , and the compounds group having a group represented by OCOR11 as a sub
described in paragraph Nos . 0013 to 0029 of JP2013- 65 stituent is preferable. The number of carbon atoms of the
195480A , the contents of which are incorporated herein by branched alkyl group is preferably 3 to 30 , and more
reference . Examples of the naphthalocyanine compound preferably 3 to 20.
 US 10,991,749 B2
27 28
It is preferable that at least one of R² or R3 is an electron group, an aryl group or a group represented by - BR44R4B ,
withdrawing group , and it is more preferable that R² repre- and still more preferably a group represented by
sents an electron withdrawing group (preferably a cyano BR44R4B. As the substituent represented by each of R44
group ) and R3 represents a heteroaryl group . The heteroaryl and R4B , a halogen atom , an alkyl group , an alkoxy group ,
group is preferably a 5- or 6 -membered ring. Further, the 5 an aryl group , or a heteroaryl group is preferable, and an
heteroaryl group is preferably a monocycle or a fused ring, alkyl group , an aryl group , or a heteroaryl group is more
a monocycle or a fused ring having 2 to 8 fusions is more preferable, and an aryl group is particularly preferable. Such
preferable ; and a monocycle or a fused ring having 2 to 4 a group may further have a substituent. Two R4's in Formula
fusions is still more preferable. The number of heteroatoms (PP ) may be the same as or different from each other.
constituting the heteroaryl group is preferably 1 to 3 , and 10 Specific examples of the compound represented by For
more preferably 1 or 2. Examples of the heteroatom include mula (PP ) include the following compounds. In the follow
a nitrogen atom , an oxygen atom , and a sulfur atom . The ing structural formulae, Me represents a methyl group and
heteroaryl group preferably has one or more nitrogen atoms. Ph represents a phenyl group . Further , examples of the
Two R2's in Formula (PP ) may be the same as or different pyrrolopyrrole compound include the compounds described
from each other. Further, two Rº's in Formula (PP ) may be 15 in paragraph Nos . 0016 to 0058 of JP2009-263614A , the
the same as or different from each other. compounds described in paragraph Nos . 0037 to 0052 of
R4 is preferably a hydrogen atom , an alkyl group , an aryl JP2011-068731A , and the compounds described in para
group, a heteroaryl group , or a group represented by graph Nos . 0010 to 0033 of WO2015 / 166873A , the contents
BR44R4B, more preferably a hydrogen atom , an alkyl of which are incorporated herein by reference.
?Me

Ph
| Ph OH

NC
CN

B
HO
Ph
Ph

OMe

Ph Ph
B?

NMe
NC
CN
MeN

Ph
Ph
 US 10,991,749 B2
29 30
-continued

Ph Ph Ph Ph

NC CN NC CN

|
?
|B
Ph Ph Ph Ph

i -C3H17

* i-C10H21
Ph Ph

NC CN

Ph Ph
i-C10H21

i -C3H17

As the squarylium compound , a compound represented by an alkyl group , an alkenyl group , or an aralkyl group , d
Formula ( SQ ) is preferable . represents 0 or 1 , and a wavy line represents a linking arm .
The number of carbon atoms of the aryl group represented
45 by each of Al and A2 is preferably 6 to 48 , more preferably
(SQ) 6 to 24 , and particularly preferably 6 to 12 .
As the heteroaryl group represented by each of A ' and A² ,
a 5- or 6 -membered ring is preferable. Further, the heteroaryl
Al 2+ A2 50 group is preferably a monocycle or a fused ring having 2 to
8 fusions, more preferably a monocycle or a fused ring
having 2 to 4 fusions, and still more preferably a monocycle
or a fused ring having 2 or 3 fusions. Examples of the
heteroatom constituting the ring of the heteroaryl group
In Formula ( SQ ) , Al and A each independently represent include a nitrogen atom , an oxygen atom , and a sulfur atom ,
55
an aryl group , a heteroaryl group , or a group represented by with the nitrogen atom or the sulfur atom being preferable.
Formula (A- 1 ) ; The number of heteroatoms constituting the heteroaryl
group is preferably 1 to 3 , and more preferably 1 or 2 .
The aryl group and the heteroaryl group may have a
(A- 1 ) 60 substituent. In a case where the aryl group and the heteroaryl
z! group have two or more substituents, the plurality of sub
Rº?N - CH = CH - C = CH nhun stituents may be the same as or different from each other.
Examples of the substituent include a halogen atom , a
cyano group , a nitro group , an alkyl group , an alkenyl group ,
65 an alkynyl group, an aryl group , a heteroaryl group , aralkyl
in Formula ( A - 1 ), Z represents a non -metal atomic group group , OR10 , COR11, COOR12 , OCOR13
that forms a nitrogen - containing heterocycle, R2 represents NR4R15 - NHCOR16 CONRI7R18
 US 10,991,749 B2
31 32
NHCONR19R20 NHCOOR21, SR22 , SO ,R23 Examples of the substituent represented by each of X4 and
SO , OR24 , - NHSO_R25 , and SO NR26R37 . R10 to R21 XB include the substituents described in Formula ( SQ ) as
each independently represent a hydrogen atom , an alkyl described above, and as the substituent, a group having
group , an alkenyl group , an alkynyl group , an aryl group , a active hydrogen is preferable, OH , SH , COOH ,
heteroaryl group , or aralkyl group . Further, in a case where 5 SOZH , NRR2, NHCORI CONRY1R -12, .

R12 in COOR12 is a hydrogen atom , the hydrogen atom NHCONRYIR 12 NHCOORI - NHSO R * ,
may be dissociated or in the form of a salt . In addition, in a B (OH ) , or -PO (OH ) , is more preferable, and OH ,
case where R24 in SOZOR24 is a hydrogen atom , the SH , or NRX1R12 is still more preferable.
hydrogen atom may be dissociated or in the form of a salt . R * i and R 12 each independently represent a hydrogen
Next, a group represented by Formula ( A - 1 ), which is 10 atom or a substituent. Examples of the substituent include an
represented by Al and A’ , will be described. alkyl group , an alkenyl group , an alkynyl group, an aryl
In Formula (A - 1 ) , R? represents an alkyl group , an alkenyl group , and a heteroaryl group , with the alkyl group being
group , or an aralkyl group , with the alkyl group being preferable.
preferable. In Formula (A - 1 ) , as the nitrogen - containing The ring A and the ring B each independently represent an
heterocycle formed by Z ' , a 5- or 6 -membered ring is 15 aromatic ring . The aromatic ring may be a monocycle or a
preferable. Further, the nitrogen -containing heterocycle is fused ring . Specific examples of the aromatic ring include a
preferably a monocycle or a fused ring having 2 to 8 fusions, benzene ring, a naphthalene ring, a pentalene ring, an indene
more preferably a monocycle or a fused ring having 2 to 4 ring, an azulene ring, a heptalene ring, an indecene ring , a
fusions, and still more preferably a fused ring having 2 or 3 perylene ring, a pentacene ring, an acenaphthene ring, a
fusions. The nitrogen - containing heterocycle may include a 20 phenanthrene ring, an anthracene ring , a naphthacene ring,
sulfur atom , in addition to a nitrogen atom . In addition, the a chrysene ring, a triphenylene ring, a fluorene ring, a
nitrogen -containing heterocycle may have a substituent. biphenyl ring , a pyrrole ring, a furan ring , a thiophene ring,
Examples of the substituent include the above -mentioned an imidazole ring, an oxazole ring , a thiazole ring, a pyridine
substituents. ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an
With regard to the details of Formula ( SQ ) , reference can 25 indolizine ring, an indole ring, a benzofuran ring , a benzo
be made to the descriptions in paragraph Nos . 0020 to 0049 thiophene ring , an isobenzofuran ring, a quinolizine ring, a
of JP2011-208101A , the contents of which are incorporated quinoline ring, a phthalazine ring, a naphthyridine ring , a
herein by reference . quinoxaline ring, a quinoxazoline ring , an isoquinoline ring,
Moreover, the cation in Formula ( SQ ) is present while not a carbazole ring, a phenanthridine ring, an acridine ring , a
being localized as below . 30 phenanthroline ring, a thianthrene ring , a chromene ring, a
xanthene ring, a phenoxathiin ring , a phenothiazine ring, and
a phenazine ring, with the benzene ring or the naphthalene
0 0 ring being preferable . The aromatic ring may be unsubsti
Al 2+ -A2 -A2 tuted or may have a substituent. Examples of the substituent
35 include the substituents described in Formula ( SQ ) as
0
described above .
X4 and G4, or XP and GP may be bonded to each other to
form a ring , and in a case where a plurality of G4's and GP's
As the squarylium compound , a compound represented by are present, they may be bonded to each other, respectively ,
Formula ( SQ - 1 ) is preferable. 40 to form a ring . The ring is preferably a 5- or 6 -membered
ring. The ring may be a monocycle or a fused ring. In a case
where X4 and G?, or XP and GP, G4's, or GP's are bonded
( SQ - 1 )
to each other to form a ring, the groups may be directly

.
X4 bonded to each other to form a ring or may be bonded to
45 each other through a divalent linking group selected from
the group consisting of an alkylene group, —CO ,
B NH , BR-, and a combination thereof to form a ring .
(GB)KB It is preferable that X4 and G4, or XP and Gº, G4's, or GP's
XB
are bonded to each other through —BR— to form a ring . R
50 represents a hydrogen atom or a substituent. Examples of the
substituent include the substituents described in Formula
The ring A and the ring B each independently represent an ( SQ ) as described above , and the substituent is preferably an
aromatic ring. alkyl group or an aryl group .
X4 and XP each independently represent a substituent. kA represents an integer of 0 to ng kB represents an
G4 and G each independently represent a substituent. 55 integer of 0 to 13, 14 represents an integer representing the
KA represents an integer of 0 to ng, and kB represents an maximum number of G \ 's which may be substituted in the
integer of 0 to ni : ring A , and ng represents an integer representing the maxi
ng and ng each represent an integer representing the mum number of ' s which may be substituted in the ring
maximum number of the groups which may be substituted in B. KA and kB are each independently preferably an integer
the ring A or the ring B. 60 of 0 to 4 , more preferably 0 to 2 , and particularly preferably
X4 and G4, or XB and may be bonded to each other to O or 1 .
form a ring , and in a case where a plurality of GA's and a Examples of the squarylium compound include the com
plurality of GP's are present, G4's and GP's may be bonded pounds described in paragraph Nos . 0044 to 0049 of
to each other to form ring structures, respectively . JP2011-208101A , the contents of which are incorporated
Examples of the substituent represented by each of G4 and 65 herein by reference.
GB include the substituents described in Formula ( SQ ) as The cyanine compound is preferably a compound repre
described above . sented by Formula ( C ) .
 US 10,991,749 B2
33 34
Formula ( C ) substituent or may be unsubstituted . Examples of the sub
stituent include the substituents described for Formula ( SQ ) .
(X !) In Formula ( C ) , L ' represents a methine chain having an
5 odd number of methine groups. L ' is preferably a methine
R101_N C - L = C N - R1 102
chain having 3 , 5 , or 7 methine groups.
(CH -CH ) (CH = CH ) The methine group may have a substituent. It is preferable
that the methine group having a substituent is a methine
?? 10 group positioned at the center (meso position ) . Specific
examples of the substituent include the substituents
described for Formula ( SQ ) and a group represented by
In the formula, Zl and Z2 are each independently a Formula (a ) . In addition, two substituents in the methine
non -metal atomic group for forming a 5- or 6 -membered chain may be bonded to each other to form a 5- or 6 -mem
nitrogen -containing heterocycle which may be fused, 15 bered ring .
R101 and R102 each independently represent an alkyl
group , an alkenyl group , an alkynyl group , an aralkyl group ,
or an aryl group, ( a)
L ' represents a methine chain having an odd number of 20
methine groups,
a and b each independently represent 0 or 1 ,
in a case where a is 0 , a carbon atom and a nitrogen atom
*

O
are bonded through a double bond ; and in a case where b is In Formula (a), represents a linking portion to the
0 , a carbon atom and a nitrogen atom are bonded through a 25 methine chain, and A ' represents 0
single bond , and In Formula (C ) , a and beach independently represent 0 or
in a case where a site represented by Cy in the formula is 1. In a case where a is 0 , a carbon atom and a nitrogen atom
a cationic site , Xl represents an anion and c represents the are bonded through a double bond . In a case where b is 0 ,
number of Xl's for balancing the charge; in a case where a 30 a carbon atom and a nitrogen atom are bonded through a
site represented by Cy in the formula is an anion site , X1 single bond . It is preferable that both a and b are 0. In a case
represents a cation , and c represents the number of Xl's for where both a and b are 0 , Formula (C ) is shown as below .
balancing the charge ; and in a case where charge of a site
represented by Cy in the formula is neutralized in a mol 35
ecule , c is 0 . ( X !).
In Formula (C ) , Z and Z are each independently a
non -metal atomic group for forming a 5- or 6 -membered
nitrogen -containing heterocycle which may be fused .
2A-- A -RE
R101 - N = C — Ll = C — N — R102

Another heterocycle, aromatic ring, or aliphatic ring may be 40 In Formula ( C ) , in a case where a site represented by Cy
fused to the nitrogen - containing heterocycle. It is preferable in the formula is a cationic moiety, Xl represents an anion
that the nitrogen - containing heterocycle is a 5 -membered and c represents the number of Xl's for balancing charge.
ring . A structure in which a benzene ring or a naphthalene Examples of the anion include an halide ion (C1- , Br", or I ' ) ,
a para - toluenesulfonate ion , an ethyl sulfate ion , PF 6 , BF4 ,
ring is fused to the 5 -membered nitrogen -containing hetero- 45 cio , , a tris (halogenoalkylsulfonyl )methide anion ( for
cycle is more preferable. Specific examples of the nitrogen- example ; (CF SO2) , C ), a di (halogenoalkylsulfonyl)imide
containing heterocycle include an oxazole ring, an isoxazole anion ( for example, (CF280 ) N-), and a tetracyanoborate
ring , a benzoxazole ring, a naphthoxazole ring , an oxazo anion .
locarbazole ring , an oxazolodibenzofuran ring , a thiazole In Formula ( C ) , in a case where a site represented by Cy
ring , a benzothiazole ring, a naphthothiazol ring , an indo- 50 in the formula is an anionic moiety, Xl represents a cation
lenine ring, a benzindolenine ring, an imidazole ring, a and c represents the number of xl's for balancing the
benzimidazole ring, a naphthoimidazole ring, a quinoline charge. Examples of the cation include an alkali metal ion
ring , a pyridine ring , a pyrrolopyridine ring , a furopyrrole Ca2(Li + , Na +, K+ , or the like ), an alkali earth metal ion (Mg2 + ,
+ , Ba2 + , Sr2 +, or the like) , a transition metal ion ( Ag +,
ring
quinoxaline ring . The nitrogen -containing heterocycle is ( A13 +Cot
, an indolizine ring , an imidazoquinoxaline ring, and a 55 Fet, , Nit, Cu2+, Zn2+, or the like), other metal ions
or the like ) , an ammonium ion, a triethylammonium
preferably a quinoline ring, an indolenine ring, a benzindo ion , a tributylammonium ion , a pyridinium ion , a tetrabuty
lenine ring , a benzoxazole ring, a benzothiazole ring, or a lammonium ion , a guanidinium ion , a tetramethylguanidium
benzimidazole ring , and particularly preferably an indole- ion , and a diazabicycloundecenium ion . As the cation , Na + ,
nine ring , a benzothiazole ring, or a benzimidazole ring. The 60 K+ , Mg2 + , Ca2 + , Zn2 +, or the diazabicycloundecenium ion is
nitrogen -containing heterocycle and the ring fused thereto preferable .
may have a substituent. Examples of the substituent include In Formula (C ) , in a case where a charge of a site
the substituents described for Formula ( SQ ) . represented by Cy is neutralized in a molecule , X ' is not
In Formula ( C ) , R101 and R102 each independently repre- 65 present. That is , c is 0 .
sent an alkyl group , an alkenyl group , an alkynyl group , an It is also preferable that the cyanine compound is a
aralkyl group , or an aryl group . These groups may have a compound represented by any of Formulae ( C - 1 ) to ( C - 3 ) .
 US 10,991,749 B2
35 36
preferably 1 to 3. The alkyl group may be in any of linear,
(C- 1 ) branched , and cyclic forms, but is preferably linear or
branched , and particularly preferably linear. The alkyl group
is particularly preferably a methyl group or an ethyl group .
1 5 L 14 and LlB each have the same definitions as Ll of
(V14)mi (V24)m2 Formula (C ) , and preferred ranges thereof are also the same .
N LIA No Examples of the substituents represented by V1A , 124 ,
1 (X ) VlB , and V2B include the substituents described for Formula
RIA R24 (SQ ).
10 ml and m2 each independently represent 0 to 4 , and are
preferably 0 to 2 .
?? The anion and the cation represented by X ! have the same
(V2B)m2 (C - 2) definitions as the ranges described for XP of Formula (C ) ,
and preferred ranges thereof are also the same .
(VB).ml 15 Examples of the cyanine compound include the com
pounds described in paragraph Nos . 0044 to 0045 of
R 1B -R2B ( X ! ). JP2009-108267A , paragraph Nos . 0026 to 0030 of JP2002
194040A , the compounds described in JP2015-172004A ,
1B the compounds described in JP2015-172102A , and the com
20 pounds described in JP2008-088426A , the contents of which
are incorporated herein by reference .
In the present invention, as the near -infrared absorbing
Cy compound, a commercially available product can also be
(C- 3 ) used . Examples of the commercially available product
25 include SDO - C33 (manufactured by Arimoto Chemical Co. ,
(V1B)m1 Ltd. ) , EXCOLOR IR - 14 , EXCOLOR IR - 10A , EXCOLOR
(V2B)m2 ( X !). TX - EX - 801B , or EXCOLOR TX - EX - 805K (manufactured
by Nippon Shokubai Co. , Ltd. ) , Shigenox NIA - 8041 , Shig
N L 1B enox NIA - 8042 , Shigenox NIA - 814 , Shigenox NIA - 820 , or
+

1 30 Shigenox NIA - 839 (manufactured by Hakkol Chemical Co. ,

RIB R2B Ltd. ) , Epolite V -63, Epolite 3801 , or Epolight 3036 (manu
factured by Epolin Inc. ) , PRO - JET 825LDI (manufactured
by Fujifilm Corporation ), NK - 3027 or NK - 5060 (manufac
?? tured by Hayashibara Co. , Ltd. ), and YKR - 3070 (manufac
35 tured by Mitsui Chemicals, Inc.).
In the formulae, R14 , R24, R1B , and R2B each indepen In a case where the composition for a near - infrared
dently represent an alkyl group , an alkenyl group , an alkynyl transmitting filter contains a near - infrared absorbing dye, the
group , an aralkyl group, or an aryl group , content of the near - infrared absorbing dye is preferably 1 %
to 30 % by mass with respect to the total solid content of the
L1A and L1B each independently represent a methine chain 40 composition for a near- infrared transmitting filter. The upper
having an odd number of methine groups, limit is preferably 25 % by mass or less , and more preferably
Y and Y2 each independently represent S 20% by mass or less . The lower limit is preferably 3 % by
NR ¥ 1 or CR2R -13 mass or more , and more preferably 5 % by mass or more .
R ¥ 1, R ¥ 2, and R ¥ 3 each independently represent a hydro- Further, the total amount of the near -infrared absorbing dye
gen atom or an alkyl group, 45 and the light shielding material is preferably 35 % to 80 % by
v14 , V24 , vlB , and V2B each independently represent a mass of the total solid content of the composition for a
substituent, near - infrared transmitting filter. The lower limit is preferably
ml and m2 each independently represent 0 to 4 , 40% by mass or more , more preferably 45 % by mass or
in a case where a site represented by Cy in the formulae more , still more preferably 50% by mass or more , and
is a cationic site , X ' represents an anion and c represents the 50 particularly preferably 55 % by mass or more . The upper
number of xl's for balancing the charge, limit is preferably 75 % by mass or less , and more preferably
in a case where a site represented by Cy in the formulae 70% by mass or less . Further, the content of the near - infrared
is an anion site , X ' represents a cation and c represents the absorbing dye in the total amount of the near -infrared
number of xl's for balancing charge , and in a case where absorbing dye and the light shielding material is preferably
charge of a site represented by Cy in the formulae is 55 5 % to 40 % by mass . The upper limit is preferably 30 % by
neutralized in a molecule , Xl is not present. mass or less , and more preferably 25 % by mass or less . The
The groups represented by R14 , R24, RIB , and R2B have lower limit is preferably 10 % by mass or more, and more
the same definitions as the alkyl group , the alkenyl group , preferably 15 % by mass or more .
the alkynyl group , the aralkyl group , and the aryl group In the composition for a near - infrared transmitting filter,
described for R101 and R102 of Formula (C) , and preferred 60 the
ranges thereof are also the same .
near-infrared absorbing dye may be used singly or in
combination of two or more kinds thereof. In a case where
Y and Y2 each independently represent S two or more kinds of the near - infrared absorbing dyes are
-NRX1 or —CR2R13_with - NR * -being preferable. used in combination , the total amount thereof is preferably
R ¥ 1, R.* ?, and R13 each independently represent a hydrogen within the range .
atom or an alkyl group , with the alkyl group being prefer- 65 << Other Near - Infrared Absorber>>
able . The number of carbon atoms of the alkyl group is The composition for a near - infrared transmitting filter can
preferably 1 to 10 , more preferably 1 to 5 , and particularly contain another near - infrared absorber, in addition to the
 US 10,991,749 B2
37 38
near - infrared absorbing dye . Examples of such another bond is , for example, preferably 15 or less , and more
near -infrared absorber include inorganic particles. The shape preferably 6 or less . Examples of the group having an
of the inorganic particles is not particularly limited and may ethylenically unsaturated bond include a vinyl group , a
have a sheet shape, a wire shape , or a tube shape, irrespec- styryl group , an allyl group , a methallyl group , and a
tive of whether or not the shape is spherical or non - spherical. 5 (meth )acryloyl group, with the (meth )acryloyl group being
As the inorganic particles, metal oxide particles or metal preferable. The radically polymerizable compound is pref
particles are preferable. Examples of the metal oxide par- erably a trifunctional to pentadecafunctional (meth )acrylate
ticles include indium tin oxide (ITO ) particles, antimony tin compound, and more preferably a trifunctional to hexafunc
oxide ( ATO ) particles, zinc oxide ( ZnO ) particles, Al-doped tional (methacrylate compound .
zinc oxide ( Al-doped ZnO ) particles, fluorine-doped tin 10 The radically polymerizable compound may be in any
dioxide ( F -doped SnO2) particles, and niobium - doped tita- form of a monomer and a polymer, with the monomer being
nium dioxide (Nb -doped TiO2 ) particles. Examples of the preferable. The monomer type of the radically polymeriz
metal particles include silver (Ag) particles, gold (Au) able compound preferably has a molecular weight of 200 to
particles, copper ( Cu ) particles , and nickel (Ni) particles. In 3,000 . The upper limit of the molecular weight is preferably
addition , as the inorganic particles, a tungsten oxide -based 15 2,500 or less , and more preferably 2,000 or less . The lower
compound can also be used . The tungsten oxide -based limit of the molecular weight is preferably 250 or more , and
compound is preferably cesium tungsten oxide . With regard more preferably 300 or more .
to the details of the tungsten oxide - based compound, refer- With regard to examples of the radically polymerizable
ence can be made to the description in paragraph No. 0080 compound, reference can be made to the descriptions in
of JP2016-006476A , the contents of which are incorporated 20 paragraph Nos . 0033 and 0034 of JP2013-253224A , the
herein by reference . contents of which are incorporated herein by reference .
In a case where the composition for a near -infrared Examples of the polymerizable compound include ethylene
transmitting filter contains another near - infrared absorber, oxy -modified pentaerythritol tetraacrylate (as a commer
the content of such the near -infrared absorber is preferably cially available product, NK ESTER ATM - 35E manufac
1 % to 30 % by mass with respect to the total solid content of 25 tured by Shin -Nakamura Chemical Co. , Ltd. ) ;
the composition for a near - infrared transmitting filter. The dipentaerythritol triacrylate ( as a commercially available
upper limit is preferably 20% by mass or less , and more product, KAYARAD D - 330 manufactured by Nippon Kay
preferably 10 % by mass or less . The lower limit is preferably aku Co. , Ltd. ) ; dipentaerythritol tetraacrylate (as a commer
3 % by mass or more , and more preferably 5 % by mass or cially available product, KAYARAD D -320 manufactured
more . 30 by Nippon Kayaku Co. , Ltd.); dipentaerythritol penta (meth )
<< Curable Compound >> acrylate (as a commercially available product, KAYARAD
The composition for a near- infrared transmitting filter D - 310 manufactured by Nippon Kayaku Co. , Ltd. ) ; dipen
preferably contains a curable compound. As the curable taerythritol hexa(meth )acrylate (as a commercially available
compound , a known compound which can be crosslinked by product, KAYARAD DPHA manufactured by Nippon Kay
a radical , an acid , or heat can be used . Examples of the 35 aku Co. , Ltd. , A - DPH - 12E , manufactured by Shin -Naka
curable compound include a compound having a group mura Chemical Co. , Ltd. ); and a compound having a struc
having an ethylenically unsaturated bond and a compound ture in which the (meth ) acryloyl group is bonded through an
having a cyclic ether group . Examples of the group having ethylene glycol and / or a propylene glycol residue. In addi
an ethylenically unsaturated bond include a vinyl group , a tion , oligomers of the above - described examples can also be
(meth )allyl group , and a (meth ) acryloyl group . Examples of 40 used . Further, with regard to this, the descriptions in para
the cyclic ether group include an epoxy group and an graph Nos . 0034 to 0038 of JP2013-253224A , the contents
oxetanyl group . In the present invention , the curable com- of which are incorporated herein by reference. Examples of
pound is preferably a radically polymerizable compound or the compound include the polymerizable monomers
a cationically polymerizable compound, and more prefer- described in paragraph No. 0477 of JP2012-208494A (para
ably the radically polymerizable compound . 45 graph No. 0585 of the corresponding US2012 /0235099A) ,
The content of the curable compound is preferably 0.1 % the contents of which are incorporated herein by reference.
to 40 % by mass with respect to the total solid content of the In addition , diglycerin ethylene oxide ( EO )-modified (meth )
composition for a near - infrared transmitting filter. The lower acrylate (as a commercially available product, M - 460 manu
limit is , for example, preferably 0.5 % by mass or more , and factured by Toagosei Co. , Ltd. ) ; pentaerythritol tetraacrylate
more preferably 1 % by mass or more . The upper limit is , for 50 ( A - TMMT manufactured by Shin -Nakamura Chemical Co. ,
example , preferably 30% by mass or less , and more prefer- Ltd. ) , or 1,6 -hexanediol diacrylate (KAYARAD HDDA
ably 20 % by mass or less . The curable compounds may be manufactured by Nippon Kayaku Co. , Ltd. ) is also prefer
used singly or in combination of two or more kinds thereof. able . Oligomers of the above -described examples can also
In a case where two or more kinds of the curable compounds be used . Examples thereof include RP - 1040 (manufactured
are used in combination, the total amount thereof is prefer- 55 by Nippon Kayaku Co. , Ltd. ) . In addition, ARONIX M - 350
ably within the range . and TO - 2349 (manufactured by Toagosei Co. , Ltd.) can also
( Radically Polymerizable Compound ) be used as the radically polymerizable compound .
The radically polymerizable compound is not particularly The radically polymerizable compound may have an acid
limited as long as it is a compound that is polymerizable by group such as a carboxyl group , a sulfonic acid group , and
the action of a radical . The radically polymerizable com- 60 a phosphoric acid group . Examples of the radically polym
pound is preferably a polymerizable compound having one erizable compound having an acid group include an ester of
or more groups having an ethylenically unsaturated bond , an aliphatic polyhydroxy compound with an unsaturated
more preferably a compound having two or more groups carboxylic acid . The radically polymerizable compound
having an ethylenically unsaturated bond , and still more having an acid group is preferably a polymerizable com
preferably a compound having three or more groups having 65 pound in which a non - aromatic carboxylic acid anhydride is
an ethylenically unsaturated bond . The upper limit of the reacted with an unreacted hydroxyl group of the aliphatic
number of the groups having an ethylenically unsaturated polyhydroxy compound to make an acid group bonded
 US 10,991,749 B2
39 40
thereto . It is particularly preferable that in this ester, the combination of two or more kinds thereof. In a case where
aliphatic polyhydroxy compound is pentaerythritol and /or two or more kinds of the radically polymerizable com
dipentaerythritol. Examples of a commercially available pounds are used in combination , the total amount thereof is
product thereof include ARONIX series M - 305 , M - 510 , and preferably within the range .
M - 520 , which are polybasic acid modified
- acryl oligomers 5 ( Cationically Polymerizable Compound )
manufactured by Toagosei, Co. , Ltd. The acid value of the Examples of the cationically polymerizable compound
polymerizable compound having an acid group is preferably include a compound having a cationically polymerizable
0.1 to 40 mgKOH/ g . The lower limit is preferably 5 group . Examples of the cationically polymerizable group
mgKOH/g or more . The upper limit is preferably 30 include a cyclic ether group such as an epoxy group and an
mgKOH / g or less . 10 oxetanyl group , and an unsaturated carbon double bond
It is also preferable that the radically polymerizable group such as a vinyl ether group and an isobutene group .
compound is a compound having a caprolactone structure . The cationically polymerizable compound is preferably a
The radically polymerizable compound having a caprolac- compound having a cyclic ether group , and more preferably
tone structure is not particularly limited as long as it has a a compound having an epoxy group .
caprolactone structure in the molecule thereof, and examples 15 Examples of the compound having an epoxy group
thereof include E - caprolactone -modified polyfunctional include a compound having one or more epoxy groups
(meth )acrylate obtained by esterification of a polyhydric within one molecule , and the compound is preferably a
alcohol, (methacrylic acid , and e - caprolactone, the polyhy- compound having two or more epoxy groups within one
dric alcohol being , for example , trimethylolethane, ditrim- molecule . The number of epoxy groups contained in one
ethylolethane, trimethylolpropane, ditrimethylolpropane, 20 molecule of the compound is preferably 1 to 100. The upper
pentaerythritol, dipentaerythritol, tripentaerythritol, glyc- limit of the number of the epoxy groups can be , for example,
erin , diglycerol, and trimethylolmelamine. With regard to preferably 10 or less , or 5 or less . The lower limit of the
examples of the polymerizable compound having a capro- number of the epoxy groups is preferably 2 or more .
lactone structure, reference can be made to the descriptions The compound having an epoxy group may be a low
in paragraph Nos . 0042 to 0045 of JP2013-253224A, the 25 molecular compound (for example, a compound having a
contents of which are incorporated herein by reference . molecular weight of less than 2,000 and a compound having
Examples of the polymerizable compound having a capro- a molecular weight of less than 1,000) , or may be a high
lactone structure include DPCA - 20 , DPCA - 30 , DPCA - 60 , molecular compound (macromolecule) ( for example , a com
DPCA - 120 , and the like which are commercially available pound having a molecular weight of 1,000 or more , and in
as KAYARAD DPCA series manufactured by Nippon Kay- 30 a case of a polymer, a compound having a weight-average
aku Co. , Ltd., SR- 494 manufactured by Sartomer, which is molecular weight of 1,000 or more ). The weight -average
a tetrafunctional acrylate having four ethyleneoxy chains , molecular weight of the compound having an epoxy group
and TPA -330 which is a trifunctional acrylate having three is preferably 200 to 100,000 , and more preferably 500 to
isobutyleneoxy chains . 50,000 . The upper limit of the weight- average molecular
As the radically polymerizable compound , the urethane 35 weight is preferably 10,000 or less , more preferably 5,000 or
acrylates described in JP1973-041708B ( JP - S48-041708B ) , less , and still more preferably 3,000 or less .
JP1976-037193A (JP - S51-037193A) , JP1990-032293B (JP- In a case where the compound having an epoxy group is
H02-032293B ) , or JP1990-016765B (JP - H02-016765B ) , or a low molecular compound, examples of the compound
the urethane compounds having an ethylene oxide skeleton include a compound represented by Formula ( EP1 ) .
described in JP1983-049860B ( JP - S58-049860B ) , JP1981- 40
017654B (JP - S56-017654B ) , JP1987-039417B (JP - S62
039417B ) , or JP1987-039418B (JP - S62-039418B ) are also ( EP1 )
suitable . In addition , the addition -polymerizable compounds REPI
having an amino structure or a sulfide structure in the QEP
molecules thereof described in JP1988-277653A ( JP - S63- 45 REP2
277653A) , JP1988-260909A (JP - S63-260909A) , or JP1989 REP3 EP
105238A ( JP - H01-105238A) can be used . Examples of a
commercially available product thereof include URE
THANE OLIGOMER UAS - 10 and UAB - 140 (manufac- In Formula (EP1 ) , REP1 to REP3 each represent a hydro
tured by Sanyo -Kokusaku Pulp Co. , Ltd. ) , UA -7200 (manu- 50 gen atom , a halogen atom , or an alkyl group, in which the
factured by Shin -Nakamura Chemical Co. , Ltd. ) , DPHA- alkyl group may have a cyclic structure or may have a
40H (manufactured by Nippon Kayaku Co. , Ltd. ), and substituent. REP1 and REP2, or REP2 and REP3 may be
UA -306H , UA - 306T, UA -3061, AH - 600 , T -600 and AI - 600 bonded with each other to form a cyclic structure . QEP
(manufactured by Kyoeisha Chemical Co. , Ltd. ) . In addi- represents a single bond or an nEP -valent organic group .
tion, it is also preferable that 8UH - 1006 or 8UH - 1012 55 REPI to REP3 may also be bonded to QEP to form a cyclic
(manufactured by Taisei Fine Chemical Co. , Ltd. ) is used as structure . nEP represents an integer of 2 or more, preferably
the radically polymerizable compound . 2 to 10 , and more preferably 2 to 6. Incidentally, in a case
In a case where the composition for a near - infrared where QEP is a single bond, ntEP is 2 .
transmitting filter contains a radically polymerizable com- With reference to the details of REPI to REP3, or EP,
pound, the content of the radically polymerizable compound 60 reference can be made to the descriptions in paragraph Nos .
is preferably 0.1 % to 40 % by mass with respect to the total 0087 to 0088 of JP2014-089408A , the contents of which are
solid content of the composition for a near - infrared trans- incorporated herein by reference . Specific examples of com
mitting filter. The lower limit is , for example, preferably pound represented by Formula ( EP1 ) include the compounds
0.5 % by mass or more , and more preferably 1 % by mass or described in paragraph 0090 of JP2014-089408A and the
more . The upper limit is preferably for example, 30% by 65 compounds described in paragraph No. 0151 of JP2010
mass or less , and more preferably 20 % by mass or less . The 054632A , the contents of which are incorporated herein by
radically polymerizable compounds may be used singly or in reference .
 US 10,991,749 B2
41 42
As a low molecular compound, a commercially available compound is used as the curable compound, it is preferable
product can also be used . Examples thereof include ADEKA that a photocationic polymerization initiator is used as the
GLYCIROL ED Series ( for example, ADEKA GLYCIROL photoinitiator. The photoinitiator is not particularly limited
ED ED - 505 ) manufactured by ADEKA Corporation, and and can be appropriately selected from known photoinitia
EPOLEAD Series ( for example, EPOLEAD GT401 ) manu- 5 tors . For example, a compound having photosensitivity with
factured by Daicel Chemical Industries, Ltd. respect to light rays in a range from an ultraviolet region to
As the compound having an epoxy group , an epoxy resin visible light region is preferable .
can be preferably used . Examples of the epoxy resin include The content of the photoinitiator is preferably 0.1 % to
an epoxy resin which is a glycidyl etherified product of a 50% by mass , more preferably 0.5 % to 30% by mass , and
phenolic compound, an epoxy resin which is a glycidyl 10 still more preferably 1 % to 20% by mass , with respect to the
etherified product of any of various novolac resins, an total solid content of the composition for a near - infrared
alicyclic epoxy resin , an aliphatic epoxy resin , a heterocyclic transmitting filter. In a case where the content of the pho
epoxy resin , a glycidyl ester - based epoxy resin , a glycidyl toinitiator is within the range, better sensitivity and pattern
amine -based epoxy resin , an epoxy resin obtained by gly- forming properties are obtained . The composition for a
cidylating a halogenated phenol, a condensate of a silicon 15 near -infrared transmitting filter may include only one kind
compounds having an epoxy group and another silicon or two or more kinds of the photoinitiators . In a case where
compound ,and a copolymer of a polymerizable unsaturated two or more kinds of the photoinitiators are included , the
compound having an epoxy group and another polymeriz- total amount thereof is preferably within the range .
able unsaturated compound. ( Photoradical Polymerization Initiator)
The epoxy equivalent of the epoxy resin is preferably 310 20 Examples of the photoradical polymerization initiator
to 3,300 g /eq, more preferably 310 to 1,700 g/eq, and still include halogenated hydrocarbon derivatives ( for example,
more preferably 310 to 1,000 g/ eq . a compound having a triazine skeleton and a compound
As the epoxy resin , a commercially available product can having an oxadiazole skeleton ), an acylphosphine com
also be used . Examples thereof include EHPE3150 (manu- pound, hexaaryl biimidazole , an oxime compound, an
factured by Daicel Chemical Industries, Ltd. ) , EPICLON 25 organic peroxide, a thio compound, a ketone compound, an
N - 695 (manufactured by DIC Corporation ), MARPROOF aromatic onium salt , an a -hydroxyketone compound, and an
G - 0150M , G - 0105SA , G -0130SP, G -0250SP, G - 1005S , a -aminoketone compound. From the viewpoint of the expo
G - 1005SA , G - 1010S , G - 2050M , G - 01100 , and G - 01758 ( all sure sensitivity, a trihalomethyl triazine compound, a benzyl
of which are manufactured by NOF Corporation , epoxy dimethyl ketal compound , an a -hydroxyketone compound ,
group containing polymer ). 30 an a - aminoketone compound, an acylphosphine compound,
In the present invention , as the compound having an a phosphine oxide compound, a metallocene compound, an
epoxy group , the compounds described in paragraph Nos . oxime compound , a triarylimidazole dimer, an onium com
0034 to 0036 of JP2013-011869A , paragraph Nos . 0147 to pound, a benzothiazole compound, a benzophenone com
0156 of JP2014-043556A , or paragraph Nos . 0085 to 0092 pound, an aminoacetopheno en compound, a cyclopentadi
of JP2014-089408A can also be used . The contents of the 35 ene -benzene - iron complex , a halomethyl oxadiazole
publications are incorporated herein by reference . compound, and a 3 - aryl- substituted coumarin compound are
In a case where the composition for a near - infrared preferable, a compound selected from an oxime compound,
transmitting filter contains a cationically polymerizable the a -hydroxyketone compound, the a -aminoketone com
compound, the content of the cationically polymerizable pound, and the acylphosphine compound is more preferable,
compound is preferably 0.1 % to 40% by mass with respect 40 and the oxime compound is still more preferable. With
to the total solid content of the composition for a near- regard to the photopolymerization initiator, reference can be
infrared transmitting filter. The lower limit is , for example,
made to the description in paragraphs 0065 to 0111 of
preferably 0.5 % by mass or more, and more preferably 1 % JP2014-130173A , the contents of which are incorporated
by mass or more . The upper limit is preferably for example, herein by reference .
30 % by mass or less , and more preferably 20 % by mass or 45 Examples of a commercially available product of the
less . The cationically polymerizable compounds may be a -hydroxyketone compound include IRGACURE - 184 ,
used singly or in combination of two or more kinds thereof. DAROCUR - 1173 , IRGACURE - 500, IRGACURE -2959 ,
In a case where two or more kinds of the cationically and IRGACURE - 127 (all of which are manufactured by
polymerizable compounds are used in combination, the total BASF ). Examples of a commercially available product of
amount thereof is preferably within the range . 50 the a - aminoketone compound include IRGACURE - 907,
In addition, in a case where the composition for a near- IRGACURE - 369, IRGACURE - 379, and IRGACURE
infrared transmitting filter include the radically polymeriz- 379EG ( all ofwhich are manufactured by BASF ) . Examples
able compound and the cationically polymerizable com- of a commercially available product of the acylphosphine
pound, the mass ratio of both the compounds is preferably compound include IRGACURE -819 and DAROCUR - TPO
radically polymerizable compound : cationically polymeriz- 55 (both of which are manufactured by BASF ) .
able compound = 100 :1 to 100 : 400 , and more preferably As the oxime compound, the compounds described in
100 : 1 to 100 : 100 . JP2001-233842A , the compounds described in JP2000
<< Photoinitiator >> 080068A , the compounds described in JP2006-342166A ,
The composition for a near - infrared transmitting filter can the compounds described in JP2016-021012A , or the like
contain a photoinitiator. Examples of the photoinitiator 60 can be used. In the present invention, examples of the oxime
include a photoradical polymerization initiator and a pho- compound which can be suitably used in the present inven
tocationic polymerization initiator. The photoinitiator is tion include 3 -benzoyloxyiminobutan - 2 - one, 3 - acetoxyimi
preferably selected depending on the type of a curable nobutan - 2 -one, 3 - propionyloxyiminobutan - 2 -one , 2- ac
compound . In a case where a radically polymerizable com- etoxyiminopentan - 3 -one, 2- acetoxyimino -1 -phenylpropan
pound is used as the curable compound, a photoradical 65 1 - one , 2 -benzoyloxyimino - 1 -phenylpropan - 1 -one, 3-(4
polymerization initiator is preferably used as the photoini- toluenesulfonyloxy )iminobutan - 2 - one, and
tiator. Further, in a case where a cationically polymerizable 2 -ethoxycarbonyloxyimino - 1 -phenylpropan - 1 -one. Other
 US 10,991,749 B2
43 44
examples of the oxime compound include the compounds -continued
described in J. C. S. Perkin II ( 1979 ) , pp . 1653 to 1660 , J. (C - 2 )
C. S. Perkin II ( 1979 ) , pp . 156 to 162 , Journal of Photopo

ra
lymer Science and Technology ( 1995 ) , pp . 202 to 232 , each CH3
of the publications of JP2000-066385A , JP2000-080068A , 5
JP2004-534797A, and JP2006-342166A . As a commercially
available product of the oxime compound, IRGACURE ci
OXE01 , IRGACURE -OXE02, IRGACURE -OXE03 , and
IRGACURE -OXE04 (all of which are manufactured by 10
CH3
BASF ) are also suitably used . In addition , TRONLY TR (C- 3 )
PBG - 304 (manufactured by CHANGZHOU Changzhou
Tronly New Electronic Materials Co. , Ltd. ) , or ADEKA
OPTOMER N - 1919 (manufactured by ADEKA Corpora
tion, the photopolymerization initiator 2 described in 15
JP2012-014052A) can also be used . In addition , it is also CI
preferable that a compound having no colorability or a
compound having high transparency and hardly changing CH3
the colors of the other components is used as the oxime ( C - 4)
compound. Examples of a commercially available product 20
of the compound include ADEKA ARKLS NC1-730 , NCI
831 , and NCI - 930 (all manufactured by ADEKA Corpora
tion ).
In the present invention , an oxime compound having a 25 CH3
fluorene ring can also be used as the photopolymerization
initiator. Specific examples of the oxime compound having
a fluorene ring include the compounds described in JP2014
137466A , the contents of which are incorporated herein by CI
reference. 30
In the present invention , an oxime compound having a (C- 5 )
fluorine atom can also be used as the photopolymerization
initiator. Specific examples of the oxime compound having CH3
a fluorine atom include the compounds described in JP2010
262028A , the compounds 24 , and 36 to 40 described in 35
JP2014-500852A , and the compounds (C - 3 ) described in
CH3 T
JP2013-164471A , each content of which is incorporated
herein by reference . CI
In the present invention , an oxime compound having a
nitro group can also be used as the photopolymerization
initiator. The oxime compound having a nitro group is also
preferably used in the form of a dimer. Specific examples of
the oxime compound having a nitro group include the (C- 6)
compounds described in paragraph Nos . 0031 to 0047 of 45

olac
JP2013-114249A and paragraph Nos . 0008 to 0012 and
0070 to 0079 of JP2014-137466A , the compounds described
in paragraph Nos . 0007 to 0025 of JP4223071B , and
ADEKA ARKLS NCI - 831 (manufactured by ADEKA Cor CH3
Br
poration ). 50

Specific examples of the oxime compound which is ??? CH3

preferably used in the present invention are shown below,
but the present invention is not limited thereto .
55
(C- 7)
(C- 1 )
CH3
60
CH3

65
 US 10,991,749 B2
45 46
-continued -continued
( C - 8) ( C - 13 )

5
F

F
F F
10

( C - 9 ) 15

Q ( C - 10 )
20

25
ON

H3C CH3 -CH3

( C - 14)

200
As the oxime compound , the compound having the maxi
mum absorption wavelength in a wavelength range of 350
30 nm to 500 nm is preferable, the compound having the
maximum absorption wavelength in a wavelength range of
360 nm to 480 nm is more preferable. Further, the oxime
compound is preferably a compound having high absor
bances at 365 nm and 405 nm .
N 35 From the viewpoint of sensitivity , the molar light absorp
tion coefficient at 365 nm or 405 nm of the oxime compound
is preferably 1,000 to 300,000 , more preferably 2,000 to
( C - 11 ) 300,000 , and particularly preferably 5,000 to 200,000 .
The molar light absorption coefficient of the compound
40 can be measured using a known method , but specifically, it
N-0 is preferably measured, for example , by means of a spec
trophotometer ( Cary - 5 spectrophotometer manufactured by
Varian ) at a concentration of 0.01 g/L using an ethyl acetate
solvent.
45 It is also preferable that the photopolymerization initiator
includes an oxime compound and an a - aminoketone com
pound . By using the oxime compound and the a -aminoke
N tone compound in combination , the developability is
improved and a pattern having excellent rectangularity is
50 likely to be formed . In a case where the oxime compound
and the a - aminoketone compound are used in combination ,
the content of the a - aminoketone compound is preferably 50
( C - 12 ) to 600 parts by mass , and more preferably 150 to 400 parts
by mass , with respect to 100 parts by mass of the oxime
55 compound.
The content of the photopolymerization initiator is pref
erably 0.1 % to 50% by mass , more preferably 0.5 % to 30 %
by mass , and still more preferably 1 % to 20 % by mass , with
respect to the total solid content of the composition for a
60 near-infrared transmitting filter. In a case where the content
of the photopolymerization initiator is within the range, the
developability is good . The composition for a near - infrared
LOC9F17 transmitting filter may include only one kind or two or more
kinds of the photopolymerization initiators . In a case where
65 two or more kinds of the photopolymerization initiators are
included , the total amount thereof is preferably within the
range .
 US 10,991,749 B2
47 48
(Photocationic Polymerization Initiator) The resin having an acid group may also be used as , for
Examples of the photocationic polymerization initiator example , an alkali - soluble resin .
include a photoacid generator. Examples of the photoacid The resin having an acid group is preferably a polymer
generator include an onium salt compound such as a diazo- having a carboxyl group in a side chain thereof, and
nium salt , a phosphonium salt , a sulfonium salt , and an 5 examples thereof include a methacrylic acid copolymer, an
iodonium salt , and a sulfonate compound such as imido tonic acrylic acid copolymer, an itaconic acid copolymer, a cro
sulfonate, oxime sulfonate , diazodisulfone, disulfone, and acid copolymer, a maleic acid copolymer, a partially
0 -nitrobenzyl sulfonate . With regard to the details of the esterified maleic acid copolymer, an alkali - soluble phenol
photocationic polymerization initiator, reference can be resin such as a novolac type resin , or the like; an acidic
made to the descriptions in paragraph Nos. 0139 to 0214 of 10 cellulose derivative having a carboxyl group in a side chain
JP2009-258603A , the contents of which are incorporated thereof ; and a product obtained by adding an acid anhydride
to a polymer having a hydroxyl group . In particular, a
herein by reference . copolymer of a (meth ) acrylic acid and another monomer
The content of the photocationic polymerization initiator which is copolymerizable therewith is preferable as the
is30preferably 0.1 % to 50 % by mass , more preferably 0.5 % to 15 alkali- soluble resin. Examples of such the other monomer
% by mass , and still more preferably 1 % to 20 % by mass , which is copolymerizable with the (methacrylic acid
with respect to the total solid content of the composition for include alkyl (methacrylate, aryl (methacrylate , and a vinyl
a near -infrared transmitting filter. In a case where the content compound. Examples of the alkyl (methacrylate and the
of the photopolymerization initiator is within the range , aryl (methacrylate include methyl (meth )acrylate, ethyl
better sensitivity and pattern forming properties are 20 (meth )acrylate, propyl (meth )acrylate, butyl (meth )acrylate,
obtained . The composition for a near - infrared transmitting isobutyl (methacrylate, pentyl (methacrylate, hexyl (meth )
filter may include only one kind or two or more kinds of the acrylate, octyl (meth )acrylate, phenyl (meth )acrylate, benzyl
photopolymerization initiators. In a case where two or more (meth )acrylate, tolyl (meth )acrylate , naphthyl (meth )acry
kinds of the photopolymerization initiators are included , the late , cyclohexyl (methacrylate, glycidyl methacrylate, and
total amount thereof is preferably within the range . 25 tetrahydrofurfuryl methacrylate; examples of the vinyl com
The composition for a near -infrared transmitting filter pound include styrene, a -methylstyrene, vinyltoluene, acry
preferably contains a resin . The resin is blended in , for lonitrile, vinyl acetate , N - vinylpyrrolidone, a polystyrene
example , an application for dispersing a pigment and the like macromonomer, and a polymethyl methacrylate mac
in a composition or an application as a binder. Incidentally, romonomer ; and examples of the N -position -substituted
a resin which is used for dispersing a pigment and the like 30 maleimide monomer disclosed in JP1998-300922A (JP
in a composition is also referred to as a dispersant. However, H10-300922A ) include N -phenylmaleimide and N -cyclo
such uses of the resin are only exemplary, and the resin can hexylmaleimide. Further, such the other monomer which is
also be used for other purposes , in addition to such uses . copolymerizable with a (meth )acrylic acid may be used
The weight -average molecular weight (Mw ) of the resin singly or in combination of two or more kinds thereof.
is preferably 2,000 to 2,000,000 . The upper limit is prefer- 35 The resin having an acid group may further have a
ably 1,000,000 or less , and more preferably 500,000 or less . polymerizable group . Examples of the polymerizable group
The lower limit is preferably 3,000 or more , and more include an allyl group, a methallyl group and a (meth )
preferably 5,000 or more . acryloyl group . Examples of a commercially available prod
Examples of the resin include a (meth )acrylic resin , an uct thereof include DIANAL NR Series (manufactured by
epoxy resin , an ene -thiol resin, a polycarbonate resin, a 40 Mitsubishi Rayon Co. , Ltd. ) , Photomer 6173 (polyurethane
polycarbonate resin , a polyether resin , a polyarylate resin , a acrylic oligomer containing COOH , manufactured by Dia
polysulfone resin , a polyethersulfone resin , a polyphenylene mond Shamrock Co. , Ltd. ) , VISCOAT R - 264 and KS
resin , a polyarylene ether phosphine oxide resin , a polyimide RESIST 106 (both manufactured by Osaka Organic Chemi
resin , a polyamideimide resin , a polyolefin resin , a cyclic cal Industry, Ltd. ) , CYCLOMER P Series (for example ,
olefin resin , a polyester resin , and a styrene resin . These 45 ACA230AA ) and PLACCEL CF200 Series ( both manufac
resins may be used singly or as a mixture of two or more tured by Daicel Corporation ), Ebecryl 3800 (manufactured
kinds thereof. As the cyclic olefin resin , a norbornene resin by Daicel -UCB Co. , Ltd. ), and ACRYCURE RD - F8 (manu
can be preferably used from the viewpoint of improvement factured by Nippon Shokubai Co. , Ltd. ) .
of heat resistance . Examples of a commercially available As the resin having an acid group , a benzyl (meth )
product of the norbornene resin include ARTON Series 50 acrylate / (methacrylic acid copolymer, a benzyl (methacry
manufactured by JSR Corporation ( for example , ARTON late / (meth )acrylic acid / 2 -hydroxyethyl (meth )acrylate copo
F4520 ) . Further, as the resin, the resins described in lymer, or a multicomponent copolymer including benzyl
Examples of WO2016 / 088645A can also be used . Further, a (methacrylate/(meth )acrylic acid / other monomers can be
resin having a repeating unit having a group having an preferably used . Further, copolymers obtained by copoly
ethylenically unsaturated bond in a side chain can also be 55 merizing 2 -hydroxyethyl (meth ) acrylate, a 2 -hydroxypropyl
used as the resin . Examples of the group having an ethyl- (meth )acrylate /polystyrene macromonomer / benzyl meth
enically unsaturated bond include a (meth ) acryloyl group . In acrylate /methacrylic acid copolymer described in JP1995
addition , the main chain of the repeating unit and the group 140654A ( JP -H07-140654A ), a 2 -hydroxy- 3 -phenoxypro
having an ethylenically unsaturated bond are preferably pylacrylate /polymethyl methacrylate macromonomer /
bonded through a divalent linking group having an alicyclic 60 benzyl methacrylate /methacrylic acid copolymer, a
structure . 2 -hydroxyethyl methacrylate /polystyrene macromonomer/
In the present invention, a resin having an acid group is methyl methacrylate /methacrylic acid copolymer, a 2 -hy
preferably used as the resin . According to this aspect , it is droxyethyl methacrylate / polystyrene macromonomer/ben
easy to form a pattern having excellent rectangularity . zyl methacrylate /methacrylic acid copolymer, and the like
Examples of the acid group include a carboxyl group , a 65 can also be preferably used .
phosphoric acid group , a sulfo group , and a phenolic It is also preferable that the resin having an acid group is
hydroxyl group , with the carboxyl group being preferable. a polymer including a repeating unit derived from a mono
 US 10,991,749 B2
49 50
mer component including a compound represented by For- Examples of the resin having an acid group include resins
mula ( ED1 ) and /or a compound represented by Formula having the following structures. In the following structural
( ED2 ) ( these compounds are hereinafter also referred to as formulae , Me represents a methyl group .
an “ ether dimer ” in some cases ) . 5

( EDI ) 60 21

10 OH
OR ! OR2

In Formula (EDI ) , R1 and R ? each independently repre

sent a hydrogen atom , or a hydrocarbon group having 1 to 15 19 70

25 carbon atoms , which may have a substituent. OH

RO
( ED2 )

til the
20

20

?? OH
25

In Formula (ED2 ) , R represents hydrogen atom or an

organic group having 1 to 30 carbon atoms. With regard to
the specific examples of Formula (ED2 ) , reference can be 30
made to the descriptions in JP2010-168539A . t
COOMe COOMe
10
th
With regard to the specific examples of the ether dimer,
reference can be made to paragraph No. 0317 of JP2013
029760A , the contents of which are incorporated herein by

fighter
reference. These ether dimers may be used singly or in 35
combination of two or more kinds thereof.
The resin having an acid group may include a repeating
unit derived from a compound represented by Formula ( X ).
40

Ri
H2C = C — C — 07R2-07n -R3
45
25
In Formula (X ) , R1 represents a hydrogen atom or a
methyl group , R , represents an alkylene group having 2 to
10 carbon atoms , and Rz represents a hydrogen atom or an OH
alkyl group having 1 to 20 carbon atoms, which may contain 50
a benzene ring . n represents an integer of 1 to 15 .
With regard to the resin having an acid group , reference The composition for a near -infrared transmitting filter can
can be made to the descriptions in paragraph Nos . 0558 to also include a resin as the dispersant. Examples of the
0571 of JP2012-208494A ( paragraph Nos . 0685 to 0700 of dispersant include an acidic dispersant ( acidic resin ) and a
the corresponding US2012/ 0235099A) and the descriptions 55 basic dispersant (basic resin ). Here, the acidic dispersant
in paragraph Nos . 0076 to 0099 of JP2012-198408A , the (acidic resin) represents a resin in which the amount of the
contents of which are incorporated herein by reference . In acid group is larger than the amount of the basic group . The
addition , as the resin having an acid group , a commercially dispersant ( acidic resin ) is preferably a resin in which the
available product can also be used . Examples of the com- amount of the acid group occupies 70% by mole or more in
mercially available product include FF - 426 (manufactured 60 a case where the total amount of the acid group and the basic
by Fujikura Kasei Co. , Ltd. ) . group is 100 % by mole , and more preferably a resin con
The acid value of the resin having an acid group is sisting substantially of only an acid group. The acid group
preferably 30 to 200 mgKOH/g . The lower limit is prefer- contained in the acidic dispersant (acidic resin ) is preferably
ably 50 mgKOH /g or more , and more preferably 70 a carboxyl group . The acid value of the acidic dispersant
mgKOH/g or more . The upper limit is preferably 150 65 (acidic resin) is preferably 40 to 105 mgKOH/ g , more
mgKOH / g or less , and more preferably 120 mgKOH / g or preferably 50 to 105 mgKOH / g , and still more preferably 60
less . to 105 mgKOH/g . In addition , the basic dispersant (basic
 US 10,991,749 B2
51 52
resin) represents a resin in which the amount of the basic Furthermore, in the present invention , it is also preferable
group is larger than the amount of the acid group . The basic that the resin (dispersant) uses an oligoimine- based disper
dispersant (basic resin ) is preferably a resin in which the sant including a nitrogen atom at at least one of a main chain
amount of the basic group occupies 50 % by mole or more in or a side chain . As the oligoimine - based dispersant, a resin
a case where the total amount of the acid group and the basic shaving a side chain including a repeating unit having a
group is 100% by mole . The basic group contained in the partial structure X having a functional group with a pKa of
basic dispersant is preferably an amino group . 14 or less and a side chain including a side chain Y having
The resin which is used as the dispersant preferably 40 to 10,000 atoms , and having a basic nitrogen atom in at
includes a repeating unit having an acid group. By incor 10 least one of the main chain or the side chain is preferable.
porating the repeating unit having an acid group into the The basic nitrogen atom is not particularly limited as long as
resin used as the dispersant, residues generated in the it is a nitrogen atom exhibiting basicity. With regard to the
underlying substrate of pixels upon formation of a pattern by oligoimine -based dispersant, reference can be made to the
descriptions in paragraph Nos . 0102 to 0166 of JP2012
photolithography can further be reduced . 255128A , the contents of which are incorporated herein by
It is also preferable that the resin used as the dispersant is 15 reference. Further, as the oligoimine-based dispersant, the
a graft copolymer. Since the graft copolymer has affinity resins described in paragraph Nos . 0168 to 0174 of JP2012
with a solvent due to its the graft chain , it is excellent in 255128 A can be used .
dispersibility of a pigment and dispersion stability after
curing. With regard to the details of the graft copolymer, 20
reference can be made to the descriptions in paragraph Nos .
0025 to 0094 of JP2012-255128A , the contents of which are
incorporated herein by reference. Further, specific examples
of the graft copolymer include the following copolymers.
ohiit LC-HS
The following resins are also resins having an acid group 25
( alkali -soluble resins ). In addition , examples of the graft
copolymer include the resins described in paragraph Nos .
0072 to 0094 of JP2012-255128A , the contents of which are
incorporated herein by reference .
014 -C-H15

th? wilaya
OH
2

ti 39
*

90.22

COOH
*

9.78

20
 US 10,991,749 B2
53 54
-continued ment derivative include a compound having a structure in
which a part of a pigment is substituted with an acidic group ,
it a basic group, a phthalimidomethyl group, or the like. As the
pigment derivative, a compound represented by Formula
5 ( B1 ) is preferable.

( B1 )
PL— ( X ) n ) m
OH 10

Nt In Formula (B1 ) , P represents a dye structure, Lrepresents

a single bond or a linking group, X represents an acid group ,
a basic group , a group having a salt structure , or a phthal
15 imidomethyl group , m represents an integer of 1 or more , n
HO2C " represents an integer of 1 or more , in a case where m
a / b / c / d / e = 36/4/35/1/24 (mol % ) represents 2 or more , a plurality of L’s and a plurality of X’s
- 48 y = 12 may be the same as or different from each other, and in a
case where n represents 2 or more , a plurality of X's may be
20 the same as or different from each other.
The dispersant is also available as a commercially avail
able product, and specific examples thereof include Dis In Formula (B1 ) , P represents a dye structure, and is
perbyk - 111 (manufactured by BYK Chemie ). Further, the preferably at least one selected from a pyrrolopyrrole dye
pigment dispersant described in paragraph Nos . 0041 to structure, a diketopyrrolopyrroles dye structure , a quinacri
0130 of JP2014-130338A , the contents of which are incor- 25 done dye structure , an anthraquinone dye structure , a dian
porated herein by reference , can also be used . Further, the thraquinone dye structure , a benzoisoindole dye structure, a
above - mentioned resin having an acid group or the like can thiazine indigo dye structure , an azo dye structure, a
also be used as the dispersant. quinophthalone dye structure, a phthalocyanine dye struc
In a case where the composition for a near -infrared ture
transmitting filter contains a resin, the content of the resin is 30 , a naphthalocyanine dye structure, a dioxazine dye
preferably 14 % to 70 % by mass with respect to the total structure , a perylene dye structure , a perinone dye structure ,
solid content of the composition for a near - infrared trans- a benzimidazolone dye structure , a benzothiazole dye struc
mitting filter. The lower limit is preferably 17 % by mass or ture, a benzimidazole dye structure , or a benzoxazole dye
more , and more preferably 20 % by mass or more . The upper structure, more preferably at least one selected from a
limit is preferably 56% by mass or less, and more preferably 35 pyrrolopyrrole dye structure, a diketopyrrolopyrroles dye
42 % by mass or less .
In a case where the composition for a near - infrared structure zolone
, a quinacridone dye structure , or a benzimida
dye structure , and still more preferably a pyrrolopy
transmitting filter includes a resin having an acid group, the
content of the resin having an acid group is preferably 14 % rrole dye structure .
to 70 % by mass with respect to the total solid content of the 40 In Formula (B1 ) , L represents a single bond or a linking
composition for a near- infrared transmitting filter. The lower group . The linking group is preferably a group formed of 1
limit is preferably 17 % by mass or more , and more prefer to 100 carbon atoms , 0 to 10 nitrogen atoms, 0 to 50 oxygen
ably 20% by mass or more . The upper limit is preferably atoms , 1 to 200 hydrogen atoms , and 0 to 20 sulfur atoms ,
56 % by mass or less , and more preferably 42 % by mass or and may be unsubstituted or may further have a substituent.
less. 45
In a case where the composition for a near - infrared In Formula (B1 ) , X represents an acid group , a basic
transmitting filter includes a radically polymerizable com- group , a group having a salt structure , or a phthalimidom
pound and a resin , the mass ratio of the radically polymer- ethyl group , with the acid group or the basic group being
izable compound to the resin is preferably radically polym- preferable. Examples of the acid group include a carboxyl
erizable compound/ resin = 0.4 to 1.4 . The lower limit of the 50 group and a sulfo group . Examples of the basic group
mass ratio is preferably 0.5 or more , and more preferably 0.6 include an amino group .
or more . The upper limit of the mass ratio is preferably 1.3 Examples of the pigment derivative include a compound
or less , and more preferably 1.2 or less . In a case where the having
mass ratio is within the range, a pattern having more pigmentthederivatives following structures . Examples of the other
include the compounds described in
excellent rectangularity can be formed . 55
JP1981-118462A ( JP - S56-118462A) , JP1988-264674A (JP
In addition , the mass ratio of the radically polymerizable S63-264674A) , JP1989-217077A (JP - H01-217077A) ,
compound to the resin having an acid group is preferably JP1991-009961A ( JP - HO3-009961A ) , JP1991-026767A
radically polymerizable compound /resin having an acid
group = 0.4 to 1.4 . The lower limit of the mass ratio is (JP - H03-026767A) , JP1991-153780A ( JP -H03-153780A ),
preferably 0.5 or more , and more preferably 0.6 or more . 60 JP1991-045662A ( JP - H030-045662A) , JP1992-285669A
The upper limit of the mass ratio is preferably 1.3 or less , (JP - H04-285669A) , JP1994-145546A (JP - H06-145546A) ,
and more preferably 1.2 or less . In a case where the mass JP1994-212088A ( JP - H06-212088A) , JP 1994-240158A
ratio is within the range , a pattern having more excellent (JP - HO6-240158A) , JP1998-030063A (JP - H10-030063A) ,
rectangularity can be formed. JP1998-195326A ( JP - H10-195326A) , paragraph Nos . 0086
<<Pigment Derivative >> 65 to 0098 of WO2011 /024896A , and paragraph Nos . 0063 to
The composition for a near - infrared transmitting filter can 0094 of WO2012 / 102399A , the contents of which are incor
further contain a pigment derivative . Examples of the pig- porated herein by reference.
 US 10,991,749 B2
55 56

Ph Ph
SO3H

NC CN
S
HO3S .
Ph Ph

OMe

Ph Ph
SO3H

NC CN

HO3S . B
Ph Ph

OMe

Ph
Ph

CN
NC

B
Ph
Ph
 US 10,991,749 B2
57 58
CI
-continued

SO3H .

Ph Ph
N NUB

NC CN

BUTTON
Ph Ph

HO3S
CI C1

In a case where the composition for a near - infrared 25 to the total amount of the organic solvent) as a solvent for
transmitting filter contains a pigment derivative, the content reasons in an environmental aspect or the like .
of the pigment derivative is preferably 1 to 50 parts by mass In the present invention , it is preferable to use an organic
with respect to 100 parts by mass of the pigment. The lower solvent having a small metal content, and for example , the
limit value is preferably 3 parts by mass or more , and more metal content of the organic solvent is preferably 10 parts
preferably 5 parts by mass or more . The upper limit value is 30 per billion (ppb ) by mass or less . The metal content of the
preferably 40 parts by mass or less , and more preferably 30 organic solvent is at a level of parts per trillion (ppt ) , as
parts by mass or less . In a case where the content of the desired , and such a high -purity solvent is provided by, for
pigment derivative is within the range , the dispersibility of example , Toyo Kasei Kogyo Co. , Ltd. ( The Chemical Daily,
the pigment can be improved, and aggregation of particles Nov. 13 , 2015 ) .
can be effectively suppressed. The pigment derivative may 35 Examples of a method for removing impurities such as a
be used singly or in combination of two or more kinds metal from the solvent include distillation ( for example,
thereof in combination . In a case where two or more kinds using molecular distillation and thin - film distillation ) and filtering
of the pigment derivatives are used , the total amount thereof filteringa filter is
. The pore diameter of a filter used for the
preferably 10 um or less , more preferably 5 um
is preferably within the range . 40 or less , and still more preferably 3 um or less . As a material
<< Solvent>> of the filter, polytetrafluoroethylene, polyethylene , or nylon
The composition for a near -infrared transmitting filter is preferable.
preferably contains a solvent. Examples of the solvent The solvent may include an isomer (a compound having
include an organic solvent. Basically, the solvent is not the same number of atoms and a different structure ). Further,
particularly limited as long as it satisfies the solubility of the 45 the solvent may include only one isomer or a plurality of
respective components or the coatability of the composition . isomers.
Examples of the organic solvent include esters , ethers, In the present invention , as the organic solvent, an organic
ketones , and aromatic hydrocarbons. With regard to the solvent containing 0.8 mmol/ L or less of a peroxide is
details of the organic solvent, reference can be made to the preferable, and an organic solvent substantially not includ
description in paragraph No. 0223 of WO2015 / 166779A , 50 ing a peroxide is more preferable.
the contents of which are incorporated herein by reference . The content of the solvent is preferably 10% to 90 % by
Further, an ester - based solvent substituted with a cyclic alkyl mass , more preferably 20 % to 80 % by mass , and still more
group or a ketone - based solvent substituted with a cyclic preferably 25 % to 75 % by mass with respect to the total
alkyl group can also be preferably used . Specific examples amount of the composition for a near - infrared transmitting
of the organic solvent include dichloromethane, methyl 55 filter. In addition , it is preferable in some cases that the
3 - ethoxypropionate , ethyl 3 - ethoxypropionate, ethyl cello- composition for a near -infrared transmitting filter does not
solve acetate , ethyl lactate, diethylene glycol dimethyl ether , contain aromatic hydrocarbons ( benzene, toluene, xylene,
butyl acetate , methyl 3 -methoxypropionate, 2 -heptanone, ethylbenzene, and the like ) as a solvent for reasons in an
cyclohexanone, ethyl carbitol acetate , butyl carbitol acetate , environmental aspect or the like .
propylene glycol methyl ether, and propylene glycol 60 << Polymerization Inhibitor>>
monomethyl ether acetate . In the present invention , the The composition for a near - infrared transmitting filter can
organic solvent may be used singly or in combination of two contain a polymerization inhibitor. Examples of the polym
or more kinds thereof. However, it is preferable in some erization inhibitor include hydroquinone, p -methoxyphenol,
cases to reduce aromatic hydrocarbons (benzene , toluene, di - tert- butyl - p -cresol, pyrogallol, tert -butylcatechol, benzo
xylene, ethylbenzene, and the like ) ( for example, the amount 65 quinone, 4,4 ' -thiobis ( 3 -methyl -6 -tert-butylphenol ), 2,2'
can be set to 50 parts per million (ppm ) by mass or less , 10 methylenebis ( 4 -methyl - 6 - t -butylphenol), and N -nitrosophe
ppm by mass or less , or 1 ppm by mass or less with respect nylhydroxylamine salt ( for example, an ammonium salt and
 US 10,991,749 B2
59 60
a cerium ( III ) salt ) . Among these , p -methoxyphenol is described in paragraph Nos . 0117 to 0132 of JP2011
preferable . The content of the polymerization inhibitor is 132503A , the contents of which are incorporated herein by
preferably 0.001 % to 5 % by mass with respect to the total reference . Examples of a commercially available product of
solid content of the composition for a near - infrared trans- the fluorine - based surfactant include MEGAFACE F171 ,
mitting filter. 5 F172 , F173 , F176 , F177 , F141 , F142 , F143 , F144 , R30 ,
<<Silane Coupling Agent>> F437 , F475 , F479 , F482 , F554 , and F780 (all of which are
The composition for a near -infrared transmitting filter manufactured by DIC Corporation ), FLUORAD FC430 ,
may contain a silane coupling agent. In the present inven FC431 , and FC171 (all of which are manufactured by
tion, the silane coupling agent means a silane compound Sumitomo 3M Ltd. ) , -SURFLON S - 382 , -SC - 101 , 393
SC,- 103 ,
having a hydrolyzable group and a functional group other
than the hydrolyzable group. Further, the hydrolyzable 10 SC -104, SC - 105 , SC 1068, SC - 381 , SC 383 , S - and
group refers to a substituent which is directly linked to a KH - 40 ( all of which are manufactured by Asahi Glass Co. ,
silicon atom and is capable of forming a siloxane bond due Ltd. ) , and PolyFox PF636 , PF656 , PF6320 , PF6520 , and
to at least one of a hydrolysis reaction or a fusion reaction . PF7002 ( all of which are manufactured by OMNOVA Solu
Examples of the hydrolyzable group include a halogen atom , 15 tions Inc. ).
Moreover, as the fluorine - based surfactant, an acrylic
an alkoxy group , and an acyloxy group , with the alkoxy compound in which by application of heat to a molecular
group being preferable. That is , it is preferable that the silane structure containing a functional group having a fluorine
coupling agent is a compound having an alkoxysilyl group . atom , in which the functional group containing a fluorine
In addition , examples of the functional group other than the atom is cut to volatilize a fluorine atom , can also be
hydrolyzable
(meth ) acryloylgroup
groupinclude a vinylgroup
, a mercapto group
, an, aepoxy
styrylgroup
group, ,ana 20 appropriately used. Examples of such a fluorine-based sur
oxetanyl group , an amino group , a ureido group , a sulfide factant include MEGAFACE DS series manufactured by
group , an isocyanate group , and a phenyl group , with the DIC Corporation (The Chemical Daily, Feb. 22 , 2016 )
(meth ) acryloyl group or the epoxy group being preferable . (Nikkei Business Daily, Feb. 23 , 2016 ) , for example,
Examples of a commercially available product of the silane 25 MEGAFACE DS - 21 , which can also be used .
As the fluorine -based surfactant, a block polymer can also
coupling agent include KBM - 602 (manufactured by Shin be used . Examples thereof include the compounds described
Etsu Chemical Co. , Ltd. ) . In addition , examples of the silane in JP2011-089090A . As the fluorine - based surfactant, a
coupling agent include the compounds described in para fluorine atom - containing polymer compound can also be
graph Nos . 0018 to 0036 of JP2009-288703A and the
compounds described in paragraph Nos . 0056 to 0066 of 30 compound used
preferably , in which the fluorine- containing polymer
includes a repeating unit derived from a (meth )
JP2009-242604A , the contents of which are incorporated acrylate compound having a fluorine atom ; and a repeating
herein by reference . unit derived from a (meth )acrylate compound having 2 or
The content of the silane coupling agent is preferably more (preferably 5 or more) alkyleneoxy groups ( preferably
0.01 % to 15.0% by mass , and more preferably 0.05 % to an ethyleneoxy group and a propyleneoxy group ). The
10.0 % by mass , with respect to the total solid content of the 35 following compound is also exemplified as the fluorine
composition for a near -infrared transmitting filter. The silane based surfactant used in the present invention .
coupling agents may be of only one kind or of two or more
kinds . In a case where two or more kinds of the silane
coupling agents are used , the total amount thereof is pref
erably within the range. 40
<< Surfactant>>
The composition for a near - infrared transmitting filter C6F13
may contain a surfactant. As the surfactant, various surfac 62 %
tants such as a fluorine -based surfactant, a nonionic surfac
tant, a cationic surfactant, an anionic surfactant, and a 45
silicone - based surfactant can be used . With regard to the
surfactant, reference can be made to paragraph Nos . 0238 to
0245 ofWO2015 / 166779A , the contents ofwhich are incor
porated herein by reference.
tytut ot?
Ni
H

In the present invention, the surfactant is preferably a 50

fluorine - based surfactant . By incorporating the fluorine
based surfactant into the composition for a near - infrared
transmitting filter, liquid characteristics ( in particular, fluid
L2 tot oto
M2
H

38 %
ity ) are further improved, and thus , the liquid saving prop L1 + N1 + L2 + N2 = 14
erties are further improved. In addition , it is possible to form 55 M1 + M2 = 17
a film having a small extent of thickness unevenness .
The fluorine content in the fluorine - based surfactant is
preferably 3 % to 40% by mass , more preferably 5 % to 30 % The weight - average molecular weight of the compound is
by mass , and particularly preferably 7 % to 25 % by mass . preferably 3,000 to 50,000 , and is , for example 14,000 . In
The fluorine - based surfactant in which the fluorine content 60 the compound, % representing the ratio of the repeating
falls within this range is effective in terms of the evenness units is % by mass .
of the thickness of the coating film or liquid saving prop- Moreover, a fluorine - containing polymer having an eth
erties, and also has a good solubility in the composition . ylenically unsaturated group in a side chain can also be used
Specific examples of the fluorine- based surfactant include as the fluorine - based surfactant. Specific examples thereof
the surfactants described in paragraph Nos . 0060 to 0064 of 65 include the compounds described in paragraph Nos . 0050 to
JP2014-041318A ( paragraph Nos . 0060 to 0064 of the 0090 and paragraph Nos . 0289 to 0295 of JP2010-164965A ,
corresponding WO2014/ 017669A) , and the surfactants for example, MEGAFACE RS - 101 , RS - 102 , RS - 718K , and
 US 10,991,749 B2
61 62
RS - 72 - K , manufactured by DIC Corporation . As the fluo -continued
rine - based surfactant, the compounds described in paragraph R301 305
(UV- 3 )
Nos . 0015 to 0158 of JP2015-117327A can also be used .
Examples of the nonionic surfactant include glycerol, R302
trimethylolpropane, trimethylolethane , and ethoxylate and 5 R304
propoxylate thereof ( for example, glycerol propoxylate and R303
glycerol ethoxylate ), polyoxyethylene lauryl ether, polyoxy
ethylene stearyl ether, polyoxyethylene oleyl ether, poly In Formula (UV - 1 ), R101 and R 102
! each independently
oxyethylene octyl phenyl ether polyoxyethylene
nyl ether, polyethylene glycol ,dilaurate nonylglycol
, polyethylene phe- 10 represent
represent 0asubstituent
, and m1 and m2 each independently
to 4 .
distearate , sorbitan fatty acid esters, PLURONIC L10 , L31 , In Formula (UV - 2 ), R201 and R202 each independently
L61 , L62 , 10R5 , 17R2 , and 25R2 (manufactured by BASF ) , represent a hydrogen atom or an alkyl group , and R203 and
TETRONIC 304 , 701 , 704 , 901 , 904 , and 150R1 (manufac R204 each independently represent a substituent.
tured by BASF ) , SOLSEPERSE 20000 (manufactured by 15 In Formula (UV - 3 ), R301 to R303 each independently
Lubrizol Japan Ltd. ) , NCW- 101 , NCW - 1001, and NCW represent a hydrogen atom or an alkyl group , and R3304 and
1002 (manufactured by Wako Pure Chemical Industries, RS305 each independently represent a substituent.
Ltd. ) , PIONIN D - 6112 , D -6112 - W , and D - 6315 (manufac- Specific examples of the compounds represented by For
tured by Takemoto Oil & Fat Co. , Ltd. ) , and OLFINE mula (UV - 1 ) to Formula (UV - 3 ) include the following
E1010 , and SURFYNOL 104 , 400 , and 440 (manufactured 20 compounds.
by Nissin chemical industry Co. , Ltd. ) .
The content of the surfactant is preferably 0.001 % to
5.0 % by mass , and more preferably 0.005 % to 3.0 % by
mass , with respect to the total solid content of the compo- 25
sition for a near -infrared transmitting filter. The surfactant
may be used singly or in combination of two or more kinds.
In a case where two or more kinds of the surfactants are
used , the total amount thereof is preferably within the range .
30
<< Ultraviolet Absorber>>
The composition for a near - infrared transmitting filter can
contain an ultraviolet absorber. As the ultraviolet absorber, O2S
a conjugated diene compound, an aminobutadiene com
pound , a methyldiebenzoyl compound, a coumarin com 35 *C3H17
pound, a salicylate compound, a benzophenone compound,
a benzotriazole compound, an acrylonitrile compound, a
hydroxyphenyltriazine compound, or the like can be used .
With regard to the details thereof, reference can be made to
the descriptions in paragraph Nos . 0052 to 0072 of JP2012- 40
208374A and paragraph Nos . 0317 to 0334 of JP2013
068814A , the contents of which are incorporated herein by
reference. Examples of commercially available products of
the conjugated diene compound include UV - 503 (manufac
tured by Daito Chemical Co. , Ltd. ) . As the benzotriazole 45
compound, MYUA series manufactured by Miyoshi The content of the ultraviolet absorber in the composition
Oil & Fat Co. , Ltd. (The Chemical Daily, Feb. 1 , 2016 ) may
be used . As the ultraviolet absorber, compounds represented for10 %
a near - infrared transmitting filter is preferably 0.01 % to
by mass , and more preferably 0.01 % to 5 % by mass ,
by Formula (UV - 1) to Formula (UV - 3 ) are preferable, the 50 with respect to the total solid content of the composition for
compound represented by Formula (UV - 1 ) or Formula ( UV a near - infrared transmitting filter. In the present invention ,
3 ) is more preferable , and the compound represented by the ultraviolet absorber may be used singly or in combina
Formula (UV - 1) is still more preferable. tion of two or more kinds thereof. In a case where two or
more kinds of the ultraviolet absorbers are used , the total
(UV- 1 )
55 amount thereof is preferably within the range .
<< Antioxidant>>

nguy
(R101) mi

R201 R203
( R102)m2
(UV- 2 )
The composition for a near - infrared transmitting filter can
contain an antioxidant. Examples of the antioxidant include
a phenol compound, a phosphite compound , and a thioether
60 compound. As the phenol compound, any of compounds
which are known as a phenol antioxidant can be used .
Preferred examples of the phenol compound include a
hindered phenol compound. A compound having a substitu
ent at a position ( ortho - position ) adjacent to a phenolic
65 hydroxyl group is preferable . As the above -mentioned sub
R202 R204 stituent, a substituted or unsubstituted alkyl group having 1
to 22 carbon atoms is preferable. Further, an antioxidant
 US 10,991,749 B2
63 64
having a phenol group and a phosphite group in the same ting filter may be mentioned , and preferred ranges thereof
molecule is also preferable. In addition , as the antioxidant, are also the same. Further, preferred contents of these
a phosphorus-based antioxidant can also be suitably used . materials are also the same as the content for the composi
Examples of the phosphorous -based antioxidant include tion for a near - infrared transmitting filter.
tris [ 2 - [ [2,4,8,10 - tetrakis (1,1 -dimethylethyl) dibenzo [ d , f ][ 1, 5 <Composition for Forming Near - Infrared Shielding Filter
3,2 ] dioxaphosphepin - 6 - yl ]oxyJethyl ]amine, tris[ 2 - [ ( 4,6,9, Layer >
11 - tetra - tert-butyldibenzo [ d , f ] [ 1,3,2 ] dioxaphosphepin - 2 - yl) Next , a composition which can be preferably used to form
oxy ] ethyl ] amine , and ethyl bis (2,4 -di-tert -butyl -6- a near - infrared shielding filter layer ( a composition for
methylphenyl) phosphite . Examples of a commercially forming a near - infrared shielding filter layer) will be
available product of the antioxidant include ADK STAB 10 described . It is preferable that the composition for forming
AO - 20 , ADK STAB AO - 30 , ADK STAB A0-40 , ADK a near -infrared shielding filter layer includes a near - infrared
STAB AO - 50 , ADK STAB AO - 50F, ADK STAB AO - 60 , absorbing dye. With regard to the details of the near - infrared
ADK STAB AO - 60G , ADK STAB AO - 80 , and ADK STAB absorbing dye, the above -mentioned near -infrared absorbing
AO - 330 (all of which are manufactured by ADEKA Corpo- dyes may be mentioned . The content of the near - infrared
ration ) 15 absorbing dye is preferably 0.1 % to 70 % by mass with
The content of the antioxidant in the composition for a respect to the total solid content of the composition for
near -infrared transmitting filter is preferably 0.01 % to 20 % forming a near - infrared shielding filter layer. The lower limit
by mass , and more preferably 0.3 % to 15 % by mass , with is preferably 0.5 % by mass or more , and more preferably
respect to the total solid content of the composition for a 1.0 % by mass or more . The upper limit is preferably 60 % by
near -infrared transmitting filter. The antioxidant may be 20 mass or less , and more preferably 50% by mass or less .
used singly or in combination of two or more kinds thereof. The composition for forming a near - infrared shielding
In a case where two or more kinds of the antioxidants are filter layer can further contain a curable compound, a
used , the total amount thereof is preferably within the range . photoinitiator, a resin , a solvent, a polymerization inhibitor,
<<Other Components >> a surfactant, a silane coupling agent, an antioxidant, or the
The composition for a near - infrared transmitting filter 25 like . With regard to the details thereof, the above -mentioned
may contain a sensitizer, a curing accelerator, a filler, a materials which are used for the above -mentioned compo
thermal curing accelerator, a plasticizer, and other auxiliary sition for a near - infrared transmitting filter may be men
agents ( for example, conductive particles, a filler, an anti- tioned, and preferred ranges thereof are also the same .
foaming agent, a flame retardant, a leveling agent, a peeling Further, preferred contents of these materials are also the
accelerator, an antioxidant, an aromatic chemical, a surface 30 same as the content for the composition for a near -infrared
tension adjuster, or a chain transfer agent), as desired . By transmitting filter.
appropriately incorporating the components into the com- < Composition for Forming Transparent Layer >
position , properties such as film physical properties can be Next, the composition for forming a transparent layer
adjusted. With regard to the details of the components, can which can be preferably used to form a transparent layer ( a
be found in , for example, paragraph No. 0183 or later of 35 composition for forming a transparent layer ) will be
JP2012-003225A ( paragraph No. 0237 of the corresponding described . It is preferable that the composition for forming
US2013 /0034812A) , paragraph Nos . 0101 to 0104 , and a transparent layer contains a resin . Examples of the resin
0107 to 0109 of JP2008-250074A , and the like , the contents include the above -mentioned materials which are used for
of which are incorporated herein by reference. the above -mentioned composition for a near - infrared trans
In a case where a film is formed , for example, by coating, 40 mitting filter, and preferred ranges thereof are also the same.
the viscosity ( 23 ° C. ) of the composition for a near - infrared Further, a preferred content of the resin is also the same as
transmitting filter is preferably in a range of 1 to 100 mPa.s. the content for the composition for a near - infrared transmit
The lower limit is preferably 2 mPa.s or more , and more ting filter.
preferably 3 mPa.s or more . The upper limit is preferably 50 The composition for forming a transparent layer may
mPa.s or less , more preferably 30 mPa.s or less , and par- 45 contain a white or colorless pigment (hereinafter also
ticularly preferably 15 mPa.s or less . referred to as a white pigment ). Examples of the white
< Composition for Forming Color Filter Layer > pigment include particles of oxides including at least one
Next, a composition which can be preferably used to form element selected from Ti , Zr, Sn , Sb , Cu , Fe , Mn , Pb , Cd , As ,
a color filter layer ( composition for forming a color filter Cr, Hg , Zn, Al , Mg , Si , P , or S. The shape of the white
layer ) will be described . It is preferable that the composition 50 pigment is not particularly limited . Examples thereof
for forming a color filter layer includes a chromatic coloring include an isotropic shape ( for example, a spherical shape
agent. The chromatic coloring agent may be either a pigment and a polyhedral shape ), an anisotropic shape ( for example ,
or a dye. With regard to the details of the chromatic coloring a needle shape, a rod shape, and a plate shape ), and an
agent, the above-mentioned ones may be mentioned . The amorphous shape. The weight - average particle diameter of
content of the chromatic coloring agent is preferably 0.1 % 55 the primary particles of the white pigment is preferably 150
to 70 % by mass with respect to the total solid content of the nm or less , more preferably 100 nm or less , and still more
composition for forming a colored layer. The lower limit is preferably 80 nm or less . The lower limit value is not
preferably 0.5 % by mass or more, and more preferably 1.0 % particularly limited, but is preferably 1 nm or more . The
by mass or more . The upper limit is preferably 60 % by mass specific surface area of the white pigment is preferably 10 to
or less , and more preferably 50 % by mass or less . 60 400 m²/ g , more preferably 20 to 200 m´/ g , and still more
The composition for forming a color filter layer can preferably 30 to 150 m² /g . The content of the white pigment
further contain a curable compound, a photoinitiator, a resin , is preferably 20 % to 70 % by mass with respect to the total
a solvent, a pigment derivative, a polymerization inhibitor, solid content of the composition for forming a transparent
a surfactant, a silane coupling agent, an ultraviolet absorber, layer. The lower limit is more preferably 25 % by mass or
an antioxidant, or the like . With regard to the details thereof, 65 more , and still more preferably 30 % by mass or more . The
the above -mentioned materials which are used for the upper limit is more preferably 65 % by mass or less , and still
above -mentioned composition for a near -infrared transmit- more preferably 60 % by mass or less .
 US 10,991,749 B2
65 66
The composition for forming a transparent layer can applying a composition including an organic material onto a
further contain a curable compound, a photoinitiator, a partition wall , followed by drying. In a case of forming the
solvent, a polymerization inhibitor, a surfactant, a silane protective layer formed of an inorganic material, the pro
coupling agent, an ultraviolet absorber, an antioxidant, or the tective layer can be formed by, for example, depositing an
like . With regard to the details thereof, the above -mentioned 5 inorganic material constituting the protective layer onto a
materials which are used for the above -mentioned compo- surface of the protective layer by a deposition method such
sition for a near -infrared transmitting filter may be men- as chemical vapor deposition (CVD ) and vacuum deposi
tioned , and preferred ranges thereof are also the same . tion , a sputtering method, or the like to form a film .
Further, preferred contents of these materials are also the Next , a near -infrared transmitting filter layer is formed in
same as the content for the composition for a near - infrared 10 a region partitioned by the partition wall on the support. The
transmitting filter. In addition , as the composition for form- near - infrared transmitting filter layer can be formed using
ing a transparent layer, the radiation -sensitive composition the above -mentioned composition for forming a near -infra
described in JP2013-254047A , the contents of which are red transmitting filter layer ( composition for a near- infrared
incorporated herein by reference, can also be used .
< Storage Container for Composition>
transmitting filter) of the embodiment of the present inven
tion . Specifically, the near - infrared transmitting filter layer
15
A storage container for each of the compositions is not can be formed through a step of applying the composition
particularly limited , and a known storage container can be for forming a near - infrared transmitting filter layer in the
used . Further, as the storage container, it is also preferable to region partitioned by a partition wall on a support, followed
use a multilayer bottle having an inner wall constituted with by drying
6 kinds of resins in 6 layers or a bottle having a 7 - layer As a method for applying the composition for forming a
structure with 6 kinds of resins for the purpose of suppress- 20 near - infrared transmitting filter layer, a known method can
ing incorporation of impurities into raw materials or com- be used . Examples of the method include a dropwise addi
positions. Examples of such a container include the con- tion method ( drop cast) ; a slit coating method ; a spraying
tainers described in JP2015-123351A . method; a roll coating method ; a rotation coating method
<Method for Producing Structure > ( spin coating ); a cast coating method; a slit-and -spin
Next, a method for producing the structure of the embodi- 25 method ; a pre -wetting method ( for example, the method
ment of the present invention will be described . The struc- described in JP2009-145395A) ; various printing methods
ture of the embodiment of the present invention can be such as ink jet ( for example, an on -demand mode , a piezo
produced through a step of forming a partition wall on a mode, and a thermal mode) , a discharge system such as
support and a step of forming a near - infrared transmitting nozzle jet, flexographic printing, screen printing, gravure
filter layer in a region partitioned by the partition wall on the 30
printing, reverse offset printing, and metal mask printing; a
support. transfer method using a mold or the like ; and a nanoimprint
The partition wall can be formed using a method known method. The application method using ink jet is not particu
in the related art. For example, the partition wall can be larly limited and examples thereof include a method (in
forming in the following manner . particular, pp . 115 to 133 ) described in “ Extension ofUse of
First , a partition wall material layer is formed on a Injector - Infinite Possibilities in Patent- (Published in Feb
support. For example, in a case of forming a silica particle 35 ruary, 2005 , S. B. Research Co. , Ltd. ) and the methods
partition wall, a partition wall material layer can be formed described in JP2003-262716A , JP2003-185831A , JP2003
by applying a curable composition including silica particles 261827A , JP2012-126830A , JP2006-169325A , or the like .
onto a support, and then performing curing or the like to The composition layer formed by applying the composi
form a film . With regard to the curable composition includ- tion for forming a near - infrared transmitting filter layer may
ing silica particles, reference can be made to the description 40 be dried (pre -baked ). The pre -baking temperature is prefer
in JP2015-166449A and JP2014-063125A , the contents of ably 150 ° C. or lower, more preferably 120 ° C. or lower, and
which are incorporated herein by reference . Further, in a still more preferably 110 ° C. or lower . The lower limit may
case of forming a partition wall using a siloxane resin or a be set to , for example, 50 ° C. or higher, or to 80 ° C. or
fluorine resin , a partition wall material layer can be formed higher. The pre -baking time is preferably 10 seconds to
by applying a resin composition including a siloxane resin or 45 3,000 seconds , more preferably 40 to 2,500 seconds , and
a fluorine resin onto a support, and then performing curing still more preferably 80 to 220 seconds . Pre - baking can be
or the like to form a film . In addition, for example, in a case performed using a hot plate , an oven , or the like .
of forming a partition wall formed of an inorganic material While the near -infrared transmitting filter layer is formed ,
such as silicon dioxide, a partition wall material layer can be a step of forming a pattern can further be included .
formed by depositing inorganic materials such as silicon Examples of the pattern forming method include a pattern
dioxide onto a support by a deposition method such as 50 forming method using photolithography and a pattern form
chemical vapor deposition (CVD ) and vacuum deposition, a ing method using a dry etching method . Hereinafter, the step
sputtering method, or the like . Subsequently, a resist pattern of forming a pattern will be described in detail.
is formed on the partition wall material layer using a mask (Case of Forming Pattern by Photolithography )
having a pattern following the shape of the partition wall . The pattern forming method by photolithography prefer
Then , the partition wall material layer is subjected to etching 55 ably includes a step of patternwise exposing a composition
by a dry etching method using this resist pattern as a mask . layer ( exposing step ) and a step of removing the composi
Subsequently, the resist pattern is peeled and removed from tion layer on the unexposed area by development to form a
the partition wall material layer, whereby a partition wall can pattern ( developing step ) . As desired , a step of baking the
be formed . With regard to the dry etching method , reference developed pattern ( post -baking step ) can be provided . Here
can be made to the description in JP2016-014856A , the 60 inafter, the respective steps will be described .
contents of which are incorporated herein by reference . << Exposing Step >>
Further, the partition wall can also be formed using the The composition layer is patternwise exposed in the
method described in JP2006-128433A . exposing step . For example , the composition layer can be
After forming the partition wall , a protective layer may be subjected to patternwise exposure by performing exposure
formed on a surface of the partition wall . The protective using an exposure device such as a stepper through a mask
layer can be formed using a method known in the related art. 65 having a predetermined mask pattern . Thus, the exposed
In a case of forming a protective layer formed of an organic area can be cured . As the radiation ( light) which can be used
material, the protective layer can be formed by, for example, during the exposure , ultraviolet rays such as g -rays and
 US 10,991,749 B2
67 68
i- rays are preferable, and the i- rays are more preferable . The complete the curing of the film . In a case of performing the
irradiation dose ( exposure dose ) is , for example, preferably post - baking , the post -baking temperature is preferably, for
0.03 to 2.5 J/cm², more preferably 0.05 to 1.0 J/cm² , and example, 50 ° C. to 240 ° C. From the viewpoint of curing of
most preferably 0.08 to 0.5 J/cm² . The oxygen concentration the film , the post -baking temperature is more preferably
during the exposure can be appropriately selected, and may 5 200 ° C. to 230 ° C. In addition , in a case of using an organic
also be performed , for example, in a low -oxygen atmosphere electroluminescence ( organic EL ) element as a light-emit
having an oxygen concentration of 19 % by volume or less ting light source of an image display device or a case of
( for example, 15 % by volume , 5 % by volume, and substan constituting a photo -electric conversion film of an image
tially oxygen - free) or in a high -oxygen atmosphere having sensor with organic materials, the post- baking temperature
anexample
oxygen, 22concentration
% by volumeof, more
30% than 21 % by, and
by volume volume
50%(byfor 10 is preferably 150° C. or lower, more preferably 120 ° C. or
volume) . Further, the exposure illuminance can be appro lower, still more preferably 100 ° C. or lower, and particu
priately set, and can be usually selected from a range of larly preferably 90 ° C. or lower. Post -baking can be per
1,000 W /m² to 100,000 W /m2 (for example, 5,000 W /m², formed continuously or batchwise using a heating unit such
15,000 W /m², or 35,000 W / m ). Appropriate conditions of as a hot plate , a convection oven ( hot -air circulating dryer ),
each of the oxygen concentration and the illuminance of 15 and a satisfies
ment high - frequency heater .so that the film after develop
the conditions
exposure energy may be combined , and for example, a
combination of an oxygen concentration of 10 % by volume ( Case of Forming Pattern by Dry Etching Method )
and an illuminance of 10,000 W /m², a combination of an Pattern formation by a dry etching method can be per
oxygen concentration of 35 % by volume and an illuminance formed by a method including, for example, curing a com
of 20,000 W /m², or the like is available . 20
position layer on a support to form a cured product layer,
<<Developing Step>> then forming a patterned photoresist layer on the cured
Next, the composition layer of the unexposed area in the product layer, and subsequently subjecting the cured product
composition layer after exposure is removed by develop
ment to form a pattern . The removal of the composition layer layer to dry -etching using an etching gas through the pat
of the unexposed area by development can be performed 25 terned photoresist layer as a mask . In the formation of the
using a developer. Thus, the composition layer of the unex- photoresist layer, it is preferable to further carry out a
posed area in the exposing step is eluted with the developer, pre -baking treatment. In particular, as a process for forming
and as a result , only a photocured portion remains. As the a photoresist, an aspect in which a post- exposure heating
developer, an organic alkali developer causing no damage on treatment or a post -development heating treatment (post
the underlying. solid
is preferable The - state imaging ofdevice
temperature the ,developer
circuit, or the
is, like
for 30 baking treatment) is performed is preferable. With regard to
example, preferably 20 ° C. to 30 ° C. , and the development the pattern formation by a dry etching method, reference can
time is preferably 20 to 180 seconds . Further, in order to be made to the descriptions in paragraph Nos . 0010 to 0067
improve residue removing properties, a step of removing the of JP2013-064993A , the contents of which are incorporated
developer by shaking every 60 second and supplying a new herein by reference .
developer again may be repeated multiple times . 35
In a case where the structure of the embodiment of the
Examples of the alkali agent used for the developer present invention further has other layers such as a color
include organic alkaline compounds such as ammonia water, filter layer and a near - infrared shielding filter layer, the
ethylamine, diethylamine, dimethylethanolamine, digly
colamine, diethanolamine, hydroxyamine, ethylenediamine, structure can be formed by performing the same steps as
tetramethylammonium hydroxide, tetraethylammonium described in the above mentioned
- near - infrared transmitting
hydroxide, tetrapropylammonium hydroxide, tetrabutylam- 40 filter layer forming step, using each of the compositions for
monium hydroxide, ethyltrimethylammonium hydroxide, forming filter layers.
benzyltrimethylammonium hydroxide, dimethyl bis(2 -hy
droxyethyl) ammonium hydroxide, choline, pyrrole, piperi EXAMPLES
dine, and 1,8 -diazabicyclo [5.4.0 ]-7 -undecene , and inorganic 45
alkaline compounds such as sodium hydroxide, potassium
hydroxide, sodium carbonate , sodium hydrogen carbonate , Hereinbelow , the present invention will be described in
sodium silicate , and sodium metasilicate . As the alkali agent, more detail with reference to Examples. The materials, the
a compound having a high molecular weight is preferable in amounts of materials used , the proportions, the treatment
consideration of the environments and the safety. As to the details, the treatment procedure, and the like shown in the
developer, an aqueous alkaline solution obtained by diluting 50 Examples below may be modified if appropriate as long as
the alkali agent with pure water is preferably used . The the modifications do not depart from the spirit of the present
concentration of the alkali agent in the aqueous alkaline
solution is preferably 0.001 % to 10% by mass , and more invention . Therefore , the scope of the present invention is
preferably 0.01 % to 1 % by mass . Moreover, a developer not limited to specific Examples shown below. In addition ,
containing a surfactant may also be used . Examples of the 55 " parts ” and “ % " are on a mass basis unless otherwise
surfactant include the above -mentioned surfactants , with the specified
non - ionic surfactant being preferable. The developer may < Preparation of Composition for Forming Near - Infrared
first be prepared as a concentrated liquid and then diluted to Transmitting Filter Layer (IR Transmitting Composition) >
a desired concentration upon use from the viewpoint of
convenience in transportation and storage , and the concen- 60 ( Preparation of Pigment Dispersion Liquids R - 1 , R - 2 ,
tration rate is not particularly limited , but can be set to a B - 1 , B - 2 , Y - 1, Y - 2 , V - 1, IR - 1 , and Bk - 2 )
range of 1.5- to 100 -times. Incidentally, in a case where a
developer including such an aqueous alkaline solution is The raw materials described in the following table were
used , it is preferable that cleaning ( rinsing) with pure water mixed , 230 parts by mass of zirconia beads with a diameter
of 0.3 mm were further added thereto , the mixture was
is performed after development.
After the development, a heating treatment ( post - baking) 65 subjected to a dispersion treatment for 5 hours , and the beads
can also be performed after carrying out drying. The post- were separated by filtration to produce each of pigment
baking is a heating treatment after development so as to dispersion liquids.
 US 10,991,749 B2
69 70
TABLE 1

Dispersion aid
Color material (Derivative, resin ) Dispersant Solvent

Parts by Parts by Parts by Parts by

Type mass Type mass Type mass Type mass

Pigment dispersion liquid R- 1 PR254 12.59 C1 4.4 J1 83.01

Pigment dispersion liquid R- 2 PR254 12.59 C3 4.4 J1 83.01
Pigment dispersion liquid B - 1 PB15 : 6 12.59 C2 4.4 J1 83.01
Pigment dispersion liquid B - 2 PB15 : 6 12.59 C3 4.4 J1 83.01
Pigment dispersion liquid Y - 1 PY139 11.00 B1 1.59 C2 4.4 J1 83.01
Pigment dispersion liquid Y - 2 PY139 11.00 B1 1.59 C3 4.4 J1 83.01
Pigment dispersion liquid Y - 1 PY23 14.20 P1 2 C4 3.8 J1 73.01
J2 10.00
Pigment dispersion liquid IR- 1 A1 11.00 B2 1.59 C3 4.4 J1 83.01
Pigment dispersion liquid Bk - 2 Pigment Black 32 12.59 C2 4.4 J1 83.01

( Preparation of R Transmitting Composition )

The raw materials described in the following table were

mixed to prepare IR transmitting compositions 1 to 4 .
TABLE 2
IR transmitting IR transmitting IR transmitting IR transmitting
composition 1 composition 2 composition 3 composition 4
Pigment R -1 19.09
dispersion R -2 25.48
liquid B- 1 29.32 13.50
B- 2 25.48
Y-1 23.79 11.59 13.50
Y-2 12.74
V -1 41.43 6.65
IR - 1 14.14
Bk - 2 40.51
Curable D1 0.91
compound D2 2.12 2.09
D3 2.09
D4 2.48
Photoinitiator 11 0.74 1.20
12 1.01
13 1.20
Resin P1 2.18 2.24
P2 1.38
Ultraviolet UV1 0.41
absorber
Surfactant F1 0.008 0.042 0.042 0.04
Polymerization G1 0.00152 0.01 0.01 0.001
inhibitor
Solvent J1 29.21 27.83 26.92 15.90

60
< Preparation of Composition for Forming Near - Infrared Dispersion liquid in the following table , in the amount of
Shielding Filter layer (IR Absorbing Composition) parts by mass described in the section of Dispersion liquid
The raw materials described in the following table were in the following table, further adding 230 parts by mass of
mixed to prepare IR absorbing compositions 1 to 3. Further,
as the dispersion liquid, a dispersion liquid produced by 65 zirconia beads with a diameter of 0.3 mm thereto, subjecting
the mixture to a dispersion treatment for 5 hours using a
mixing a near- infrared absorber, a derivative, a dispersant,
and a solvent, each in a type described in the section of paint shaker, and separating the beads by filtration was used .
 US 10,991,749 B2
71 72
TABLE 3
Dispersion liquid
Near -infrared Curable
absorbing dye Derivative Dispersant Solvent Resin compound

Parts by Parts by Parts by Parts by Parts by Parts by

Type mass Type mass Type mass Type mass Type mass Type mass

IR absorbing A3 2.5 B2 0.5 C3 1.8 J1 39 P1 5.5 ? 5 ?4 3.2

composition 1 3.2
IR absorbing A4 2.5 B2 0.5 C3 1.8 J1 39 P1 5.5 D5D4 3.2
composition 2 3.2
IR absorbing A2 2.5 B4 0.5 C3 1.8 J1 39 P1 5.5 ? 5 ?4 3.2
composition 3 3.2

Ultraviolet Polymerization
Photoinitiator absorber Surfactant inhibitor Antioxidant Solvent

Parts by Parts by Parts by Parts by Parts by Parts by

Type mass Type mass Type mass Type mass Type mass Type mass

IR absorbing 14 1 UV3 1.6 F1 0.025 G1 0.003 A01 0.2 J1 41.472

composition 1
IR absorbing 14 1 UV3 1.6 F1 0.025 G1 0.003 A01 0.2 J1 41.472
composition 2
IR absorbing 14 1 UV3 1.6 F1 0.025 G1 0.003 A01 0.2 J1 41.472
composition 3

The raw materials described in the table are as follows. Pigment Black 32 : C. I. Pigment Black 32
( Color Material) 35
PR254 : C. I. Pigment Red 254 A1 to A4 : Compounds having the following structures
PB15 : 6 : C. I. Pigment Blue 15 : 6 ( near- infrared absorbing dyes ). In the following formulae,
PY139: C. I. Pigment Yellow 139 Me represents a methyl group and Ph represents a phenyl
PV23 : C. I. Pigment Violet 23 group .

(A1 )
OMe

Ph
Ph OH
S

NC
CN

HO Ph |
Ph

OMe
 US 10,991,749 B2
73 74
-continued
(A2)

Ph
Ph
B

NMe
NC
CN
MeN

Ph
Ph N

CI

(A3) (A4 )

Ph Ph
Ph Ph

NC CN
NC CN
N
N B
Ph Ph
Ph Ph
 US 10,991,749 B2
75 76
(Derivative )
B1 , B2 , and B4 : Compound having the following struc
tures. In the following structural formulae, Ph represents a
phenyl group.

(B1)

tostamine ?
NH

(B2 )

Ph

com * SO3H

They
NC

HO3S
Ph

CI
(B4)

Econo
NC

BUITEN
CN

N
SO3H .

Ph Ph

HO3S
CI CI
 US 10,991,749 B2
77 78
( Dispersant) and the numerical value described together with the side
C1 : Resin having the following structure . ( The numerical chain is the number of repeating units. Mw = 26,000 )
value described together with the main chain is a molar ratio , C3 : Resin having the following structure. ( The numerical
and the numerical value described together with the side value described together with the main chain is a molar ratio ,
chain is the number of repeating units . Mw = 21,000 ) 5 and the numerical value described together with the side
C2 : Resin having the following structure . ( The numerical chain is the number of repeating units . Mw = 21,000 )
value described together with the main chain is a molar ratio , C4 : Disperbyk -111 (manufactured by BYK Chemie )
(C1 )

24

enny ??

thengenden (C2)

themi (C3 )
Myt
Tintint -C7H15
X
tirtine -C-H15

" the HO2C

'N

OH
a / b / c / d / e = 36/4/35/1/24 (mol % ) x = 48 y = 12
 US 10,991,749 B2
79 80
(Resin) (Ultraviolet Absorber )
P1 : Resin having the following structure . (The numerical UV1: UV -503 (manufactured by Daito Chemical Co. ,
value described together with the main chain is a molar ratio . Ltd. )
Mw = 10,000, acid value =70 mgKOH/g ) 5
UV3 : Compound having the following structure
P2 : Resin having the following structure. (The numerical
value described together with the main chain is a molar ratio .
Mw = 10,000 , acid value =70 mgKOH/g ) (UV3)

10
( P1 )

Dax
COOMe COOMe
t 45

15

( Surfactant)
F1 : The following mixture (Mw = 14,000 ). In the follow
10

th OH
20
ing formula , % representing a ratio of the repeating units is
in % by mass .

OH
25

30
I 62 %
C6F13

H
(P2) otNi

tho t 35 H
OH
L2
M2 otN2

38 %
L1 + N1 + L2 + N2 = 14
M1 + M2 = 17
40

OH (Polymerization Inhibitor )
G1 : p -Methoxyphenol
45
( Antioxidant)
(Curable Compound ) A01 : ADK STAB A0-80 (manufactured by ADEKA
D1 : KAYARAD RP - 1040 (manufactured by Nippon Kay Corporation )
aku Co. , Ltd., radically polymerizable compound ) ( Solvent)
D2 : ARONIX TO - 2349 (manufactured by Toagosei Co. , J1 : Propylene glycol monomethyl ether acetate ( PGMEA)
Ltd. , radically polymerizable compound ) 50
< Preparation of Composition for Forming Protective
Layer >
D3 : ARONIX M - 305 (manufactured by Toagosei Co. , (Composition 1 for Forming Protective Layer )
Ltd. , radically polymerizable compound )
D4 : NK ester A - TMMT (manufactured by Shin -Naka The following raw materials were mixed to prepare a
mura Chemical Co. , Ltd. , radically polymerizable com composition 1 for forming a protective layer.
pound ) 55 A 54 % -by - mass propylene glycol monomethyl ether
D5 : KAYARAD DPHA (manufactured by Nippon Kay (PGME ) solution of the resin 1 ... 0.7 parts by mass
aku Co. , Ltd., radically polymerizable compound ) A 0.2 % -by -mass propylene glycol monomethyl ether
( Photoinitiator ) acetate ( PGMEA) solution of the surfactant 1 ... 0.8 parts
11 : IRGACURE OXE02 (manufactured by BASF, pho by mass
toradical polymerization initiator)
60 PGMEA 98.5 parts by mass
Resin 1 : Cyclomer P ( ACA )230AA (manufactured by
12 : IRGACURE OXEO3 (manufactured by BASF, pho Daicel Chemical Industries, Ltd. , acid value=30 mgKOH/g ,
toradical polymerization initiator) Mw = 15,000 )
13 : IRGACURE OXE04 (manufactured by BASF, pho Surfactant 1 : The surfactant F1
toradical polymerization initiator ) 65 < Preparation of Composition for Forming Color Filter
14 : IRGACURE OXE01 (manufactured by BASF, pho Layer >
toradical polymerization initiator) ( Red Composition 1 )
 US 10,991,749 B2
81 82
The raw materials shown below were mixed , stirred , and 139 , 6.8 parts by mass of a dispersant (Disperbyk - 161,
then filtered through a nylon -made filter with a pore diam- manufactured by BYK Chemie ), and 79.3 parts by mass of
eter of 0.45 um (manufactured by Nihon Pall Ltd. ) to prepare PGMEA was mixed and dispersed using a beads mill
Red Composition 1 . (zirconia beads with a diameter of 0.3 mm ) for 3 hours to
Red pigment dispersion liquid ... 51.7 parts by mass 5 prepare a pigment dispersion liquid. Thereafter, the mixture
A 40 % -by-mass PGMEA solution of the resin 2 ... 0.6 was further subjected to a dispersion treatment at a flow rate
parts by mass of 500 g/min under a pressure of 2,000 kg/cm3 using a
Curable compound 1 ... 0.6 parts by mass high -pressure dispersing machine with pressure reducing
Photoinitiator 1 0.3 parts by mass mechanism , NANO - 3000-10 (manufactured by Nippon
A 0.2 % -by - mass PGMEA solution of the surfactant 1 .. 10 BEE Chemical Co. , Ltd. ). This dispersion treatment was
4.2 parts by mass repeated ten times to obtain a red pigment dispersion liquid .
PGMEA ... 42.6 parts by mass Green Pigment Dispersion Liquid
(Green Composition 1 ) A mixed liquid formed of 6.4 parts by mass of C. I.
The raw materials shown below were mixed , stirred, and Pigment Green 36 , 5.3 parts by mass of C. I. Pigment Yellow
then filtered through a nylon -made filter with a pore diam- 15 150 , 5.2 parts by mass of a dispersant ( Disperbyk - 161,
eter of 0.45 um (manufactured by Nihon Pall Ltd. ) to prepare manufactured by BYK Chemie ), and 83.1 parts by mass of
Green Composition 1 . PGMEA was mixed and dispersed using a beads mill
Green pigment dispersion liquid ... 73.7 parts by mass (zirconia beads with a diameter of 0.3 mm ) for 3 hours to
A 40 % -by -mass PGMEA solution of the resin 2 ... 0.3 prepare a pigment dispersion liquid . Thereafter, the mixture
parts by mass 20 was further subjected to a dispersion treatment at a flow rate
Curable compound 2 ... 1.2 parts by mass of 500 g/min under a pressure of 2,000 kg/cm using a
Photoinitiator 1 0.6 parts by mass high -pressure dispersing machine with pressure reducing
A 0.2 % -by -mass PGMEA solution of the surfactant 1 .. mechanism , NANO - 3000-10 (manufactured by Nippon
4.2 parts by mass BEE Chemical Co. , Ltd.). This dispersion treatment was
Ultraviolet absorber 1 . 0.5 parts by mass 25 repeated ten times to obtain a green pigment dispersion
PGMEA 19.5 parts by mass liquid .
(Blue Composition 1 ) Blue Pigment Dispersion Liquid
The raw materials shown below were mixed , stirred , and A mixed liquid formed of 9.7 parts by mass of C. I.
then filtered through a nylon -made filter with a pore diam- Pigment Blue 15 : 6 , 2.4 parts by mass of C. I. Pigment Violet
eter of0.45 um (manufactured by Nihon Pall Ltd. ) to prepare 30 23 , 5.5 parts by mass of a dispersant ( Disperbyk - 161,
Blue Composition 1 . manufactured by BYK Chemie ), and 82.4 parts by mass of
Blue pigment dispersion liquid ... 44.9 parts by mass PGMEA was mixed and dispersed using a beads mill
A 40% -by - mass PGMEA solution of the resin 2 . 2.1 (zirc beads with a diameter of 0.3 mm ) for 3 hours to
parts by mass prepare a pigment dispersion liquid . Thereafter, the mixture
Curable compound 1 1.5 parts by mass 35 was further subjected to a dispersion treatment at a flow rate
Curable compound 3 . 0.7 parts by mass of 500 g/min under a pressure of 2,000 kg/cm² using a
Photoinitiator 2 ... 0.8 parts by mass high - pressure dispersing machine with pressure reducing
A 0.2 % -by -mass PGMEA solution of the surfactant 1 .. mechanism , NANO - 3000-10 (manufactured by Nippon
4.2 parts by mass PGMEA 45.8 parts by mass BEE Chemical Co. , Ltd.). This dispersion treatment was
The raw materials used for the composition for forming a 40 repeated ten times to obtain a blue pigment dispersion liquid .
color filter layer are as follows. Resin 2 : The Resin P1
Red pigment dispersion liquid Surfactant 1 : The Surfactant F1
A mixed liquid formed of 9.6 parts by mass of C. I. Curable compound 1 : Compound having the following
Pigment Red 254 , 4.3 parts by mass of C. I. Pigment Yellow structure

mom
 US 10,991,749 B2
83 84
Curable compound 2 : A mixture of compounds having the -continued
following structures ( a mixture of the left compound
and the right compound at a molar ratio of 7 : 3 )
5
not N1
H

10
oth
38%
that ote
L1 + N1 + L2 + N2 = 14
OH M1 + M2 = 17

15 < Production of Structure >

Test Example 1
Examples 1-1 to 1-15 and Comparative Examples
20 1-2 to 1-4
A partition wall material layer was formed on a silicon
wafer using a partition wall material described in the fol
lowing table , and the partition wall material layer was
25 patterned by a dry etching method under the conditions
described in paragraph Nos . 0128 to 0133 of JP2016
014856A to form partition walls (a width of 50 nm and a
Curable compound 3 : ARONIX M - 305 ( 55 % to 63 % by height of 1 um ) in a lattice form at an interval of 1 um . The
mass of triacrylate included, manufactured by Toagosei dimension (a region partitioned by the partition wall on the
Co. , Ltd. ) 30 silicon wafer) of the partition wall on the silicon wafer was
Photoinitiator 1 : The photoinitiator 14 1 um verticalx1 um horizontal. Next, patterning was per
Photoinitiator 2 : The photoinitiator 12 formed on the silicon wafer having the partition walls
Photoinitiator 3 : The photoinitiator 13 formed thereon by photolithography using an IR transmit
Ultraviolet absorber 1 : The ultraviolet absorber UV1 ting composition described in the following table to form a
< Preparation of Composition for Forming Transparent 35 near -infrared transmitting filter layer ( a thickness of 1 um )
Layer > in a region partitioned by the partition wall on the silicon
( White Composition ) wafer. Subsequently, a lens was formed on the near - infrared
The raw materials shown below were mixed , stirred , and transmitting filter layer to produce a structure shown in FIG .
then filtered through a nylon -made filter with a pore diam- 1.
eter of 0.45 um (manufactured by Nihon Pall Ltd.) to prepare 40
a white composition . Comparative Examples 1-1 , and 1-5 to 1-7
Resin ( a polymer 1 produced by the method described in
paragraph Nos. 0213 to 0216 of JP2013-254047A ) ... 20.5 Patterning was performed by photolithography using an
parts by mass IR transmitting composition described in the following table
Curable compound (ARONIX M - 510 , manufactured by
Toagosei Co. , Ltd. ) ... 12.2 parts by mass
45 on a silicon wafer to form a 1 - um? near - infrared transmitting
Photoinitiator ( IRGACURE -OXE02, manufactured by ) filter layer (a thickness of 1 um ). Subsequently, a lens was
BASF ... 1.1 parts by mass Ultraviolet absorber (UV -503 formed on the near- infrared transmitting filter layer to pro
duce a structure .
(manufactured by Daito Chemical Co. , Ltd. ) ... 1.8 parts ( Evaluation of Near - Infrared Recognition Ability )
by mass 50 Each of the structures was introduced into an optical
PGMEA 52.7 parts by mass sensor according to a known method and its near - infrared
Cyclohexanone ... 11.4 parts by mass recognition ability was evaluated . Further, for the structure
Silane coupling agent (Shin - Etsu silicone , KBM - 602 ) .. using the IR transmitting composition 1 , an ability to rec
.0.1 parts by mass ognize the light in a wavelength range of 720 nm was
Polymerization inhibitor (p -methoxyphenol) ... 0.1 parts 55 evaluated . In addition , for the structure using the IR trans
by mass
Surfactant (the following mixture (Mw = 14,000 , % rep mitting composition 2 or 3 , an ability to recognize the light
resenting the ratio of the repeating units is in % by atstructure a wavelength of 850 nm was evaluated . Further, for the
using the IR transmitting composition 4 , an ability
mass ) ... 0.1 parts by mass to recognize the light at a wavelength of 940 nm was
60 evaluated .
( Evaluation Standard )
4 : There was almost no noise and the near - infrared
recognition ability was good .
C6F13 3 : Noise was slightly generated, but the near - infrared
65 recognition ability was good .
62 % 2 : Noise was more or less generated, but the near - infrared
recognition ability was good .
 US 10,991,749 B2
85 86
1 : The structure has a near - infrared recognition ability but TABLE 4
there was much noise .
Near - infrared Near- infrared
The partition wall materials described in the following Partition wall transmitting recognition
table are as follows. 5
material filter layer ability
Partition wall material 1 : Silicon dioxide ( a minimum Example 1-1 Partition wall IR transmitting 3
value of the refractive index with respect to light in a material 1 composition 2
wavelength range of 700 to 1,000 nm = 1.46 ). The partition Example 1-2 Partition wall IR transmitting 4
material 2 composition 2
wall material layer was formed by a chemical deposition Example 1-3 Partition wall IR transmitting 4
method. 10 material 3 composition 2
Example 1-4 Partition wall IR transmitting 4.
Partition wall material 2 : Fluorine resin (CYTOP, manu material 4 composition 2
factured by Asahi Glass Co. , Ltd., the minimum value of the Example 1-5 Partition wall
material 5
IR transmitting
composition 2
4
refractive index with respect to light in a wavelength range Example 1-6 Partition wall IR transmitting 4
of 700 to 1,000 nm = 1.34 ). The partition wall material layer 15 material 6 composition 2
was formed by applying a composition including a fluorine Example 1-7 Partition wall
material 1
IR transmitting
composition 1
3
resin onto a support, followed by heating at 220 ° C. for 5 Example 1-8 Partition wall IR transmitting 3
minutes . material 1 composition 3
Partition wall material 3 : Siloxane resin ( the resin of A03 Example 1-9 Partition wall IR transmitting 3
material 1 composition 4
in paragraph No. 0345 of JP2014-063125A , the minimum 20 Example 1-10 Partition wall IR transmitting 4
value of the refractive index with respect to light in a material 2 composition 1
wavelength range of 700 to 1,000 nm = 1.36 ). The partition Example 1-11 Partition wall
material 3
IR transmitting
composition 3
4

wall material layer was formed by applying a composition Example 1-12 Partition wall IR transmitting 4
including the siloxane resin onto a support, followed by material 4 composition 4
heating at 220 ° C. for 5 minutes . 25 Example 1-13 Partition wall IR transmitting 4.
material 5 composition 1
Partition wall material 4 : The composition 107 described Example 1-14 Partition wall IR transmitting 4
in paragraph No. 0160 of JP2015-166449A ( a composition material 6 composition 3
Example 1-15 Partition wall IR transmitting 4
including silica particles. The silica particles included in the material 4 composition 4
composition had the minimum value of the refractive index 30 Comparative Partition wall IR transmitting
composition 2
2
with respect to light in a wavelength range of 700 to 1,000 Example 1-1
Comparative
not existed
Comparative IR transmitting 2
nm of 1.24 ) . The partition wall material layer was formed by Example 1-2 Partition wall composition 2
applying the composition 107 onto a support, followed by material 1
heating at 220 ° C. for 5 minutes . Comparative Comparative IR transmitting 2
35 Example 1-3 Partition wall composition 2
Partition wall material 5 : The composition A02 described material 2
in paragraph No. 0345 of JP2014-063125A ( a composition Comparative
Example 1-4
Comparative
Partition wall
IR transmitting
composition 2
2
including silica particles. The silica particles included in the material 3
composition A02 had the minimum value of the refractive Comparative Partition wall IR transmitting 2
index with respect to light in a wavelength range of 700 to 40 Example 1-5
Comparative
not existed
Partition wall
composition 1
IR transmitting 2
1,000 nm of 1.28 ) . The partition wall material layer was Example 1-6 not existed composition 3
formed by applying the composition onto a support, fol Comparative Partition wall IR transmitting 2
lowed by heating at 220 ° C. for 5 minutes . Example 1-7 not existed composition 4
Partition wall material 6 : Siloxane resin (the composition
described in Example 2 of JP2011-084672A . The siloxane 45 Furthermore, in Examples 1-1 to 1-15 , the refractive
resin ( cage - type siloxane resin ) included in the composition index of the partition wall at at least a portion of the
has the minimum value of the refractive index with respect wavelengths of the near - infrared light transmitted by the
to light in a wavelength range of 700 to 1,000 nm of 1.32 ) . near - infrared transmitting filter layer was smaller than the
The partition wall material layer was formed by applying the refractive index of the near - infrared transmitting filter layer.
siloxane resin onto a support, followed by heating at 220 ° C. 50 wallIn addition , in Examples 1-6 and 1-14 in which the partition
was formed using the partition wall material 6 , the
for 5 minutes .
Comparative partition wall material 1 : Sin (the minimum refractiverefractive index of the partition wall was smaller than the
index of the near - infrared transmitting filter layer
value of the refractive index with respect to light in a by 0.2 or more .
wavelength range of 700 to 1,000 nm is 2.02 ) . The partition 55 On the other hand, in Comparative Examples 1-2 , 1-3 , and
wall material layer was formed by chemical deposition 1-4 , in which partition walls were formed using the com
method. parative partition wall materials 1 to 3 , the refractive index
Comparative partition wall material 2 : Tio , ( the mini- of the partition wall with respect to the near - infrared light
mum value of the refractive index with respect to light in a transmitted
larger than
by the near -infrared transmitting filter layer was
thelayer
refractive index of the near - infrared trans
wavelength range of 700 to 1,000 nm is 2.83 )
.
wall material layer was formed by chemical deposition
The partition 60 mitting filter .
method . As shown in the table , the structures of Examples had an
excellent near - infrared recognition ability, and thus could
Comparative partition wall material 3 : Tungsten (the detect the near - infrared light with good sensitivity. In a case
minimum value of the refractive index with respect to light where the partition walls were formed using the partition
in a wavelength range of 700 to 1,000 nm is 3.84 ) . The 65 wall materials 2 , 3 , and 6 , it was possible to form partition
partition wall material layer was formed by chemical depo- walls having less deviation in the width dimension or
sition method . defects .
 US 10,991,749 B2
87 88
In each of Examples, even in a case where the width of the silicon wafer was 1 um verticalx1 um horizontal. Next,
partition wall was changed to 20 nm , 100 nm , or 200 nm , the patterning was performed on the silicon wafer having the
same good recognition ability as in each of Examples was partition walls formed thereon by photolithography using an
obtained . IR transmitting composition described in the following table
In addition , in each of Examples, even in a case where the 5 to form a near - infrared transmitting filter layer (a thickness
height of the partition wall was changed to 0.5 um or 1.5 um , of 1 um ) in a region partitioned by the partition wall on the
the same good recognition ability as in each of Examples silicon wafer. Next , patterning was performed by photoli
was obtained . thography using an IR absorbing composition to form a
In addition , even in a case where in each of Examples, the 10 near -infrared shielding layer ( a thickness of 1 um ) in a
dimension of the opening of the partition wall on the silicon region partitioned by the partition wall on the support.
wafer was changed to 5 um verticalx5 um horizontal, 20 um Subsequently, a lens was formed on the near -infrared trans
verticalx20 um horizontal, or 100 um verticalx100 um mitting filter layer and the near - infrared shielding filter layer
horizontal, the same good recognition ability as in each of to produce a structure shown in FIG . 2 .
Examples was obtained . 15
In addition , in each of Examples, even in a case where an Comparative Examples 2-1 , and 2-5 to 2-7
underlying material ( CT- 4000L , manufactured by FUJIF
ILM Electronic Materials Co. , Ltd.) was applied onto a Patterning was performed on a silicon wafer by photoli
silicon wafer such that the film thickness became 100 nm , thography using an IR transmitting composition described in
and heated at 220 ° C. for 5 minutes to form an underlayer, 20 the following table to form a 1 -um ? near - infrared transmit
the same good recognition ability as in each of Examples ting filter layer ( a thickness of 1 um ). Next , patterning was
was obtained .
In addition, in a case where the following protective layer performed by photolithography using an IR absorbing com
1 was formed on a surface of the partition wall formed using thickness ofform
position to a 1 -um ? near - infrared shielding layer ( a
the partition wall material 6 , it was possible to effectively 25 infrared shielding )layer
1 um to form a structure having the near
provided on an area having no
suppress the components from the adjacent near - infrared pattern formed thereon in the near - infrared transmitting filter
transmitting filter layer from being incorporated into the layer . Subsequently , a lens was formed on the near - infrared
partition wall . In addition , in a case where the following
protective layer 2 was formed on a surface of the partition transmitting filter layer and the near -infrared shielding filter
wall formed using the partition wall material 4 , the adhe 30 layer to produce a structure.
( Evaluation of Ability to Recognize Near - Infrared Light
siveness between the near - infrared transmitting filter layer
and the partition wall was particularly excellent. The pro and Visible Light)
tective layers 1 and 2 were formed by the following method. Each of the structures was introduced into an optical
Protective layer 1 : Silicon dioxide was deposited onto a sensor according to a known method and its ability to
surface of the partition wall by a chemical deposition 35 recognize near - infrared light and visible light was evaluated .
method to form a film , whereby a silicon dioxide film Further, for the structure using the IR transmitting compo
(protective layer 1 ) with a thickness of 20 nm was formed . sition 1 , an ability to recognize the light in a wavelength
Protective layer 2 : The above -mentioned composition for range of 720 nm was evaluated . In addition , for the structure
forming a protective layer 1 was applied onto a surface of using the IR transmitting composition 2 or 3 , an ability to
the partition wall by a spin coating method , followed by 40
recognize the light at a wavelength of 850 nm was evaluated .
heating at 100 ° C. for 2 minutes using a hot plate , and then Further, for the structure using the IR transmitting compo
heating at 230 ° C. for 2 minutes using a hot plate, whereby sition 4 , an ability to recognize the light at a wavelength of
an organic product layer (protective layer 2 ) with a film 940 nm was evaluated . The evaluation standard for the
thickness of 15 nm was formed . near - infrared recognition ability is the same as in Test
45
Example 1. The visible light recognition ability was evalu
Test Example 2 ated as follows.
( Evaluation Standard for Visible Light Recognition Abil
Examples 2-1 to 2-15 and Comparative Examples ity )
2-2 to 2-4 4 : There was almost no noise and the visible light recog
50
nition ability was good.
A partition wall material layer was formed on a silicon 3 : Noise was slightly generated, but the visible light
wafer using a partition wall material described in the fol- recognition ability was good .
lowing table , and the partition wall material layer was 2 : Noise was more or less generated, but the visible light
patterned by a dry etching method to form partition walls ( a recognition ability was good .
width of 50 nm and a height of 1 um ) in a lattice form at an 1 : The structure has a visible light recognition ability but
interval of 1 um . The dimension of the partition wall on the there was much noise .
TABLE 5
Near- infrared Near - infrared Near -infrared Visible light
Partition wall shielding transmitting recognition recognition
material filter layer filter layer ability ability
Example 2-1 Partition wall IR absorbing IR transmitting 3 3
material 1 composition 2 composition 2
Example 2-2 Partition wall IR absorbing IR transmitting 4 4
material 2 composition 2 composition 2
Example 2-3 Partition wall IR absorbing IR transmitting 4 4
material 3 composition 2 composition 2
 US 10,991,749 B2
89 90
TABLE 5 - continued
Near - infrared Near -infrared Near - infrared Visible light
Partition wall shielding transmitting recognition recognition
material filter layer filter layer ability ability
Example 2-4 Partition wall IR absorbing IR transmitting 4 4
material 4 composition 2 composition 2
Example 2-5 Partition wall IR absorbing IR transmitting 4 4
material 5 composition 2 composition 2
Example 2-6 Partition wall IR absorbing IR transmitting 4. 4
material 6 composition 2 composition 2
Example 2-7 Partition wall IR absorbing IR transmitting 3 4
material 1 composition 1 composition 1
Example 2-8 Partition wall IR absorbing IR transmitting 3 4
material 1 composition 2 composition 3
Example 2-9 Partition wall IR absorbing IR transmitting 3 4
material 1 composition 3 composition 4
Example 2-10 Partition wall IR absorbing IR transmitting 4 4
material 2 composition 1 composition 1
Example 2-11 Partition wall IR absorbing IR transmitting 4. 4
material 3 composition 2 composition 3
Example 2-12 Partition wall IR absorbing IR transmitting 4 4
material 4 composition 3 composition 4
Example 2-13 Partition wall IR absorbing IR transmitting 4
material 5 composition 1 composition 1
Example 2-14 Partition wall IR absorbing IR transmitting 4 4
material 6 composition 2 composition 3
Example 2-15 Partition wall IR absorbing IR transmitting 4 4
material 4 composition 3 composition 4
Comparative Partition wall IR absorbing IR transmitting 2 2
Example 2-1 not existed composition 2 composition 2
Comparative Comparative IR absorbing IR transmitting 2 2
Example 2-2 Partition wall composition 2 composition 2
material 1
Comparative Comparative IR absorbing IR transmitting 2 2
Example 2-3 Partition wall composition 2 composition 2
material 2
Comparative Comparative IR absorbing IR transmitting 2 2
Example 2-4 Partition wall composition 2 composition 2
material 3
Comparative Partition wall IR absorbing IR transmitting 2 2
Example 2-5 not existed composition 1 composition 1
Comparative Partition wall IR absorbing IR transmitting 2 2
Example 2-6 not existed composition 2 composition 3
Comparative Partition wall IR absorbing IR transmitting 2 2
Example 2-7 not existed composition 3 composition 4
40
Moreover, in Examples 2-1 to 2-15 , the refractive index of In addition, in each of Examples, the dimension of the
the partition wall at at least a portion of the wavelengths of opening of the partition wall on the silicon wafer was
the near - infrared light transmitted by the near -infrared trans changed to 5 um verticalx5 um horizontal, 20 um verticalx
mitting filter layer was smaller than the refractive index of 20 um horizontal, or 100 um verticalx100 um horizontal, the
the near - infrared transmitting filter layer. Further, in 45 same good recognition ability as in each of Examples was
Examples 2-6 and 2-14 in which a partition wall was formed obtained .
using the partition wall material 6 , the refractive index of the
partition wall was smaller than the refractive index of the In addition, in each of Examples, even in a case where an
near -infrared transmitting filter layer by 0.2 or more . underlying material (CT -4000L , manufactured by FUJIF
On the other hand, in Comparative Examples 2-2 , 2-3 , and 50 ILM Electronic Materials Co. , Ltd. ) was applied onto the
2-4 in which partition walls were formed using the com- silicon wafer such that the film thickness became 100 nm ,
parative partition wall materials 1 to 3 , the refractive index and heated at 220 ° C. for 5 minutes to form an underlayer,
of the partition wall with respect to the near - infrared light the same good recognition ability as in each of Examples
transmitted by the near - infrared transmitting filter layer was was obtained .
larger than the refractive index of the near - infrared trans- 55 In addition , in a case where the protective layer 1 was
mitting filter layer. formed on a surface of the partition wall formed using the
As shown in the table, the structures of Examples had partition wall material 6 , it was possible to effectively
excellent near - infrared recognition ability, and could detect suppress the components from the adjacent near - infrared
the near - infrared light with good sensitivity. In addition, the 60 transmitting filter layer or near- infrared shielding filter layer
visible light recognition ability was also excellent.
In each of Examples, even in a case where the width of the from being incorporated into the partition wall . In addition ,
partition wall was changed to 20 nm , 100 nm , or 200 nm , the in a case where the protective layer 2 was formed on a
same good recognition ability as in Examples was obtained . surface of the partition wall formed using the partition wall
In addition , in each of Examples, even in a case where the material 4 , the adhesiveness between the near - infrared trans
height of thepartition wall was changed to 0.5 um or 1.5 um , 65 mitting filter layer and the partition wall , and between the
the same good recognition ability as in Examples was near - infrared shielding filter layer and the partition wall was
obtained . particularly excellent.
 US 10,991,749 B2
91 92
Test Example 3 the following table to form a 1 -um ? near -infrared transmit
Examples 3-1 to 3-15 and Comparative Examples ting filter layer ( a thickness of 1 um ). Next , patterning was
3-2 to 3-4
performed by photolithography using an IR absorbing com
5 position to form a near - infrared shielding layer ( a thickness
A partition wall material layer was formed on a silicon of 0.5 um ) in a region partitioned by the partition wall on the
wafer using a partition wall material described in the fol- support. Next, was performed by photolithography using
lowing table , and the partition wall material layer was Red Composition 1 , Green Composition 1 , and Blue Com
patterned by a dry etching method to form partition walls ( a
width of 50 nm and a height of 1 um ) in a lattice form at an 10 position
color
1 on the near - infrared shielding layer to form a
filter layer including a red colored layer, a green
interval of 1 um . The dimension of the partition wall on the
silicon wafer was 1 um verticalx1 um horizontal. Next , colored layer, and a blue colored layer. Subsequently, a lens
patterning was performed on the silicon wafer having the was formed on the near - infrared transmitting filter layer and
partition walls formed thereon by photolithography using an the color filter layer to produce a structure .
IR transmitting composition described in the following table
to form a near -infrared transmitting filter layer (a thickness 15 ( Evaluation of Ability to Recognize Near - Infrared Light
of 1 um ) in a region partitioned by the partition wall on the and Visible Light)
silicon wafer. Next, patterning was performed by photoli Each of the structures was introduced into an optical
thography using an IR absorbing composition to form a sensor according to a known method and its ability to
near - infrared shielding layer ( a thickness of 0.5 um ) in a
region partitioned by the partition wall on the support.Next, 20 recognize near- light and visible light was evaluated . Further,
was performed by photolithography using Red Composition for the structure using the IR transmitting composition 1 , an
1 , Green Composition 1 , and Blue Composition 1 on the ability to recognize the light in a wavelength range of 720
near- infrared shielding layer to form a color filter layer nm was evaluated . In addition, for the structure using the IR
including a red colored layer, a green colored layer, and a transmitting composition 2 or 3 , an ability to recognize the
blue colored layer. Subsequently, a lens was formed on the 25 light at a wavelength of 850 nm was evaluated . Further, for
near - infrared transmitting filter layer and the color filter the structure using the IR transmitting composition 4 , an
layer to produce a structure shown in FIG . 3 . ability to recognize the light at a wavelength of 940 nm was
Comparative Examples 3-1 , and 3-5 to 3-7 evaluated . The evaluation standard for the near- infrared
recognition ability is the same as in Test Example 1. The
Patterning was performed on a silicon wafer by photoli- 30 evaluation standard for the visible light recognition ability is
thography using an IR transmitting composition described in the same as in Test Example 2 .
TABLE 6
Near Near Visible
Color filter layer infrared Near- infrared infrared light
Partition Red colored Green colored Blue colored shielding transmitting recognition recognition
wall material layer layer layer filter layer filter layer ability ability
Example 3-1 Partition wall Red Green Blue IR absorbing IR transmitting 3 3
material 1 composition 1 composition 1 composition 1 composition 2 composition 2
Example 3-2 Partition wall Red Green Blue IR absorbing IR transmitting 4 4
material 2 composition 1 composition 1 composition 1 composition 2 composition 2
Example 3-3 Partition wall Red Green Blue IR absorbing IR transmitting 4
material 3 composition 1 composition 1 composition 1 composition 2 composition 2
Example 3-4 Partition wall Red Green Blue IR absorbing IR transmitting 4 4
material 4 composition 1 composition 1 composition 1 composition 2 composition 2
Example 3-5 Partition wall Red Green Blue IR absorbing IR transmitting 4 4
material 5 composition 1 composition 1 composition 1 composition 2 composition 2
Example 3-6 Partition wall Red Green Blue IR absorbing IR transmitting 4 4
material 6 composition 1 composition 1
composition 1 composition 2 composition 2
Example 3-7 Partition wall Red Green Blue IR absorbing IR transmitting 3 4
material 1 composition 1 composition 1 composition 1 composition 1 composition 1
Example 3-8 Partition wall Red Green Blue IR absorbing IR transmitting 3 4
material 1 composition 1 composition 1 composition 1 composition 2 composition 3
Example 3-9 Partition wall Red Green Blue IR absorbing IR transmitting 3 4.
material 1 composition 1 composition 1 composition 1 composition 3 composition 4
Example 3-10 Partition wall Red Green Blue IR absorbing IR transmitting 4 4
material 2 composition 1 composition 1 composition 1 composition 1 composition 1
Example 3-11 Partition wall Red Green Blue IR absorbing IR transmitting 4 4
material 3 composition 1 composition 1 composition 1 composition 2 composition 3
Example 3-12 Partition wall Red Green Blue IR absorbing IR transmitting 4 4
material 4 composition 1 composition 1 composition 1 composition 3 composition 4
Example 3-13 Partition wall Red Green Blue IR absorbing IR transmitting 4 4
material 5 composition 1 composition 1 composition 1 composition 1 composition 1
Example 3-14 Partition wall Red Green Blue IR absorbing IR transmitting 4 4
material 6 composition 1 composition 1 composition 1 composition 2 composition 3
Example 3-15 Partition wall Red Green Blue IR absorbing IR transmitting 4 4
material 4 composition 1 composition 1 composition 1 composition 3 composition 4
Comparative Partition wall Red Green Blue IR absorbing IR transmitting 2 2
Example 3-1 not existed composition 1 composition 1 composition 1 composition 2 composition 2
 US 10,991,749 B2
93 94
TABLE 6 - continued
Near Near Visible
Color filter layer infrared Near -infrared infrared light
Partition Red colored Green colored Blue colored shielding transmitting recognition recognition
wall material layer layer layer filter layer filter layer ability ability
Comparative Comparative Red Green Blue IR absorbing IR transmitting 2 2
Example 3-2 Partition wall composition 1 composition 1 composition 1 composition 2 composition 2
material 1
Comparative Comparative Red Green Blue IR absorbing IR transmitting 2 2
Example 3-3 Partition wall composition 1 composition 1 composition 1 composition 2 composition 2
material 2
Comparative Comparative Red Green Blue IR absorbing IR transmitting 2 2
Example 3-4 Partition wall composition 1 composition 1 composition 1 composition 2 composition 2
material 3
Comparative Partition wall Red Green Blue IR absorbing IR transmitting 2 2
Example 3-5 not existed composition 1 composition 1 composition 1 composition 1 composition 1
Comparative Partition wall Red Green Blue IR absorbing IR transmitting 2 2
Example 3-6 not existed composition 1 composition 1 composition 1 composition 2 composition 3
Comparative Partition wall Red Green Blue IR absorbing IR transmitting 2 2
Example 3-7 not existed composition 1 composition 1 composition 1 composition 3 composition 4

Moreover, in Examples 3-1 to 3-15 , the refractive index of transmitting composition 1 , the same good recognition abil
the partition wall at at least a portion of the wavelengths of ity as in Example 3-7 was obtained .
the near - infrared light transmitted by the near - infrared trans- In addition , in a case where the protective layer 1 was
mitting filter layer was smaller than the refractive index of 25 formed on a surface of the partition wall formed using the
the near - infrared transmitting filter layer. Further, in partition wall material 6 , it was possible to effectively
Examples 3-6 and 3-14 in which a partition wall was formed suppress the components from the near - infrared transmitting
using the partition wall material 6 , the refractive index of the filter layer or each of the colored layers from being incor
partition wall was smaller than the refractive index of the porated into the partition wall . In addition , in a case where
near - infrared transmitting filter layer by 0.2 or more . 30 the protective layer 2 was formed on a surface of the
On the other hand, in Comparative Examples 3-2 , 3-3 , and partition wall formed using the partition wall material 4 , the
3-4 in which partition walls were formed using the com- adhesiveness between the near - infrared transmitting filter
parative partition wall materials 1 to 3 , the refractive index layer and the partition wall , and the adhesiveness between of
of the partition wall with respect to the near -infrared light the colored layers and the partition wall were particularly
transmitted by the near - infrared transmitting filter layer was 35 excellent.
larger than the refractive index of the near - infrared trans- In Test Examples 1 to 3 , even with substitution of the
mitting filter layer. near - infrared absorbing dye in the IR transmitting compo
As shown in the table, the structures of Examples had sition 4 , and the IR absorbing compositions 1 to 3 with the
excellent near - infrared recognition ability, and could detect near - infrared absorbing dye described in the present speci
the near - infrared light with good sensitivity . In addition , the 40 fication , the same effect was obtained .
visible light recognition ability was also excellent.
In each of Examples, even in a case where the width of the Test Example 4
partition wall was changed to 20 nm , 100 nm , or 200 nm , the
same good recognition ability as in Examples was obtained . The structures described in FIGS . 5 , 6 , and 8 to 18 were
In addition , in each of Examples, even in a case where the 45 produced by the same methods in Test Examples 1 to 3. The
height of the partition wall was changed to 0.5 um or 1.5 um , structure produced in such a manner was introduced into an
the same good recognition ability as in Examples was optical sensor according to a known method and its ability
obtained . to recognize near - infrared light and visible light was evalu
In addition , in each of Examples, the dimension of the ated . These structures had an excellent near- infrared recog
opening of the partition wall on the silicon wafer was 50 nition ability and could detect the near - infrared light with
changed to 5 um verticalx5 um horizontal, 20 um verticalx good sensitivity. In addition, the visible light recognition
20 um horizontal, or 100 um verticalx100 um horizontal, the ability was also excellent.
same good recognition ability as in each of Examples was In the structures described in FIGS . 5 , 6 , and 8 to 18 , the
obtained . partition walls 2 , 2a , and 2b were formed using the partition
In addition , in each of Examples, even in a case where an 55 wall materials 1 to 6. The black matrix 5 was formed using
underlying material ( CT- 4000L , manufactured by FUJIF- tungsten. The colored layer 31 was formed by photolithog
ILM Electronic Materials Co. , Ltd. ) was applied onto the raphy or a dry etching method using Red Composition 1 .
silicon wafer such that the film thickness became 100 nm , The colored layer 32 was formed by photolithography or a
and heated at 220 ° C. for 5 minutes to form an underlayer, dry etching method using Green Composition 1. The colored
the same good recognition ability as in each of Examples 60 layer 33 was formed by photolithography or a dry etching
was obtained . method using Blue Composition 1. The near -infrared shield
Furthermore, in Example 3-7 , in a case where a near- ing filter layers 22 and 23 were formed by photolithography
infrared transmitting filter layer including a laminate of a red or a dry etching method using the IR absorbing composition
colored layer (a thickness of 0.5 um ) formed using Red 2. The near - infrared transmitting filter layer 11 was formed
Composition 1 and a blue colored layer (a thickness of 0.5 65 by photolithography or a dry etching method using the IR
um ) Ruined using Blue Composition 1 was used instead of transmitting composition 2. The transparent layers 41 and 42
a near - infrared transmitting filter layer formed using the IR were formed by photolithography or a dry etching method
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95 96
using the composition 1 for forming a transparent layer. In In the structure shown in FIG . 17 , the partition wall 2 had
the structures, the pixel size of the near - infrared transmitting a width of 50 nm and a height of 1 um . The near - infrared
filter layer 11 was 1 um ?. Further, the pixel size of the transmitting filter layer 11 had a thickness of 0.5 um . The
colored layers 31 to 33 was 1 um ?. In addition, the pixel size colored layers 31 to 33 each had a thickness of 0.5 um . The
of the transparent layer 42 was 1 um ?. 5 near - infrared shielding layer 22 had a thickness of 0.5 um .
In the structure shown in FIG . 5 , the partition wall 2 had TheIn transparent
the
layer 41 had a thickness of 0.5 um .
structure shown in FIG . 18 , the partition wall 2 had
a width of 50 nm and a height of 1 um . The near - infrared
transmitting filter layer 11 had a thickness of 1 um . The a width of 50 nm and a height of 1 um . The near - infrared
colored layers 31 to 33 each had a thickness of 0.5 um . The transmitting filter layer 11 had a thickness of 1 um . The
near - infrared shielding layer 22 had a thickness of 0.5 um . 10 near
colored layers 31 to 33 each had a thickness of 0.5 um . The
-infrared shielding layer 22 had a thickness of 0.5 um .
In the structure shown in FIG . 6 , the partition wall 2 had
a width of 50 nm and a height of 1 um . The near - infrared EXPLANATION OF REFERENCES
transmitting filter layer 11 had a thickness of 1 um . The
colored layers 31 to 33 each had a thickness of 1 um . 15 1 : support
In the structure shown in FIG . 8 , the partition wall 2 had 2 , 2a , 2b : partition walls
a width of 50 nm and a height of 1 um , and the partition wall 4 : underlayer
2a had a width of 50 nm and a height of 0.5 um . The 3 : protective layer
near - infrared transmitting filter layer 11 had a thickness of 1 5 : black matrix
um . The colored layers 31 to 33 each had a thickness of 0.5 20 11 : near - infrared transmitting filter layer
um . The near - infrared shielding layer 22 had a thickness of 21 , 22 , 23 : near - infrared shielding filter layers
0.5 um . 30 : color filter layer
In the structure shown in FIG . 9 , the partition wall 2 had 31 , 32 , 33 : colored layers
a width of 50 nm and a height of 1 um , and the partition wall 41 , 42 : transparent layers
2b had a width of 50 nm and a height of 0.5 um . The 25 50 : lens
near - infrared transmitting filter layer 11 had a thickness of 1 101 to 118 : structures
um . The colored layers 31 to 33 each had a thickness of 0.5 What is claimed is :
um . The near- infrared shielding layer 22 had a thickness of 1. A structure comprising:
0.5 um . a support;
In the structure shown in FIG . 10 , the partition wall 2 had 30 a partition wall provided on the support; and
a width of 50 nm and a height of 1 um . The near - infrared a near - infrared transmitting filter layer provided in a
transmitting filter layer 11 had a thickness of 1 um . The region partitioned by the partition wall , that shields
colored layers 31 to 33 each had a thickness of 0.5 um . The visible light and transmits at least a portion of near
near - infrared shielding layer 22 had a thickness of 0.5 um . infrared light,
In the structure shown in FIG . 11 , the partition wall 2 had 35 wherein the refractive index of the partition wall is
a width of 50 nm and a height of 1 um . The near - infrared smaller than the refractive index of the near - infrared
transmitting filter layer 11 had a thickness of 1 um . The transmitting filter layer structure at at least a portion of
colored layers 31 to 33 each had a thickness of 1 um . The the wavelengths of the near -infrared light transmitted
near - infrared shielding layer 22 had a thickness of 0.5 um . by the near- infrared transmitting filter layer, and
In the structure shown in FIG . 12 , the partition wall 2 had 40 wherein the partition wall includes at least one selected
a width of 50 nm and a height of 1 um . The near - infrared from silica particles, a siloxane resin, a fluorine resin ,
transmitting filter layer 11 had a thickness of 1 um . The or silicon dioxide .
colored layers 31 to 33 each had a thickness of 0.5 um . The 2. The structure according to claim 1 ,
near - infrared shielding layer 22 had a thickness of 0.2 um . wherein the refractive index of the partition wall is
In the structure shown in FIG . 13 , the partition wall 2 had 45 smaller than the refractive index of the near - infrared
a width of 50 nm and a height of 1 um . The near - infrared transmitting filter layer by 0.2 or more at at least a
transmitting filter layer 11 had a thickness of 1 um . The portion of the wavelengths of the near -infrared light
colored layers 31 to 33 each had a thickness of 0.5 um . The transmitted by the near -infrared transmitting filter
near - infrared shielding layer 22 had a thickness of 0.2 um . layer.
The transparent layer 41 had a thickness of 0.3 um . 50 3. The structure according to claim 1 ,
In the structure shown in FIG . 14 , the partition wall 2 had wherein the refractive index of the partition wall is
a width of 50 nm and a height of 1 um . The near - infrared smaller than the refractive index of the near - infrared
transmitting filter layer 11 had a thickness of 1 um . The transmitting filter layer at an entire wavelength in a
colored layers 31 to 33 each had a thickness of 0.5 um . The wavelength range of 700 to 1,000 nm .
near - infrared shielding layers 22 and 23 each had a thickness 55 4. The structure according to claim 1 ,
of 0.5 um . The transparent layer 42 had a thickness of 0.5 wherein a maximum value of the refractive index with
um . respect to light in a wavelength range of 700 to 1,000
In the structure shown in FIG . 15 , the partition wall 2 had nm of the partition wall is 1.4 or less .
a width of 50 nm and a height of 1 um . The near - infrared 5. The structure according to claim 1 ,
transmitting filter layer 11 had a thickness of 1.5 um . The 60 wherein a maximum value of the refractive index with
colored layers 31 to 33 each had a thickness of 0.5 um . The respect to light in a wavelength range of 400 to 1,000
near - infrared shielding layer 22 had a thickness of 0.5 um . nm of the partition wall is 1.4 or less .
In the structure shown in FIG . 16 , the partition wall 2 had 6. The structure according to claim 1 , further comprising
a width of 50 nm and a height of 1 um . The near - infrared a protective layer on a surface of the partition wall .
transmitting filter layer 11 had a thickness of 0.5 um . The 65 7. The structure according to claim 1 ,
colored layers 31 to 33 each had a thickness of 0.5 um . The wherein the structure has a plurality of regions partitioned
near - infrared shielding layer 22 had a thickness of 0.5 um . by partition walls on the support, a near - infrared trans
 US 10,991,749 B2
97 98
mitting filter layer is provided in at least one region of transmitting filter layer at an entire wavelength in a
the regions partitioned by the partition walls , and at wavelength range of 700 to 1,000 nm .
least one layer selected from a color filter layer or a 14. The structure according to claim 11 ,
near -infrared shielding filter layer is provided in at least wherein a maximum value of the refractive index with
one region of the remaining regions partitioned by the 5 respect to light in a wavelength range of 700 to 1,000
partition walls . nm of the partition wall is 1.4 or less .
8. The structure according to claim 1 , 15. The structure according to claim 11 ,
wherein a content of the color material included in the wherein a maximum value of the refractive index with
near -infrared transmitting filter layer is 50% to 75 % by respect to light in a wavelength range of 400 to 1,000
mass . 10
9. A composition for forming a near -infrared transmitting nm of the partition wall is 1.4 or less .
filter layer, comprising: 16. The structure according to claim 11 ,
a color material; and wherein the structure has a plurality of regions partitioned
a curable compound , by partition walls on the support, a near - infrared trans
wherein the composition is used for the formation of the 15 mitting filter layer is provided in at least one region of
near- infrared transmitting filter layer in the structure the regions partitioned by the partition walls , and at
according to claim 1 . least one layer selected from a color filter layer or a
10. An optical sensor comprising the structure according near - infrared shielding filter layer is provided in at least
to claim 1 . one region of the remaining regions partitioned by the
11. A structure comprising: 20 partition walls .
a support; 17. The structure according to claim 11 ,
a partition wall provided on the support; wherein a content of the color material included in the
a protective layer on a surface of the partition wall ; and near - infrared transmitting filter layer is 50% to 75 % by
a near- infrared transmitting filter layer provided in a mass .
region partitioned by the partition wall , that shields 25 ting18.filter
A composition for forming a near - infrared transmit
layer, comprising:
visible light and transmits at least a portion of near a color material; and
infrared light, a curable compound,
wherein the refractive index of the partition wall is wherein the composition is used for the formation of the
smaller than the refractive index of the near - infrared
transmitting filter layer structure at at least a portion of 30 near- infrared transmitting filter layer in the structure
the wavelengths of the near - infrared light transmitted according to claim 11 .
by the near - infrared transmitting filter layer. 19. An optical sensor comprising the structure according
to claim 11 .
12. The structure according to claim 11 , 20. The structure according to claim 11 ,
wherein the refractive index of the partition wall is
smaller than the refractive index of the near - infrared 35 wherein the protective layer is formed using a composi
transmitting filter layer by 0.2 or more at at least a tion including a compound having a group having an
portion of the wavelengths of the near - infrared light ethylenically unsaturated bond or is constituted from
transmitted by the near - infrared transmitting filter inorganic materials .
layer. 21. The structure according to claim 11 ,
13. The structure according to claim 11 , 40 wherein the protective layer is constituted from a silicon
wherein the refractive index of the partition wall is dioxide and the partition wall includes silica particles.
smaller than the refractive index of the near- infrared