USOO9388532B2

(12) United States Patent (10) Patent No.: US 9,388,532 B2

Koyama et al. (45) Date of Patent: Jul. 12, 2016
(54) WATER-DISPERSIBLE PAPER (58) Field of Classification Search
CPC .......... B41M5/41; B41M 5/508; B41M 5/50:
(71) Applicant: NIPPON PAPER PAPYLIACO. Y10T 428/24934; Y1OT 428/31993
LTD., Fuji-shi, Shizuoka (JP) USPC .................. 428/32.21, 211.1, 537.5; 503/200
See application file for complete search history.
(72) Inventors: Munenaka Koyama, Fuji (JP); Masaki
Kishimoto, Fuji (JP); Yoshiaki Ishino, (56) References Cited
Fuji (JP)
U.S. PATENT DOCUMENTS
(73) Assignee: NIPPON PAPER PAPYLIACO.
LTD., Fuji-Shi (JP) 2006/0216537 A1
2008.OO71078 A1
9, 2006 Natsui et al.
3/2008 Kizer et al.
(*) Notice: Subject to any disclaimer, the term of this FOREIGN PATENT DOCUMENTS
patent is extended or adjusted under 35
U.S.C. 154(b) by 0 days. GB 1125956 A 9, 1968
JP S43-001 214 B 1, 1968
(21) Appl. No.: 14/451,016 JP HO3-008897. A 1, 1991
JP HO6-184984 A T 1994
(22) Filed: Aug. 4, 2014 JP H1O-310960 A 11, 1998
JP 2000-1701.00 A 6, 2000
(65) Prior Publication Data JP 2004-314623 A 11, 2004
JP 2006-299.498 A 11, 2006
US 2014/0338851A1 Nov. 20, 2014 JP 2009-052152. A 3, 2009
JP 2010-504376 A 2, 2010
Related U.S. Application Data OTHER PUBLICATIONS
(63) Continuation of application No. 13/812.824, filed as International Search Report (ISR) mailed Nov. 1, 2011, issued for
application No. PCT/JP2011/067237 on Jul. 28, 2011, corresponding International application No. PCT/JP2011/067237.
now Pat. No. 8,877,678. Notification of Transmittal of Translation of the International Pre
(30) Foreign Application Priority Data liminary Reporton Patentability (PCT/IB/338) mailed Feb. 14, 2013,
with International Preliminary Reporton Patentability (PCT/IB/373)
Jul. 28, 2010 (JP) ................................. 2010-169561 and Written Opinion of the International Searching Authority (PCT/
ISA/237), for corresponding international application PCT/JP2011/
O67237.
(51) Int. Cl. Non-final Office action issued by the USPTO, dated May 5, 2014, for
B4LM 5/24 (2006.01)
B4LM 5/50 (2006.01) U.S. Appl. No. 13/812,824.
D2 IIH I3/02 (2006.01)
D2 IIH II/20 (2006.01) Primary Examiner — Bruce H Hess
D2 IIH II/00 (2006.01) (74) Attorney, Agent, or Firm — Law Office of Katsuhiro
G09F 3/00 (2006.01) Arai
D2 IIH (9/12 (2006.01)
D2 IH (9/36 (2006.01) (57) ABSTRACT
(52) U.S. Cl. A water dispersion paper made of wood pulp and/or non
CPC ................. D2IH 13/02 (2013.01); B4IM 5/41 wood pulp is characterized in that purified pulp containing
(2013.01): B4 IM5/508 (2013.01); D21H II/00 C.-cellulose by 88 percent by weight or more accounts for 15
(2013.01); D21H II/20 (2013.01); D2IH 19/12 to 95 percent by weight of all pulp. The water dispersion
(2013.01); G09F3/0291 (2013.01); D21H paper has quick water dispersion property and high strength
19/36 (2013.01); Y10T 428/24802 (2015.01); (printability) and its paper Surface pH is 6 to 8 (neutral range).
Y10T 428/24934 (2015.01); Y10T 428/2848
(2015.01); Y10T 428/31993 (2015.04) 14 Claims, No Drawings
 US 9,388,532 B2
1. 2
WATER-DSPERSIBLE PAPER material containing water-insoluble fiber carboxy alkyl cel
lulose and alkalization agent, with a coating layer provided on
CROSS-REFERENCE TO RELATED top (Patent Literature 7).
APPLICATIONS
RELATED ART REFERENCES
This application is a continuation of U.S. patent applica
tion Ser. No. 13/812,824, filed Apr. 8, 2013 (S371(c)(1), (2), Patent Literature 1: Examined Japanese Patent Laid-openNo.
(4) Date), which is the U.S. National Phase under 35 U.S.C. Sho 43-001 214
S371 of International Application PCT/JP2011/067237, filed Patent Literature 2: Japanese Patent Laid-open No. Hei
10 O3-008897
Jul. 28, 2011, which claims priority to Japanese Patent Appli
cation No. 2010-169561, filed Jul. 28, 2010, each disclosure Patent Literature 3: Japanese Patent Laid-open No. 2009
of which is herein incorporated by reference in its entirety. 0521.52
The International Application was published under PCT Patent Literature 4: Japanese Patent Laid-open No. Hei
Article 21(2) in the language other than English. O6-184984
15
The applicant herein explicitly rescinds and retracts any Patent Literature 5: Japanese Patent Laid-open No. 2000
prior disclaimers or disavowals made in any parent, child or 1701OO
related prosecution history with regard to any Subject matter Patent Literature 6: Japanese Patent Laid-open No. 2004
Supported by the present application. 314623
Patent Literature 7: Japanese Patent Laid-open No. 2006
BACKGROUND OF THE INVENTION 299498
Patent Literature 8: Published Japanese Translation of PCT
1. Field of the Invention International Patent Application No. 2010-504376
The present invention refers to a paper that disperses
quickly in water. This type of paper is called “water disper 25 SUMMARY OF THE INVENTION
sion paper' or “water-dispersible paper.”
Water dispersion papers are sometimes used for confiden However, a water dispersion paper made by mixing paper
tial documents because they can be dispersed in water for making fibers and fiber carboxymethyl cellulose and then
disposal. Products that take advantage of the water absorb adding an alkali metal compound, or one made by mixing a
ability and property to disperse/disintegrate in water of these 30 water-insoluble or low-water-soluble inorganic powder into
papers include flushable toilet papers and toilet cleaning papermaking fibers or carboxymethyl cellulose, is alkaline
papers. For their water absorbability, water dispersion papers and the water in which the paper is dispersed also exhibits
are also utilized for semination sheets and other agricultural alkalinity. Accordingly, use of Such paper may be limited in
materials, as well as sanitary materials and medical materials. applications involving plant or animal, medical applications,
2. Description of the Related Art
35 applications where the paper comes in contact with food, etc.,
Water dispersion papers proposed so far include one made or film lamination applications.
by mixing papermaking fibers and fiber carboxymethyl cel For example, when the germination ratio and growth rate of
germination roots of radish six days after the sawing date
lulose and then adding an alkali metal compound (Patent were studied using a semination sheet using a water disper
Literature 1), and one made by mixing a water-insoluble or 40 sion paper made by mixing papermaking fibers and fiber
low-water-soluble inorganic powder into papermaking fibers carboxymethyl cellulose and then adding an alkali metal
or carboxymethyl cellulose (Patent Literature 2). In addition compound (water-soluble paper 60MDP by Nippon Paper
to the above, a water dispersion paper made by coating a Papylia with a paper surface pH of 8.8) and another using a
water-soluble binder onto a Support made by mixing paper non-water-dispersible filter paper with a paper surface pH of
making fibers and regenerated cellulose fibers (Patent Litera 45 7.0 (made by Toyo Roshi), the germination ratio was 97%
ture 3) is also proposed, among others. Other water dispersion with the filter paper and 85% with 60MDP, while the root
papers being proposed include one made by blending an length and stem length were 41.0 mm and 46.2 mm with the
alkali metal salt or alkali earth metal salt of carboxymethyl filter paper, respectively, and 15.9 mm and 39.9 mm with
cellulose into papermaking fibers (Patent Literature 4) and 60MDP, respectively. If a water dispersion paper is laminated
one made by coating a water-soluble polymer onto a base 50 with a water-soluble resin film, the ester group contained in
paper made by blending hydrophobic low-molecular com the water-soluble resin film or water-soluble adhesive used to
pound into papermaking water-dispersible fibers (Patent Lit laminate the water-soluble resin film and water dispersion
erature 5), and the like. paper will react with the alkaline water dispersion paper and
Reflecting a growing interest in environmental issues of may cause the water solubility of the water-soluble resin film
late, returnable containers are drawing the attention. Return
55 to drop or cause adhesive failure.
able containers generally bear an adhesive label made of a A water dispersion paper made by adding an aqueous solu
press-printed or printer-printed coated paper having an adhe tion of water-soluble binder to a sheet obtained by mixing
papermaking fibers and rayon or other regenerated cellulose
sive layer provided on the back side. However, separating this fibers presents such problems as difficulty achieving suffi
label from the container after use requires a cumbersome 60 cient strength and the quality of the water dispersion paper not
cleaning process. becoming uniform, because the regenerated cellulose does
To ease Such trouble of cleaning, an adhesive sheet that not easily bond strongly with the papermaking fibers via the
disintegrates in water is disclosed, which is made of a water water-soluble binder. This water dispersion paper also pre
soluble or water-dispersible base material having a coating sents problems in screen printing, gravure printing, flexo
layer appropriate for each of various recording methods pro 65 printing, Sublimation printing, thermal transfer printing, etc.,
vided on top (Patent Literature 6). A coated paper that sepa as the regenerated cellulose fibers produce lint or detach to
rates in water is also disclosed, which is made of a base generate paper powder, resulting in unfavorable printability.
 US 9,388,532 B2
3 4
A water dispersion paper made by blending an alkali metal The primary constitutions of the present invention are as
salt or alkali earth metal salt of carboxymethyl cellulose into follows:
papermaking fibers provides a neutral paper, but it is difficult 1 A water dispersion paper made of wood pulp and/or
to provide a water dispersion paper which needs to have quick non-wood pulp, wherein said paper is characterized in that
water dispersion property because, as carboxymethyl cellu purified pulp containing C-cellulose by 88 percent by weight
lose is added to water in the form of water-soluble salt during or more accounts for 15 to 95 percent by weight of all pulp.
the course of papermaking, a film of carboxymethyl cellulose 2 A water dispersion paper made of wood pulp and/or
salt is formed after drying and the rate of water dispersion non-wood pulp, wherein said paper is characterized in that
slows. Also, a water dispersion paper made by coating a purified pulp containing hemi-cellulose by less than 12 per
water-soluble polymer onto a base paper made by blending 10 cent by weight accounts for 15 to 95 percent by weight of all
hydrophobic low-molecular compound into papermaking pulp.
water-dispersible fibers is such that, because water dispersion 3A water dispersion paper according to 1 or 2, char
property is enhanced by the inter-fiber bonding-strength acterized in that it does not contain regenerated cellulose
reducing effect of the hydrophobic low-molecular com fiber, fiber carboxymethyl cellulose or fiber carboxymethyl
15 cellulose Nasalt.
pound, increasing the additive amount of the hydrophobic 4A water dispersion paper according to 1 or 2, char
low-molecular compound with the intention of achieving acterized in that its paper surface pH is 6 to 8.
quick water dispersion property causes the hydrophilicity of 5A water dispersion paper according to 1 or 2, char
base paper Surface and strength of base paper to drop by an acterized in that its floc water dispersion time, measured by
extreme degree and these lowered hydrophilicity and strength putting a test piece of 3x3 cm square in water in a beaker and
of base paper cannot easily be recovered by coating the water then agitating the water with a stirrer at 650 rpm until the test
soluble polymer. Thus it is difficult to provide a water disper piece tears into two or more pieces, is within 30 seconds.
sion paper which needs to have quick water dispersion prop 6A water dispersion coated paper, consisting of a base
erty. material being a water dispersion paper according to 1 or
Furthermore, the thermo-sensitive recording sheet that dis 25 2, with a coating layer primarily constituted by water-based
integrates in water, as described in Patent Literature 6, can be coating material provided on top.
used for a label that easily separates from the returnable 7A water dispersion coated paper according to 6, char
container, because the sheet consists of a base material made acterized in that its coating layer is a thermo-sensitive record
of water-soluble paperor water dispersion paper, with a sealer ing layer, inkjet recording layer or general printing layer.
layer constituted by non-water-soluble resin and a coating 30 8A water dispersion coated paper according to 6, char
layer (thermo-sensitive recording layer) provided on top, but acterized in that a water-soluble sealer layer is provided
this application present problems, one of which is that the between the base material and coating layer and/or on the
sealer layer of non-water-soluble resin separates like a film uncoated side of the base material.
and clogs the wastewater pipe. The coated paper that sepa 9A water dispersion coated paper according to 6, char
rates in water as described in Patent Literature 7 expresses 35 acterized in that a water-soluble or water-redispersible pres
good separation performance in water as the non-water Sure-sensitive adhesive is used to provide a pressure-sensitive
soluble carboxy alkyl cellulose fibers contained in the base adhesive layer on another side of the base material opposite to
material turn into a metal salt of water-soluble carboxyalkyl one side on which the coating layer is formed.
cellulose fibers due to the alkalization agent. However, it is 10 A water dispersion coated paper according to 6.
difficult to add just the right amount of alkalization agent 40 characterized in that it is a printing paper for confidential
needed to neutralize the carboxyalkyl cellulose, which makes document.
it necessary to add an excessive amount of alkalization agent 11 A water dispersion coated paper according to 9.
to achieve complete neutralization. As a result, the coated characterized in that it is a label displaying information of
paper that separates in water according to Patent Literature 7 food material, etc., on the coating layer.
changes color over time due to excessive alkalization agent. 45
In light of the above, an object of the present invention is to Effects of the Invention
provide a water dispersion paper having quick water disper
sion property and high strength (printability) as well as paper The present invention realizes a paper offering excellent
Surface pH of 6 to 8 (neutral range), and also to achieve a water dispersion property by using specific purified pulp con
water dispersion coated paper ensuring quick water disper 50 taining C-cellulose by 88 percent by weight or more to
sion property and prevention of discoloration over time. account for 15 to 95 percent by weight of all pulp. According
The present invention was completed following the discov to the present invention, a water dispersion paper with a paper
ery that a water dispersion paper made of wood pulp and/or Surface pH of 6 to 8, having quick water dispersion property
non-wood pulp, where 15 to 95 percent by weight of the pulp and high strength (printability), can be obtained. Also accord
represents purified pulp containing C-cellulose by 88 percent 55 ing to the present invention, a coated paper that disperses
by weight or more, would exhibit quick water dispersion water, ensuring quick water dispersion property and preven
property even when the paper Surface pH is adjusted to a tion of discoloration over time, can be obtained.
range of 6 to 8. The present invention was also completed A water dispersion paper according to the present inven
following the discovery that a water-dispersible coated paper tion consists of two or more types of wood pulp and/or non
constituted by a base material made of wood pulp and/or 60 wood pulp of different degrees of refining blended together,
non-wood pulp and at least one water-based coating layer where regenerated cellulose fibers and other fibers whose
provided on top, where 15 to 95 percent by weight of the pulp inter-fiber bonding is excessively weak are not used, and
constituting the base material represents purified pulp con therefore the paper offers high tensile strength and surface
taining C-cellulose by 88 percent by weight or more and no strength while having quick water dispersion property, pro
alkalization agent is needed as a result, would ensure quick 65 duces less paper breakage and lint when used in offset print
water dispersion property and prevention of discoloration ing and other printing applications, and exhibits excellent
over time. printability.
 US 9,388,532 B2
5 6
A water dispersion paper according to the present inven A water-dispersible paper according to the present inven
tion does not use fiber carboxymethyl cellulose, which elimi tion, and coated paper using said water-dispersible paper, are
nates the need for alkalization agent to neutralize the carboxyl suitable for applications where the paper is put in water to be
group and therefore prevents excessive alkalization agent disintegrated into fine pieces. For example, they can be used
from remaining in the paper and causing the paper to exhibit as use-by date labels on food trays used at restaurants, etc.,
alkalinity. As a result, the paper does not yellow (change to recycled container labels, returnable container marking
yellow) over time and its storage stability improves. Further sheets, and so on, where the label/sheet is put in water
more, various coated papers made by coating a thermo-sen together with the container ortray and as the water is agitated
sitive recording layer, inkjet recording layer or general print and container/tray cleaned, the water dispersion paper sepa
ing layer on the water dispersion paper being the base 10 rates and disintegrates into Small pieces and is discharged
material, and processed papers made by laminating the water with wastewater. If the paper is used for semination sheets or
dispersion paper with a water-soluble resin film, can be pro labels for food packing materials, alkalinity does not present
cessed just like any general neutral paper, without causing the harmful effects. Semination sheets can be implemented
directly in crop fields and nursery fields and improve the
quality of the coating layer or water-soluble resin film to drop, 15 efficiency of semination process and germination ratio due to
because the base material is neutral. their water absorbability and disintegration property. If the
A water dispersion paper according to the present inven paper is used for food packing material labels, there is no
tion has a water-soluble sealer layer between the base mate concern that alkaline content will remain on the label-at
rial and coating layer and/or on the uncoated side of the base tached tray after cleaning and the efficiency of cleaning pro
material, and this prevents excessive permeation of coating cess improves.
Solution into the base material when the coating layer is Other applications of a water-dispersible paper according
formed, thereby allowing for formation of uniform coating to the present invention and a coated paper using said water
layer. If a pressure-sensitive adhesive layer is provided on the dispersible paper, include printing papers for confidential
uncoated side of the base material, the sealer layer prevents information. For example, ATM transaction statements at
migration of the pressure-sensitive adhesive agent into the 25 banks and other financial institutions, insurance drug dis
paper or coating layer, which in turn prevents drop in pres pensing statements and other documents bearing personal
sure-sensitive adhesive force over time or desensitization of information, and confidential paper documents used by com
the thermo-sensitive recording layer due to the pressure-sen panies, are often shredded. In the U.S. and other countries,
sitive adhesive component. however, many crimes are reported where these shreds are
A water dispersion paper and water dispersion coated 30 reconstituted and the restored confidential information is
paper according to the present invention are Suitable for use used for ill purposes. A water-dispersible paper according to
by date labels on food trays, marking sheets for returnable the present invention and a coated paper using said water
containers and other media that attach variable information to dispersible paper can be easily printed with confidential
a container and are washed away when the container is information using a thermo-sensitive printer, inkjet printer,
cleaned after use, as well as for printing papers for confiden 35 printing, etc., but once the paper is dispersed in water after
tial information that can be dispersed in water for disposal. use, the confidential information can be eliminated com
pletely with ease.
DETAILED DESCRIPTION OF EMBODIMENTS <Purified Pulp>
Purified pulp used by the present invention is, for example,
The present invention is a water-dispersible paper made 40 mercerized pulp or dissolving pulp made of wood from
primarily of pulp and offering excellent dispersion property needle-leaved trees, broad-leaved trees, etc., or non-wood
in water. The present invention is a paper offering excellent Such as hemp and linter, where the cooking conditions for
water dispersion property, made by blending purified pulp manufacturing of pulp are reinforced and hemi-cellulose,
containing C-cellulose by 88 percent by weight or more to etc., are removed by a chemical process before or after cook
account for 15 to 95 percent by weight of all pulp, and pulp 45 ing to increase the purity of cellulose, or specifically pulp that
other than purified pulp accounting for the rest. The present has been purified to an O-cellulose content of 88 percent by
invention also provides a water-dispersible coated paper con weight or more.
sisting of this water-dispersible paper as the base material, As for the relationship between the C-cellulose content and
and a coating layer provided on it, to exhibit improved print hemi-cellulose content of pulp, Published Japanese Transla
ing characteristics as well as water dispersion property. 50 tion of PCT International Patent Application No. 2010
The water-dispersible paper provided by the present inven 504376 (Patent Literature 8) classifies various types of pulp
tion exhibits dispersion property in water, whereby it dis into three grades according to the degree of refining, or
perses finely within 30 seconds and disintegrate into fibers namely "acetate grade' representing highly purified pulp.
within 80 seconds. The water-dispersible paper proposed by “viscose grade' representing purified pulp, and “paper/fluff
the present invention has high paper strength and printability, 55 grade' representing unpurified pulp, and indicates the con
So it permits clean printing on a coating layer formed on it. tents for each grade. "Acetate grade pulp normally contains
Since the paper is neutral, it has high resistance to yellowing C.-cellulose by 95 percent by weight or more and hemi-cellu
and other discoloration. lose by approx. 1 to 3 percent, while “viscose grade” pulp
Under the present invention, it is important to blend puri contains C-cellulose by 88 to 95 percent by weight and hemi
fied pulp and unpurified pulp, and use of either one of them 60 cellulose by approx. 5 to 12 percent. “Paper/fluff grade” pulp
alone cannot ensure Sufficient quality. It is also inappropriate contains C-cellulose by 80 to 88 percent by weight and hemi
to use cellulose fibers of high C.-cellulose content that have cellulose by approx. 12 to 20 percent.
been purified through a process of obtaining regenerated cel Based on the above, hemi-cellulose contained in purified
lulose (such as short rayon fibers), because it causes the paper pulp used by the present invention is less than 12 percent by
strength to drop and presents other problems. Under the 65 weight.
present invention, a preferred mode is to use pulp fibers It should be noted that, under the present invention, pulp is
maintaining a natural pulp fiber form. defined as 'Aggregate of cellulose fibers extracted from wood
 US 9,388,532 B2
7 8
or other plant by a mechanical or chemical process” (Kami pulp, C.-cellulose content and hemi-cellulose content can be
Parupu Jiten (Dictionary of Pulp and Paper), Feb. 20, 2000, calculated separately for the purified pulp portion and unpu
Japan TAPPI, Kanehara & Co., Ltd.), which is considered a rified pulp portion.
general definition of pulp. Under the present invention, the water retention level of
Purified pulp under the present application for patent purified pulp whose C.-cellulose content is 88 percent by
excludes rayon and other regenerated cellulose fibers, fiber weight or more (hereinafter also referred to simply as “puri
carboxymethyl cellulose and fiber carboxymethyl cellulose fied pulp') is 140 percent by less, or preferably 120 percent by
Nasalt. less, when the purified pulp is beaten to a freeness of 450 ml
Mercerized pulp refers to pulp obtained by soaking kraft CSF based on the Canadian Standard Freeness (hereinafter
pulp or Sulfite pulp in strong alkali solution and then washing 10 referred to as “freeness'), from the viewpoint of water dis
the pulp in water to remove the alkali component. persion property.
Dissolving pulp refers to pulp of high cellulose purity Purified pulp having a water retention level in this range
obtained by means of sulfite cooking or prehydrolysis kraft consists of fibers that are difficult to swell and fibrillate, so
cooking, where pulp of varying cellulose purity can be more of beating energy is used to break fibers. As a result, the
15 beaten purified pulp has low inter-fiber bonding capacity and
obtained by combining a post-cooking bleaching and selec short fibers, resulting in a sheet offering high water dispersion
tion process. property. On the other hand, purified pulp whose water reten
The reason why excellent dispersion property can be tion level at a freeness of 450 ml CSF exceeds 14.0% under
obtained under the present invention is presumed as follows. goes swelling and fibrillation of fibers, when beaten, and
Purified pulp has a very low hemi-cellulose content that con inter-fiber bonding increases, which makes it difficult to
tributes to Swelling of fibers and agglutination among fibers, obtain a sheet that disperses into single fibers. Note that water
so in an unbeaten form, this pulp forms a weak, bulky sheet retention level is an indicator of swelling level of pulp as
offering high water dispersion property. Once purified pulp is specified in JAPAN TAPPI No. 26, representing the ratio to
beaten, its low hemi-cellulose content Suppresses Swelling the total weight of pulp of the water content that has been
and fibrillation offibers due to beating, which in turn prevents 25 taken in and retained in swollen fibers.
the water retention level from increasing much, makes the Under the present invention, the average fiber length of
fiber rigid and straight and easy to break, and thereby purified pulp is 0.1 to 5 mm, or preferably 0.5 to 3 mm, or
increases short fibers. As a result, a sheet formed from beaten more preferably 0.8 to 2 mm.
purified pulp effectively retains its original water dispersion The water dispersion paper proposed by the present inven
property because, although its strength increases and bulki 30 tion was developed with a focus on using a blend of normal
ness decreases somewhat as compared to the unbeaten state, unpurified wood pulp and/or non-wood pulp (hereinafter also
short fibers that contribute to improvement of water disper referred to simply as “pulp’) and purified pulp containing
sion property increase. C.-cellulose by 88 percent by weight or more and thereby
Under the present invention, C.-cellulose content is used as offering characteristics different from normal pulp, and the
an indicator for cellulose purity of purified pulp. The C-cel 35 paper exhibits both excellent water dispersion property and
lulose content of purified pulp must be 88 percent by weight high strength.
or more, or preferably 92 percent by weight or more, or more <Unpurified Pulp>
preferably 95 percent by weight or more. If purified pulp In the water dispersion paper proposed by the present
contains C-cellulose by less than 88 percent by weight, it invention, examples of wood pulp and/or non-wood pulp
becomes difficult for the pulp to disperse as single fibers and 40 other than purified pulp containing C-cellulose by 88 percent
therefore its dispersion property in water drops. Note that, by weight or more include, among others, wood pulp from
under the present invention, C-cellulose content is measured needle-leaved trees, broad-leaved trees, etc., and non-wood
based on the O.-cellulose specified in the TAPPI Standard pulp from hemp, linter, kenaf, bagasse, manila hemp, etc. The
T203om-83 (JIS P8101-1994 (already obsolete)). aforementioned examples of wood pulp and/or non-wood
Under the present invention, hemi-cellulose content is used 45 pulp other than purified pulp have a high hemi-cellulose
as another indicator of cellulose purity of purified pulp. The content that contributes to formation of inter-fiber bonding,
hemi-cellulose content of purified pulp must be less than 12 and as their fibers swell and fibrillate easily, they form a
percent by weight, or preferably less than 8 percent by weight, dense, strong paper with low water dispersion property. This
or more preferably less than 5 percent by weight. If purified trend becomes more prominent when pulp is beaten further,
pulp contains hemi-cellulose by 12 percent by weight or 50 which suggests that a paper that offers good water dispersion
more, it becomes difficult for the pulp to disperse as single property and is also strong cannot be obtained only from
fibers and therefore its dispersion property in water drops. unpurified pulp.
Note that, under the present invention, hemi-cellulose content Pulp of fiber carboxymethyl cellulose Nasalt and regener
is measured by acid-hydrolyzing purified pulp or unpurified ated cellulose fibers are not used. Pulp offiber carboxymethyl
pulp into monosaccharides and then quantifying the compo 55 cellulose Nasalt, which is made by alkali-treating fiber car
sitions of monosaccharides by the alditol acetate method. boxymethyl cellulose, is inappropriate because alkali may
Specifically, the monosaccharides obtained by hydrolysis of have negative effects depending on the application and the
pulp are reduced by sodium borohydride into equivalentaldi pulp changes color easily. Regenerated cellulose fibers are
tol acetate, which is then acetylated with acetic anhydride and also inappropriate because poor sheet strength and Smooth
pyridine into an alditol acetate derivative, after which this 60 ness result in poor printability.
alditol acetate derivative is analyzed by gas chromatography <Pulp Blending and Papermaking>
to identify and quantify the component saccharides. The water dispersion paper proposed by the present inven
Note that C.-cellulose content and hemi-cellulose content tion must be such that purified pulp containing C-cellulose by
can also be measured for a paper made by blending purified 88 percent by weight or more accounts for 15 to 95 percent by
pulp and unpurified pulp, as with a paper made only of each 65 weight, or preferably 20 to 80 percent by weight, or more
pulp. In addition, by observing the fiber form of pulp and preferably 20 to 60 percent by weight, of all pulp constituting
obtaining the blending ratio of purified pulp and unpurified the water dispersion paper. If the blending ratio of purified
 US 9,388,532 B2
9 10
pulp is less than 15 percent by weight, inter-fiber bonding of or animal, medical applications, film lamination applications
fibers that form the sheet becomes too strong and sufficient and other applications where use of Such paper has not been
water dispersion property cannot be obtained. possible.
If the blending ratio of purified pulp exceeds 95 percent by Under the present invention, the method to adjust the paper
weight, on the other hand, sheet strength decreases consider Surface pH is not limited in any way, and basically a water
ably and ease of handling in practical situations drops. dispersion paper is manufactured by using a neutral material
Under the present invention, purified pulp and pulp can be as the primary constituent. Or, a water dispersion paper can be
beaten separately and then blended (hereinafter referred as manufactured by neutralizing an alkaline or acid water dis
“separate beating), or they can be blended first and then persion paper with an acid substance or alkaline Substance.
beaten (hereinafter referred to as “mixed beating'), but mixed 10 Note, however, that, if a water dispersion paper, which is
beating is preferred as it improves water dispersion property. made by mixing conventional papermaking fibers and fiber
Although the specific reason why it is preferred is not clear, it carboxymethyl cellulose and then adding an alkali metal
is probably because mixed beating induces some kind of compound, is neutralized with an acid substance, the fiber
carboxymethyl cellulose becomes insoluble. Accordingly, a
interaction between purified pulp and pulp and causes unex 15 problem is that the water dispersion property drops signifi
pected benefits to manifest. cantly.
Under the present invention, the beating level of paper <Water Dispersion Propertyd
material made of a blend of purified pulp and pulp is 450 to Under the present invention, water dispersion property can
700 ml CSF in freeness, or preferably 550 to 650 ml CSF, be evaluated by floc water dispersion time and fiber water
based on freeness, regardless of whether separate beating or dispersion time. The floc water dispersion time, defined as the
mixed beating is used. If the freeness is less than 450 ml CSF, time until a test piece of 3x3 cm square, put in a 300-ml
inter-fiber bonding becomes stronger and favorable water beaker containing 300 ml of deionized water, tears into two or
dispersion property drops. If the freeness is 700 ml CSF or more pieces when agitated with a stirrer at 650 rpm, is within
more, on the other hand, inter-fiber bonding weakens and 30 seconds, or preferably within 20 seconds, or more prefer
sheet strength drops. 25 ably within 10 seconds. When this floc water dispersion time
Under the present invention, it is preferable to use purified becomes longer, the drain or piping gets clogged by the
pulp whose water retention level at 450 ml CSF is 140 percent flushed water dispersion paper.
or less if purified pulp and pulp are put through mixed beating On the other hand, the fiber dispersion time, defined as the
until the aforementioned freeness. When purified pulp whose time until a test piece of 3x3 cm square, put in a 300-ml
water retention level at 450 ml CSF is 140 percent or less is 30 beaker containing 300 ml of deionized water, completely
used, beating energy is consumed for breaking the purified disintegrates into single fibers when agitated with a stirrer at
pulp, which produces short purified-pulp-derived fibers with 650 rpm, is within 80 seconds, or preferably within 40 sec
minimal Swelling and fibrillation and Suppresses excessive onds, or more preferably within 20 seconds. When this fiber
beating of pulp, resulting in manifestation of excellent water dispersion time becomes longer, the contaminant catch at the
dispersion property. 35 drain gets clogged by the flushed water dispersion paper.
On the other hand, purified pulp whose water retention <Additional Processing of Water Dispersion Papers
level at a freeness of 450 ml CSF exceeds 140 percent pro The water dispersion paper proposed by the present inven
vides significantly lower water dispersion property because tion can be calendered using a machine calender, Super cal
separate or mixed beating promotes Swelling and fibrillation ender, soft nip calender or other general papermaking cal
of fibers and increases inter-fiber bonding, as is the case of 40 ender to improve Smoothness for printing applications, etc.
pulp. If such purified pulp is used without beating, drawbacks It is also possible to laminate a water-soluble resin film to
Such as easy detachment of pulp fibers from the sheet and increase Smoothness and air resistance. For the water-soluble
increase of paper powder will result. resin film, water-soluble polyvinyl alcohol, polyalkylene
The water dispersion paper proposed by the present inven oxide, polyalkylene oxide copolymer or other water-soluble
tion can be manufactured from a paper material constituted by 45 resin is used in film form.
purified pulp and pulp using any known papermaking tech Preferably a water-soluble polymer is impregnated into or
nology. Any paper machine can be used, such as cylinder (vat) coated onto the water dispersion paper proposed by the
paper machine, inclined tanmo paper machine, fourdrinier present invention in order to improve water dispersion prop
paper machine or twin-wire paper machine, and an appropri erty (particularly the fiber dispersion time) and dry strength.
ate machine can be selected according to the required strength 50 By impregnating or coating the below-mentioned water
and water dispersion property. If a cylinder paper machine is soluble polymer into/onto a water dispersion paper consti
used, for example, a base paper that is weaker in lateral tuted by wood pulp and/or non-wood pulp containing 15 to 95
direction than longitudinal direction due to significant percent by weight of purified pulp that contains C-cellulose
strength anisotropy and thus tears easily in water in lateral by 88 percent by weight or more (hereinafter also referred to
direction can be manufactured. 55 as “base paper), voids between fibers in the base paper are
The base paper can be made as a single-layer sheet, or a filled by the water-soluble polymer and the dry strength of the
paper machine having two or more wire cloths can be used to water dispersion paper increases as a result, while the water
manufacture multiple wet papers from the same paper mate soluble polymer in voids between fibers swells as it comes in
rial and then the papers can be combined to manufacture a contact with water and pushes fibers away from each other to
heavier sheet, or sheets made from different paper materials 60 allow for easy separation of fibers.
can be combined into a single paper. Under the present invention, preferred forms of the water
<Paper Surface pH> soluble polymer include those whose dry film easily re-dis
The paper Surface pH of the water dispersion paper pro Solves in water, Such as carboxyalkyl cellulose salt, alginate,
posed by the present invention is adjusted to a range of 6 to 8 pectate, polyacrylate, polymethacrylate, carboxy alkylated
(neutral range), or preferably to a range of 6.2 to 7.2. By 65 starch, starch phosphate, anionic polyacrylamide and other
adjusting the paper Surface pH to these ranges, the water anionic polymeric electrolyte salts, methyl cellulose,
dispersion paper can be used in applications involving plant hydroxyalkyl cellulose, polyvinyl alcohol, polyvinyl pyrroli
 US 9,388,532 B2
11 12
done, polyalkylene oxide, polyvinyl ethyl ether, hydroxy cationic fixer, it is preferable to use a polyamine resin
ethylated Starch, oxidized Starch, alpha starch and other poly expressed by General Formula (I) below:
meric non-electrolytes, cyamoposis gum, trant gum, Xanthan
gum, gum arabic, carrageenan, galactomannan, pullulan,
dextran, dextrin and other water-soluble polysaccharides, 5 Chemical Formula 1
gelatin, casein and other water-soluble proteins, etc., where (1)
any one type of the foregoing may be used or two or more R
types of them may be combined. Among the above, using
carboxymethyl cellulose salt is preferable from the viewpoint CH-CH-CH2-N'
of improving water dispersion property and strength. 10 OH
| Cr pi
R2
Under the present invention, it is preferable, from the view
point of improving water dispersion property, that the water
soluble polymer permeates uniformly in the voids between In General Formula (I), R1 represents an alkyl group with
fibers in the base paper. Accordingly, the water-soluble poly 1 to 10 carbons that may include a hydroxyl group,
mer to be impregnated or coated intofonto the base paper 15 hydroxymethyl group, hydroxyethyl group or other Substitu
preferably has a viscosity of 1 to 20 mPa is in 2 weight-percent tion group (but Such substitution group is not counted toward
aqueous solution at 20° C. the carbon number), R2 represents a hydrogen atom or alkyl
Under the present invention, the additive amount (dry group with 1 to 10 carbons that may contain a hydroxyl group,
weight) of the water-soluble polymer to be impregnated or hydroxymethyl group, hydroxyethyl group or other Substitu
coated is 2 to 14 percent by weight, or preferably 3 to 12 tion group (but Such substitution group is not counted toward
percent by weight, or more preferably 6 to 10 percent by the carbon number), and n represents a positive integer.
weight, relative to the base paper. If the additive amount of the Polyamine resin, if used as the cationic fixer, has a cation
water-soluble polymer is less than 2 percent by weight rela equivalent of 0.1 to 20 milligram equivalent/g, or preferably
tive to the base paper, the sufficient effect on the water dis 1 to 15 milligram equivalent/g, or more preferably 2 to 10
persion property and the strength cannot be expected. If the 25 milligram equivalent/g, in a pH range of 3 to 9. The number
additive amount is greater than 14 percent by weight, on the average molecular weight of such polyamine resin is 5000 to
other hand, water dispersion property and strength will not 100000, or preferably 5000 to 70000, or more preferably
improve further. 5000 to 20OOO.
The water-soluble polymer can be added to the base paper Under the present invention, the contents of water-soluble
using any method selected, as deemed appropriate, from the 30 polymeric electrolyte salt and cationic fixer in the base paper
group that includes impregnation methods using a mangle, are adjusted as deemed appropriate according to the required
sizing press, etc., and Surface coating methods using a gate quality and not specifically limited, but if a water-soluble
roll coater, blade coater, bar coater, gravure coater, die coater, polymeric electrolyte Salt and cationic fixer are added as an
curtain coater, spray coater, etc. aqueous solution to the slurry of paper material (purified pulp
Under the present invention, when impregnating or coating 35 and pulp) before it is put through the papermaking process,
a water-soluble polymer to improve the water dispersion preferably their additive quantities are adjusted to the ranges
property and dry strength of the water dispersion paper, it is specified below.
preferable that the base paper contains a water-soluble poly If a water-soluble polymeric electrolyte salt is used
meric electrolyte salt so as to add enough strength to the base together with a cationic fixer, the additive amount (equivalent
paper to withstand the impregnation or coating. 40 solid content) of the water-soluble polymeric electrolyte salt
Under the present invention, such water-soluble polymeric is preferably 0.5 to 10 percent by weight, or more preferably
electrolyte salt can be added, for example, as an aqueous 2 to 6 percent by weight, of the total amount of purified pulp
Solution to the slurry of paper material (purified pulp and and pulp. If the additive amount of the water-soluble poly
pulp) before it is put through the papermaking process, or to meric electrolyte salt is less than 0.5 percent by weight,
the produced paper when still wet using a roll coater, curtain 45 strength does not improve much and there is no point in
coater, spray coating machine, etc., and then extracting water adding the water-soluble polymeric electrolyte salt. If the
and drying the paper. additive amount of the water-soluble polymeric electrolyte
Under the present invention, the water-soluble polymeric salt is greater than 10 percent by weight, on the other hand, no
electrolyte salt to be contained in the base paper must have further improvement in strength and water dispersion prop
adhesion strength to boost inter-fiber bonding as well as water 50 erty is expected.
solubility to dissolve easily when the sheet is wetted so as to The additive amount of the cationic fixer is preferably 0.2
allow the fibers to separate. As long as these requirements are to 4.0 percent by weight, or more preferably 0.5 to 2.0 percent
met, any anionic or amphoteric polymeric electrolyte salt can by weight, of the total amount of purified pulp and pulp. If the
be used, where examples include carboxymethyl cellulose additive amount of the cationic fixer is 0.2 percent by weight
salt and other carboxy alkyl cellulose salts, alginate, car 55 or less, the fixation ratio of the water-soluble polymeric elec
boxymethylated Starch, polyacrylate, polymethacrylate, trolyte salt drops and strength needed in the Subsequent pro
anionic polyacrylamide and amphoteric polyacrylamide, of cesses cannot be obtained. If the additive amount of the cat
which carboxymethyl cellulose sodium and carboxymethy ionic fixer is 4.0 percent by weight or more, on the other hand,
lated starch are preferred. Two or more types of such water excessive inter-fiber bonding in the base paper causes loss of
soluble polymeric electrolyte salts can be added. 60 water dispersion property (especially fiber dispersion time),
Under the present invention, preferably a cationic fixer is which is not desirable.
also used in order to improve the fixation ratio of the water Preferably the cationic fixer is added to the paper material
soluble polymeric electrolyte salt, because purified pulp and or wet paper before the water-soluble polymeric electrolyte
pulp are both anionic. salt, so that cationic property is added to the fibers before the
This cationic fixer must have an effect of fixing the water 65 water-soluble polymeric electrolyte salt is added.
soluble polymeric electrolyte salt onto the base paper fibers Under the present invention, it is desirable to add a water
without any loss of the water dispersion property, so for the soluble dispersant to the slurry of base paper material (puri
 US 9,388,532 B2
13 14
fied pulp and pulp) before it is put through the papermaking vided between the back side of the base material and the
process, in order to improve the formation of base material pressure-sensitive adhesive layer, or on both sides of the base
and the yield of paper material. The additive amount (equiva material.
lent solid content) of this water-soluble dispersant is prefer Smoothness of the base material surface on which to coat
ably 0.01 to 5.0 percent by weight, or more preferably 0.1 to the sealer layer is not limited in any way, but extra-Smooth
1.0 percent by weight, of the total amount of purified pulp and Surface is generally preferred and Yankee dryer-contacted
pulp. If the additive amount of the water-soluble dispersant is surface or calendered surface is used favorably.
less than 0.01 percent by weight, not enough improvement is (Composition of Sealer Layer)
expected in formation or yield of paper material and there is In terms of its composition, the sealer layer is primarily
no point in adding the water-soluble dispersant. If the additive 10 constituted by pigment, binder and various additives.
amount of the water-soluble dispersant is greater than 5.0 Examples of pigment that may be used in the sealer layer
percent by weight, on the other hand, no further improvement are as follows: Silica, calcium carbonate, clay, kaolin, sin
in formation and yield of paper material is expected. The tered kaolin, diatomaceous earth, talc, titanium oxide, alumi
water-soluble dispersant may be cyamoposis gum, polyacry num hydroxide, magnesium carbonate, Zinc oxide, aluminum
15 oxide, magnesium hydroxide, barium sulfate, calcium Sul
lamide, polyethylene oxide, Viscous liquid of abelmoschus fate, Zinc sulfate, calcium silicate, aluminum silicate, magne
manihot, or the like, where two or more types of the foregoing sium silicate, alumino-silicate Soda, magnesium alumino
can be added together. silicate and other inorganic pigments; melamine resin, urea
Water Dispersion Coated Paper formalin resin, polyethylene powder, nylon powder and other
The water dispersion coated paper as proposed by the organic pigments; cellulose powder, carboxymethylcellulose
present invention consists of the aforementioned water dis salt powder of 0.35 or less in substitution degree, and other
persion paper and a coating layer formed on top which is polysaccharides powders.
made by coating at least one layer of water-based coating Examples of binder used for the sealer layer are as follows:
material. The coated paper proposed by the present invention Completely-Saponified polyvinyl alcohol, partially-Saponi
has a coated Surface formed on the water dispersion paper and 25 fied polyvinyl alcohol, carboxy-modified polyvinyl alcohol,
thus constitutes a coated printing paper that disperses in amide-modified polyvinyl alcohol, sulfonic acid-modified
water. A sealer layer can be formed between a coating layer polyvinyl alcohol, butylal-modified polyvinyl alcohol and
and the water dispersion paper. This coated paper that dis other modified polyvinyl alcohols, hydroxyethyl cellulose,
Solves in water also has a pressure-sensitive adhesive layer on methyl cellulose, carboxymethyl cellulose salt, starch, gela
the back side that can be adhered and separated. Preferably 30 tin, casein, Sodium alginate, polyvinyl pyrrolidone, polyacry
these coating layer, sealer layer, printing and pressure-sensi lamide, acrylamide/acrylic ester copolymer, acrylate/acrylic
tive adhesive are made of materials and have constitutions ester copolymer, alkali salt of styrene/maleic anhydride
that do not prevent dispersion in water. copolymer, alkali salt of ethylene/maleic anhydride copoly
The coating layer constituting the coated paper that dis mer and other water-soluble resins; polyvinyl acetate, vinyl
35 acetate/acrylic ester copolymer, ethylene/vinyl acetate
Solves in water as proposed by the present invention may copolymer, polyacrylic ester, styrenefacrylic ester copoly
consist of a single layer or multiple layers as long as each mer, polyurethane resin, polyvinyl butylal, polystyrene and
layer is formed by coating and drying water-soluble coating copolymers thereof, polyamide resin, silicon resin, petroleum
material, and the coating method, etc., are not limited in any resin, terpene resin, ketone resin, coumarone resin and other
way. Additionally any constituent material of coating layer 40 non-water-soluble resins.
can be selected as deemed appropriate for the press-printing These polymeric Substances are used by dissolving them in
method (offset press, gravure press, etc.) or printer-printing water, alcohol, ketone, ester, hydrocarbon or other solvent, or
method (inkjet printer, thermo-sensitive printer, laser beam emulsifying them, or dispersed them into paste form, in water
printer, etc.) used. or other medium, and two or more substances may be used
Examples of coating layers Suitable for thermo-sensitive 45 together according to the required quality.
printer, inkjet printer and general printing are shown below. Among the above, water-soluble resins and water-dispers
<Sealer Layerd ible resins are preferred binders from the viewpoint of water
The water dispersion coated paper as proposed by the dispersion property. It is desirable to use starch, hydroxyethyl
present invention preferably has a sealer layer between the cellulose, methyl cellulose, carboxymethyl cellulose salt,
base material and coating layer. The primary constituents of 50 gelatin, casein, Sodium alginate, polyvinyl alcohol, modified
the sealer layer are pigment and binder. Specifically, the polyvinyl alcohol or polyvinyl pyrrolidone as the primary
sealer layer is provided between the base material and the constituent of the binder.
coating layer which is a thermo-sensitive recording layer, The binder used for the sealer layer normally has 5 to 100
undercoat layer, inkjet recording layer, general printing layer, parts by weight of solid content relative to 100 parts by weight
etc. The sealer layer prevents drop in operability which may 55 of filler.
be otherwise caused by permeation of excessive coating solu In addition to pigment and binder, the sealer layer can also
tion into the base material when the coating layer is coated, contain various additives that are customarily used. Examples
and also prevents the ions or the plasticizer, etc., contained in of these various additives include pigment dispersant,
the pressure-sensitive adhesive from migrating into the coat defoaming agent, lubricant, sizing agent, preservative and
ing layer. Because the aforementioned base material is a 60 Wetting agent, among others.
porous layer with weak inter-fiber bonding, providing the (Coating of Sealer Layer)
sealer layer embodies a thermo-sensitive recording medium The sealer layer is obtained by dispersing and mixing other
whose base material offers good color development, resis additives in/with the aforementioned pigment and binder and
tance to attachment of contaminants and anti-sticking prop then coating the obtained sealer using a coating machine,
erty. 65 followed by heating and drying with a dryer. The coating
If a pressure-sensitive adhesive layer is provided on the amount of the sealer layer, in weight after drying, is normally
back side of the base material, the sealer layer may be pro 0.5 to 30 g/m, or preferably 3 to 15 g/m. The coating
 US 9,388,532 B2
15 16
machine may be an air knife coater, bar coater, roll coater, In addition to pigment and binder, the under coat layer can
blade coater, curtain coater, Champlex coater, gravure coater, also contain various additives that are customarily used.
etc. Examples of these various additives include pigment dispers
<Coating Layers ant, defoaming agent, lubricant, UV absorbent, sizing agent,
The coating layer constituting the water dispersion coated sensitizer, fluorescent dye and preservative, among others.
paper as proposed by the present invention may consist of a The under coat layer is obtained by dispersing and mixing
single layer or multiple layers as long as each layer is formed other additives in/with the aforementioned pigment and
by coating and drying water-soluble coating material, and the binder and then coating the obtained coating material in one
coating method, etc., are not limited in any way. Additionally layer or multiple layers using a coating machine, followed by
any constituent material of coating layer can be selected as 10 heating and drying with a dryer. The coating amount of the
deemed appropriate for the press-printing method (offset under coat layer, in weight after drying, is normally 0.5 to 50
press, gravure press, etc.) or printer-printing method (inkjet g/m, or preferably 3 to 15 g/m. The coating machine may be
printer, thermo-sensitive printer, laser beam printer, etc.) an air knife coater, bar coater, roll coater, blade coater, curtain
used.
coater, Champlex coater, gravure coater, etc.
15 The thermo-sensitive recording layer is coated on top of the
Examples of coating layers Suitable for thermo-sensitive under coat layer. Composition-wise, constituents of the
printer, inkjet printer and general printing are shown below. thermo-sensitive recording layer include dye, color devel
(Thermo-Sensitive Recording Medium) oper, binder and auxiliary additives.
The coating layer for thermo-sensitive printer is provided For the dye, any known leuco dye may be used alone or two
by forming an undercoat layer and athermo-sensitive record or more types of Such dyes can be mixed together, where a
ing layer, in this order, on top of the water dispersion paperor leuco compound of triphenylmethane dye, fluoran dye, phe
sealer layer coated on the water dispersion paper. Addition nothiazine dye, auramine dye, Spiropyran dye, indolinoph
ally, a protective layer can be provided. If the water dispersion thalide dye, etc., is particularly preferred.
coated paper as proposed by the present invention is to be Specific examples of dye include the following com
adapted to printing by a thermo-sensitive printer, it is prefer 25 pounds: 3,3-bis(p-dimethylaminophenyl)-phthalide, 3.3-bis
able to coat onto the aforementioned base material a under (p-dimethyl aminophenyl)-6-dimethyl aminophthalide (also
coat layer that contains pigment and binder as primary con known as crystal violet lactone), 3.3-bis(p-dimethyl ami
stituents, and athermo-sensitive recording layer that contains nophenyl)-6-diethyl aminophthalide, 3.3-bis(p-dimethyl
colorless or light-colored electron-donating leuco dye and aminophenyl)-6-chlorophthalide, 3.3-bis(p-dibutyl ami
electron-receiving color developeras primary constituents, in 30 nophenyl) phthalide, 3-cyclohexyl amino-6-chlorofluoran,
this order. 3-dimethylamino-5,7-dimethyl fluoran, 3-diethyl amino-7-
In general, the base material surface on which to coat the chlorofluoran, 3-diethyl amino-7-methyl fluoran, 3-diethyl
under coat layer is preferably very smooth, and Yankee dryer amino-7,8-benzofluoran, 3-diethyl amino-6-methyl-7-chlo
contacted Surface or calendered Surface is used favorably. rofluoran, 3-(N-p-tolyl-N-ethylamino)-6-methyl-7-anilinof
In the thermo-sensitive recording medium, the under coat 35 luoran, 3-pyrrolidino-6-methyl-7-anilinofluoran, 2-N-(3'-
layer is provided make the base material Surface Smoother trifluoromethyl phenyl)amino)-6-diethyl aminofluoran,
and thereby achieve sharpness and high sensitivity of the 2-3,6-bis(diethylamino)-9-(o-chloroanilino) xanthylic lac
image, and is composed of known pigment, binder and vari tam benzoate, 3-diethyl amino-6-methyl-7-(m-trichlorom
ous additives. ethyl anilino) fluoran, 3-diethyl amino-7-(o-chloroanilino)
Examples of the pigment component of the under coat 40 fluoran, 3-di-n-butylamino-7-(o-chloroanilino) fluoran, 3-N-
layer include, among others, silica, calcium carbonate, clay, methyl-N, n-amyl amino-6-methyl-7-anilino fluoran, 3-N-
kaolin, sintered kaolin, diatomaceous earth, talc, titanium methyl-N-cyclohexyl amino-6-methyl-7-anilinofluoran,
oxide, aluminum hydroxide, magnesium carbonate, Zinc 3-diethyl amino-6-methyl-7-anilinofluoran, 3-(N,N-diethyl
oxide, aluminum oxide, magnesium hydroxide, barium Sul amino)-5-methyl-7-(N,N-dibenzyl amino) fluoran, benzoyl
fate, calcium Sulfate, Zinc sulfate, calcium silicate, aluminum 45 leucomethylene blue, 6'-chloro-8-methoxy-benzoindolino
silicate, magnesium silicate, alumino-silicate Soda, magne spiropyran, 6'-bromo-3'-methoxy-benzoindolino-spiropy
sium alumino-silicate and other inorganic fillers, or melamine ran, 3-(2-hydroxy-4-dimethyl aminophenyl)-3-(2-meth
resin filler, urea-formalin resin filler, polyethylene powder, oxy-5'-chlorophenyl) phthalide, 3-(2-hydroxy-4-dimethyl
nylon powder and other organic fillers. aminophenyl)-3-(2-methoxy-5'-nitrophenyl)phthalide,
For the binder component of the under coat layer, water 50 3-(2-hydroxy-4-diethyl aminophenyl)-3-(2-methoxy-5'-
soluble resins or water-dispersible resins are preferred. Spe methyl phenyl)phthalide, 3-(2-methoxy-4-dimethyl ami
cific examples include starch, hydroxyethyl cellulose, methyl nophenyl)-3-(2-hydroxy-4'-chloro-5'-methyl phenyl)phtha
cellulose, carboxymethyl cellulose, gelatin, casein, sodium lide, 3-(N-ethyl-N-tetrahydrofurfuryl)amino-6-methyl-7-
alginate, polyvinyl alcohol, modified polyvinyl alcohol, anilinofluoran, 3-N-ethyl-N-(2-ethoxy propyl)amino-6-
polyvinyl pyrrolidone, polyacrylamide, acrylamide/acrylic 55 methyl-7-anilinofluoran, 3-N-methyl-N-isobutyl-6-methyl
ester copolymer, styrene/maleic anhydride copolymer and 7-anilinofluoran, 3-morpholino-7-(N-propyl-trifluoromethyl
alkali salt thereof, ethylene/maleic anhydride copolymer and anilino) fluoran, 3-pyrrolidino-7-m-trifluoromethyl anilinof
alkali salt thereof, and polyacrylic Soda, among others. Of luoran, 3-diethyl amino-5-chloro-7-(N-benzyl-trifluorom
these, water-soluble resins. Such as starch, hydroxyethyl cel ethyl anilino) fluoran, 3-pyrrolidino-7-(di-p-chlorophenyl)
lulose, methyl cellulose, carboxymethyl cellulose, gelatin, 60 methylaminofluoran, 3-diethylamino-5-chloro-7-(CL-phenyl
casein, Sodium alginate, polyvinyl alcohol, modified polyvi ethyl amino) fluoran, 3-(N-ethyl-p-toluidino)-7-O-phenyl
nyl alcohol and polyvinyl pyrrolidone, are preferred as the ethyl amino) fluoran, 3-diethyl amino-7-(o-methoxy carbo
primary constituents of the binder from the viewpoint of nyl phenyl amino) fluoran, 3-diethyl amino-5-methyl-7-(C.-
water dispersion property. phenyl ethyl amino) fluoran, 3-diethyl amino-7-piperidino
The binder used for the under coat layer normally has 5 to 65 fluoran, 2-chloro-3-(N-methyl toluidino)-7-(p-n-butyl
100 parts by weight of solid content relative to 100 parts by anilino) fluoran, 3-(N-methyl-N-isopropylamino)-6-methyl
weight of pigment. 7-anilinofluoran, 3-di-n-butyl amino-6-methyl-7-anilinof
 US 9,388,532 B2
17 18
luoran, 3,6-bis(dimethylamino) fluolene Spiro (9.3)-6-dim phenyl)acetate, 1.7-bis(4-hydroxy phenyl thio) 3,5-dioxa
ethylamino phthalide, 3-(N-benzyl-N-cyclohexyl amino)-5, heptane, 1.5-bis(4-hydroxy phenylthio) 3-oxapentane, dim
6-benzo-7-O-naphthyl amino-4'-bromofluoran, 3-diethyl ethyl 4-hydroxy phthalate, 4-hydroxy-4-methoxy diphenyl
amino-6-chloro-7-anilinofluoran, 3-diethylamino-6-methyl Sulfone, 4-hydroxy-4'-ethoxy diphenyl Sulfone, 4-hydroxy
7-mesitidino-4,5'-benzofluoran, 3-N-methyl-N-isopropyl-6- 4-isopropoxy diphenyl Sulfone, 4-hydroxy-4'-propoxy
methyl-7-anilinofluoran, 3-N-ethyl-N-isoamyl-6-methyl-7- diphenyl sulfone, 4-hydroxy-4-butoxy diphenyl sulfone,
anilinofluoran, 3-diethyl amino-6-methyl-7-(2,4'-dimethyl 4-hydroxy-4-isobutoxy diphenyl Sulfone, 4-hydroxy-4'-sec
anilino) fluoran, etc. butoxy diphenyl sulfone, 4-hydroxy-4-tert-butoxy diphenyl
The water-dispersible coated paper proposed by the sulfone, 4-hydroxy-4-benzyloxy diphenyl sulfone, 4-hy
present invention may be used in applications where the paper 10 droxy-4'-phenoxydiphenyl Sulfone, 4-hydroxy-4-(m-methyl
is flushed into the drain after use, so use of highly safe dye is benzyloxy)diphenyl sulfone, 4-hydroxy-4-(p-methylbenzy
preferable in consideration of environment. For such highly loxy)diphenyl sulfone, 4-hydroxy-4-(o-methyl benzyloxy)
safe dye, 3-diethylamino-6-methyl-7-anilinofluoran, 3-dibu diphenyl sulfone, 4-hydroxy-4-(p-chlorobenzyloxy)diphe
tyl amino-6-methyl-7-anilinofluoran, 3-(N-cyclohexyl-N- nyl Sulfone, etc.
methylamino)-6-methyl-7-anilinofluoran, 3-(N-ethyl-N-iso 15 The water-dispersible coated paper proposed by the
pentyl amino)-6-methyl-7-anilinofluoran, 3-N-di-n-pentyl present invention may be used in applications where the paper
amino-6-methyl-7-anilinofluoran, 3-diethyl amino-7-(3-trif is flushed into the drain after use. Environmentally safe color
luoromethyl anilino) fluoran, 3-(N-ethyl-N-4-methyl phenyl developers that can be used include, among others, color
amino)-6-methyl-7-anilinofluoran, 3-diethyl amino-6-me developer compositions that contain 4,4'-dihydroxy diphenyl
thyl-7-(3-methyl anilino) fluoran, 3,3'-bis(dimethyl amino sulfone, 2,4'-dihydroxy diphenyl sulfone, 4-hydroxy-4-iso
phenyl)-6-dimethyl amino phthalide, 3-(4-diethyl amino-2- propoxy diphenyl Sulfone, benzyl para-hydroxy benzoate,
ethoxy phenyl)-3-(1-ethyl-2-methyl indole-3-yl)-4-azaph 4-hydroxy-4'-propoxy diphenyl sulfone, 3-(phenyl amino)
thalide, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl carbonyl)aminobenzene sulfone amide, N-(4-hydroxyphe
amino) fluoran, 3.3-bis(1-n-butyl-2-methyl-indole-3-yl)ph nyl thio)acetyl-2-hydroxy aniline, 1:1 mixture of N-(4-hy
thalide, 1,3-dimethyl-6-diethyl amino fluoran, 3-bromo-3- 25 droxy phenyl thio)acetyl-4-hydroxy aniline and N-(4-hy
methyl-6-dibutyl amino fluoran, etc., can be used favorably. droxy phenyl thio)acetyl-2-hydroxy aniline, 4,4'-bis (3-
The thermo-sensitive recording layer contains color devel (phenoxy carbonyl amino)methyl phenyl ureido)diphenyl
oper in addition to leuco dye. For this color developer, any sulfone and 2,2'-bis(4-(4-hydroxy phenyl sulfone) phenoxy
phenol, organic acid, inorganic acidorester or salt thereof can diphenyl ether; and condensed compositions that contain
be used, among others. 30 2,2'-methylene bis(4-t-butyl phenol) by 55% (specifically,
Specific examples of color developer include the following condensed compositions that contain 2,2'-methylene bis(4-t-
compounds: Gallic acid, salicylic acid, 3-isopropyl salicylic butyl phenol) by 55%, with the remainder being correspond
acid, 3-cyclohexyl salicylic acid, 3.5-di-tert-butyl salicylic ing 3-nuclear condensation product (29%), 4-nuclear con
acid, 3.5-di-O-methyl benzyl salicylic acid, 4,4'-isopropy densation product (11%), 5-nuclear condensation product
lidene diphenol. 1,1'-isopropylidene bis(2-chlorophenol), 35 (4%) and other (1%)).
4,4'-isopropylidene bis(2,6-dibromo phenol), 4,4'-isopropy For the binder, any known binder can be used.
lidene bis(2,6-dichloro phenol), 4,4'-isopropylidene bis(2- Specific examples of binder include, among others, com
methyl phenol), 4,4'-isopropylidene bis(2,6-dimethyl phe pletely-Saponified polyvinyl alcohol, partially-Saponified
nol), 4.4-isopropylidene bis(2-tert-butyl phenol), 4,4'-sec polyvinyl alcohol, carboxy-modified polyvinyl alcohol,
butylidene diphenol. 4,4'-cyclohexylidene bis phenol, 4,4'- 40 amide-modified polyvinyl alcohol, sulfonic acid-modified
cyclohexylidene bis(2-methyl phenol), 4-tert-butyl phenol, polyvinyl alcohol, butylal-modified polyvinyl alcohol and
4-phenyl phenol, 4-hydroxy diphenoxide, C.-naphthol, other modified polyvinyl alcohols, hydroxyethyl cellulose,
B-naphthol, 3.5-xylenol, thymol, methyl-4-hydroxy ben methyl cellulose, carboxymethyl cellulose, starch, gelatin,
Zoate, 4-hydroxyacetophenone, novolak-type phenolic resin, casein, Sodium alginate, polyvinyl pyrrolidone, polyacryla
2,2'-thiobis(4,6-dichlorophenol), catechol, resorcine, hydro 45 mide, acrylamide/acrylic ester copolymer, alkali Salt of Sty
quinone, pyrogallol, phloroglycine, phloroglycine carboxylic rene? maleic anhydride copolymer, alkali salt of ethylene/ma
acid, 4-tert-octyl catechol. 2,2'-methylene bis(4-chlorophe leic anhydride copolymer and other water-soluble resins,
nol), 2,2'-methylene bis(4-methyl-6-tert-butyl phenol), 2,2'- styrene-butadiene copolymer, acrylonitrile/butadiene
dihydroxy diphenyl, ethyl p-hydroxybenzoate, propyl p-hy copolymer, methyl acrylate/butadiene copolymer, acryloni
droxybenzoate, butyl p-hydroxybenzoate, benzyl p-hydroxy 50 trile/butadiene/styrene tertiary copolymer, ethyl cellulose,
benzoate, p-chlorobenzyl p-hydroxybenzoate, o-chloroben acetyl cellulose and other cellulose derivatives, polyvinyl
Zyl p-hydroxy benzoate, p-methyl benzyl p-hydroxy ben chloride, polyvinyl acetate, vinyl acetate/acrylic ester
Zoate, n-octyl p-hydroxybenzoate, benzoic acid, Zinc salicy copolymer, ethylene/vinyl acetate copolymer, polyacrylic
late, 1-hydroxy-2-naphthoic acid, 2-hydroxy-6-naphthoic ester, styrenefacrylic ester copolymer, polyurethane resin,
acid, Zinc 2-hydroxy-6-naphtholic acid, 4-hydroxy diphenyl 55 polyvinylbutylal, polystyrol and copolymers thereof, polya
sulfone, 4-hydroxy-4'-chlorodiphenyl sulfone, bis(4-hy mide resin, silicon resin, petroleum resin, terpene resin,
droxy phenyl)sulfide, 2-hydroxy-p-toluic acid, Zinc 3,5-di ketone resin, coumarone resin and other non-water-soluble
tert-butyl salicylate, tin 3,5-di-tert-butyl salicylate, tartaric resins.
acid, oxalic acid, maleic acid, citric acid. Succinic acid, Stearic These polymeric Substances are used by dissolving them in
acid, 4-hydroxy phthalic acid, boric acid, thiourea derivative, 60 water, alcohol, ketone, ester, hydrocarbon or other solvent, or
4-hydroxy thiophenol derivative, bis(4-hydroxy phenyl)ac emulsifying them, or dispersed them into paste form, in water
etate, ethyl bis(4-hydroxyphenyl)acetate, n-propyl bis(4-hy or other medium, and two or more substances may be used
droxy phenyl)acetate, n-butyl bis(4-hydroxy phenyl)acetate, together according to the required quality.
phenyl bis(4-hydroxy phenyl)acetate, benzyl bis(4-hydroxy For the binder, it is preferable, among the above, to use
phenyl)acetate, phenethyl bis(4-hydroxy phenyl)acetate, bis 65 water-soluble resin as the primary constituent, such as starch,
(3-methyl-4-hydroxyphenyl)acetate, methylbis(3-methyl-4- hydroxyethylcellulose, methylcellulose, carboxymethylcel
hydroxy phenyl)acetate, n-propyl bis(3-methyl-4-hydroxy lulose, gelatin, casein, sodium alginate, polyvinyl alcohol,
 US 9,388,532 B2
19 20
modified polyvinyl alcohol or polyvinyl pyrrolidone, from fier, after which binder and various additive materials are
the viewpoint of water dispersion property. added according to the purpose and mixed into a coating
For the thermo-sensitive recording layer, auxiliary additive Solution.
components are used, as necessary, along with the aforemen The method for forming the thermo-sensitive recording
tioned leuco dye, color developer and binder. For these aux layer is not limited in any way. For example, the thermo
iliary components, sensitizers, pigments, p-nitrobenzoate sensitive recording layer can be formed by coating a coating
metal salts (Ca, Zn), monobenzyl ester phthalate metal salts material onto the base material using planographic printing or
(Ca, Zn) and other stabilizers, aliphatic metal salts and other any one of various other printing methods or by means of air
mold release agents, waxes and other lubricants, pressure? knife coating, rod blade coating, bar coating, blade coating,
color development inhibitors, benzophenone-type or triazol 10 gravure coating, curtain coating, etc., and then drying the
type UV absorbents, glyoxal and other water-proofing agents, coated material. The coating amount of coating Solution is
dispersants, and defoaming agents can be used, for example. normally in a range of approx. 2 to 12 g, or preferably in a
range of approx. 3 to 10 g.
For sensitizers that improve thermal response, thermo A protective layer can be provided on the thermo-sensitive
fusible Substances, or specifically thermo-fusible organic 15 recording layer. Such protective layer can improve the com
compounds having a melting point of approx. 50 to 200°C., patibility with the thermal head, etc., and preservability of
can be used. recorded images. Constituents of the protective layer include
Specific examples of sensitizer include, among others, binder and various additives, among others.
Stearic amide, palmitic amide, N-hydroxy methyl Stearic For the binder of the protective layer, any of the same types
amide, N-Stearyl Stearic amide, ethylene bis-Stearic amide, of binder mentioned above for the thermo-sensitive recording
N-stearyl urea, benzyl-2-naphthyl ether, m-terphenyl, 4-ben layer can be used.
Zylbiphenyl, 2,2'-bis(4-mthoxyphenoxy) diethyl ether, C.C.'- Specific examples include completely-Saponified polyvi
diphenoxy Xylene, bis(4-methoxyphenyl)ether, diphenyl azi nyl alcohol, partially-Saponified polyvinyl alcohol, carboxy
pate, dibenzyl oxalate, di(4-chlorobenzyl) oxalate ester, modified polyvinyl alcohol, amide-modified polyvinyl alco
dimethyl terephthalate, dibenzyl terephthalate, phenyl ben 25 hol, sulfonic acid-modified polyvinyl alcohol, butylal
Zene Sulfonate ester, bis(4-aryl oxy phenyl)sulfone, 4-acetyl modified polyvinyl alcohol and other modified polyvinyl
acetophenone, anilide acetoacetates, aliphatic anilides, mon alcohols, hydroxyethyl cellulose, methyl cellulose, car
tan wax, polyethylene wax, benzyl p-benzyl oxybenzoate, boxymethyl cellulose, starch, gelatin, casein, sodium algi
di-p-tolyl carbonate, phenyl-O-naphtyl carbonate, 1,4-di nate, polyvinyl pyrrolidone, polyacrylamide, acrylamide/
ethoxy naphthalene, phenyl 1-hydroxy-2-naphthoate ester, 30 acrylic ester copolymer, alkali salt of styrene/maleic
1.2-di-(3-methyl phenoxy) ethane, di(p-methyl benzyl) anhydride copolymer, alkali Salt of ethylene/maleic anhy
oxalate, B-benzyl oxy naphthalene, 4-biphenyl p-tolyl ether, dride copolymer and other water-soluble resins, styrene-buta
o-xylylene-bis-(phenyl ether) and 4-(m-methyl phenoxy diene copolymer, acryronitrile/butadiene copolymer, methyl
methyl) biphenyl. acrylate/butadiene copolymer, acrylonitrile/butadiene/sty
The water-dispersible coated paper proposed by the
35 rene tertiary copolymer, ethyl cellulose, acetyl cellulose and
other cellulose derivatives, polyvinyl chloride, polyvinyl
present invention may be used in applications where the paper acetate, vinyl acetate/acrylic ester copolymer, ethylene/vinyl
is flushed into the drain after use. In consideration of envi acetate copolymer, polyacrylic ester, styrenefacrylic ester
ronment, highly safe sensitizers such as Stearic amide, palm copolymer, polyurethane resin, polyvinylbutylal, polystyrol
itic amide, ethylene bis-Stearoamide, benzyl parabenzyl oxy 40 and copolymers thereof, polyamide resin, silicon resin, petro
benzoate, 4-biphpenyl paratolyl ether, bis(paramethylben leum resin, terpene resin, ketone resin, coumarone resin and
Zyl) oxalate, bis(parachlorobenzyl) oxalate, parabenzyl other non-water-soluble resins. These polymeric Substances
biphenyl, 1.2-bis(phenoxy methyl)benzene, paratoluene Sul are used by dissolving them in water, alcohol, ketone, ester,
fone amide, orthotoluene Sulfone amide, diphenyl Sulfone, hydrocarbon or other solvent, or emulsifying them, or dis
benzyl oxy naphthalane, paraphenyl acetophenone and 1.2- 45 persed them into paste form, in water or other medium, and
bis(3-methyl phenoxy) ethane are desirable. two or more Substances may be used together according to the
Examples of pigment include, among others, silica, cal required quality. For the binder, it is preferable, among the
cium carbonate, clay, kaolin, sintered kaolin, diatomaceous above, to use water-soluble resin as the primary constituent,
earth, talc, titanium oxide, aluminum hydroxide, magnesium Such as starch, hydroxyethyl cellulose, methyl cellulose, car
carbonate, Zinc oxide, aluminum oxide, magnesium hydrox 50 boxymethyl cellulose, gelatin, casein, Sodium alginate, poly
ide, barium sulfate, calcium sulfate, Zinc sulfate, calcium vinyl alcohol, modified polyvinyl alcohol or polyvinyl pyr
silicate, aluminum silicate, magnesium silicate, alumino-sili rolidone, from the viewpoint of water dispersion property.
cate Soda, magnesium alumino-silicate and other inorganic Examples of various additives used for the protective layer
fillers; and melamine resin filler, urea-formalin resin filler, include fillers, Surface active agents, thermo-fusible Sub
polyethylene powder, nylon powder and other organic fillers. 55 stances (or lubricants) and pressure/color development
The amounts of organic color developer and leuco dye, and inhibitors, among others.
types and amounts of other various constituents, are deter Here, the specific examples of filler and thermo-fusible
mined according to the required performance and recordabil Substance are the same as those cited for the thermo-sensitive
ity and not limited in any way. Normally it is appropriate to recording layer above.
use 0.5 to 10 parts by weight of organic color developer and 60 The protective layer is obtained by dispersing and mixing
0.5 to 10 parts by weight of sensitizer, relative to 1 part by various additives in/with the aforementioned binder and then
weight of leuco dye, and use 5 to 50 percent by weight of coating the obtained coating material in one layer or multiple
binder relative to the total solid content. layers using a coating machine, followed by heating and
The aforementioned organic color developer, leuco dye drying with a dryer. The coating amount of coating material,
and other materials to be added as necessary are atomized to 65 in weight after drying, is normally 0.2 to 10 g/m, or prefer
particle size of several microns or less using a ball mill, ably 0.5 to 5 g/m. The coating machine is not limited in any
attritor, sand grinder or other crusher or appropriate emulsi way and an air knife coater, bar coater, roll coater, blade
 US 9,388,532 B2
21 22
coater, curtain coater, Champlex coater, gravure coater or any clear coat layer. Constitution-wise, pigment and water-based
other known coating machine can be used. binder are the primary constituents of the pigment coat layer.
Under the present invention, it is preferable to increase the Water-based binder is the primary constituent of the clear coat
Surface Smoothness of the thermo-sensitive recording layer layer. Various additives can also be blended in as deemed
using a calender, Super calender, soft nip calender or other 5 appropriate. Their blending amounts can be adjusted as
Smoothing machine for the purpose of improving the sharp deemed appropriate according to the required quality.
ness of image and sensitivity. The Beck Smoothness of Examples of pigment in the pigment coat layer include
thermo-sensitive recording layer surface is preferably 50 to calcium carbonate, clay, kaolin, sintered kaolin, diatoma
2000s, or more preferably 100 to 2000s. If the Beck smooth ceous earth, talc, titanium oxide, aluminum hydroxide, mag
ness is less than 50 s, the Smoothing process will have no 10 nesium carbonate, Zinc oxide, aluminum oxide, magnesium
effect as any improvement in printed image quality will be hydroxide, barium sulfate, calcium sulfate, Zinc sulfate, cal
minimal. If the Beck smoothness exceeds 2000s, on the other cium silicate, aluminum silicate, magnesium silicate, alu
hand, water dispersion property will drop notably due to mino-silicate Soda, magnesium alumino-silicate, silica, col
improved density of the base material, which is undesirable. loidal silica, calcium carbonate combined silica and other
(Inkjet Recording Medium) 15 inorganic fillers, or melamine resin filler, urea-formalin resin
For the coating layer for inkjet printer, it is appropriate to filler, polyethylene powder, nylon powder, styrene, Styrene
form a pigment coat layer or clear coat layer on top of the acrylic, acrylic and other organic fillers.
water dispersion paper or on top of the sealer layer coated on For the binder for the pigment coat layer and/or clear coat
the water dispersion paper proposed by the present invention. layer, water-soluble resins or water-dispersible resins are pre
Composition-wise, pigment and water-based binder are the ferred. Specific examples include starch, hydroxyethyl cellu
primary constituents of the pigment coat layer. Cationic resin lose, methyl cellulose, carboxymethyl cellulose, gelatin,
and/or water-based binder is/are the primary constituent(s) of casein, Sodium alginate, polyvinyl alcohol, modified polyvi
the clear coat layer. Various additives can be blended in as nyl alcohol, polyvinyl pyrrolidone, polyacrylamide, acryla
deemed appropriate. Their blending amounts can be adjusted mide/acrylic ester copolymer, styrene? maleic anhydride
as deemed appropriate according to the required quality. 25 copolymer and alkali salt thereof, ethylene/maleic anhydride
Examples of pigment in the pigment coat layer include copolymer and alkali salt thereof, styrenefbutadiene copoly
silica, colloidal silica, calcium carbonate, clay, kaolin, sin mer, pollyacrylate Soda, vinyl acetate, ethylene-vinyl acetate,
tered kaolin, diatomaceous earth, talc, titanium oxide, alumi acrylate copolymer, methacrylate copolymer and acrylate/
num hydroxide, magnesium carbonate, Zinc oxide, aluminum methacrylate copolymer, among others. It is preferable,
oxide, magnesium hydroxide, barium sulfate, calcium Sul 30 among the above, to include water-soluble resin as the binder,
fate, Zinc sulfate, calcium silicate, aluminum silicate, magne Such as starch, hydroxyethyl cellulose, methyl cellulose, car
sium silicate, alumino-silicate Soda, magnesium alumino boxymethyl cellulose, gelatin, casein, sodium alginate, poly
silicate, calcium carbonate combined silica and other vinyl alcohol, modified polyvinyl alcohol or polyvinyl pyr
inorganic fillers, or melamine resin filler, urea-formalin resin rolidone, from the viewpoint of water dispersion property.
filler, polyethylene powder, nylon powder, styrene, Styrene 35 Examples of various additives include cationic resin (print
acrylic, acrylic and other organic fillers. Of those, silica, ability improving agent), pigment dispersant, defoaming
alumina, sintered kaolin and calcium carbonate are preferred agent, lubricant, UV absorbent, sizing agent, fluorescent dye
from the viewpoints of ink absorbency and color development and preservative, among others.
property. The coating machine is not limited in any way, and an air
For the binder for the pigment coat layer and/or clear coat 40 knife coater, bar coater, roll coater, blade coater, curtain
layer, water-soluble resins or water-dispersible resins are pre coater, cast coater, Champlex coater, gravure coater, 2-roll
ferred, where specific examples include starch, hydroxyethyl coater, transfer roll coater, etc., can be used.
cellulose, methyl cellulose, carboxymethylcellulose, gelatin, <Pressure-Sensitive Adhesive Layers
casein, Sodium alginate, polyvinyl alcohol, modified polyvi The pressure-sensitive adhesive layer is provided on the
nyl alcohol, polyvinyl pyrrolidone, polyacrylamide, acryla 45 opposite side of the water dispersion paper Surface on which
mide/acrylic ester copolymer, styrene/maleic anhydride the coating layer is provided. The water-dispersible coated
copolymer and alkali salt thereof, ethylene/maleic anhydride paper proposed by the present invention can be used as a
copolymer and alkali salt thereof, styrenefbutadiene copoly pressure-sensitive adhesive sheet or label by providing a pres
mer, pollyacrylate Soda, vinyl acetate, ethylene-vinyl acetate, sure-sensitive adhesive layer on top of the opposite side of the
acrylate copolymer, methacrylate copolymer and acrylate/ 50 coating layer (i.e., press-printed Surface or printer-printed
methacrylate copolymer, among others. Of those, polyvinyl Surface) or on top of the sealer layer coated on the opposite
alcohol and modified polyvinyl alcohol, among others, are side. For the pressure-sensitive adhesive to constitute this
preferred from the viewpoints of ink absorbency and color pressure-sensitive adhesive layer, Suitable choices are water
development property. soluble or water-redispersible pressure-sensitive adhesives,
Examples of various additives include cationic resin (dye 55 particularly acrylic pressure-sensitive adhesives.
fixer), pigment dispersant, defoaming agent, lubricant, UV Examples of water-soluble acrylic pressure-sensitive adhe
absorbent, sizing agent, fluorescent dye and preservative, sive include those that contain, as the base polymer, a copoly
among others. Of those, it is preferable to use cationic resinas mer of alkoxy alkyl acrylate and styrene Sulfonate or other
it significantly improves the water resistance and color devel copolymeric monomer, or copolymer of (meth)acrylate or
opment property of image. 60 other carboxyl-group-containing vinyl monomer and
The coating machine is not limited in any way, and an air hydroxyl-group-containing monomer or other polymerable
knife coater, bar coater, roll coater, blade coater, curtain monomer that can be used depending on the purpose, among
coater, cast coater, Champlex coater, gravure coater, 2-roll others. Additionally, examples of water-redispersible acrylic
coater, transfer roll coater, etc., can be used. pressure-sensitive adhesive include those that contain, as the
(General Printing) 65 base polymer, a copolymer of (meth)acrylate alkyl ester, car
As a coating layer Suitable for offset printing and gravure boxyl-group-containing vinyl monomer, alkoxy-group-con
printing, it is appropriate to provide a pigment coat layer or taining vinyl monomer and other polymerable monomer that
 US 9,388,532 B2
23 24
can be used depending on the purpose, or copolymer of car measure the time until the test piece tears into two or more
boxylated-rosin-ester-containing vinyl monomer, carboxyl pieces and the time until it completely disintegrates into
group-containing vinyl monomer and water-soluble vinyl fibers, and the averages of five measurements were taken as
monomer, among others. The carboxyl groups in these the floc water dispersion time and fiber water dispersion time,
copolymers may be partially or fully alkali-neutralized salts, respectively.
as necessary, where alkali metal salts, amine salts and alkanol 2) Tensile Strength
amine salts are Suitable choices. Tensile strength was measured according to JIS P 8113.
Cross-linking agent can be blended into these acrylic pres 3) Printability
Sure-sensitive adhesives in order to adjust the pressure-sen Solid printing was performed using a flexo-press (KPrint
sitive adhesive force and water solubility or water dispersion 10
ing Proofer manufactured by Matsuo Sangyo) and the condi
property. Such cross-linking agent is not specifically limited, tion of paper surface was evaluated in terms of lint and fiber
and any of the cross-linking agents customarily used in con detachment. For the ink, solvent-type flexo-ink (H151UPF
ventional acrylic pressure-sensitive adhesives can be selected manufactured by Toyo Ink, Zahn cup No. 4, 25°C., 30 sec
and used as deemed appropriate.
Examples include, among others, 1.2-ethylene diisocyan 15 onds) was used.
ate and other isocyanate cross-linking agents, digly Evaluation standards
cidylethers and other epoxy cross-linking agents, melamine (9: Good solid-printing result
resin, urea resin, dialdehydes, methylol polymer, metal che O: Printing does not produce any problem affecting prac
tical use
late compound, metal alkoxide and metal salts. A: Paper surface had lint
It is also possible to blend into the aforementioned acrylic x: Fibers attached to the rubber printing roll
pressure-sensitive adhesive, any known plasticizer, pressure
sensitive adhesiveness adding agent, colorant, thickener, 4) Paper Surface pH
defoaming agent, leveling agent, plasticizer, fungicide, anti Paper surface pH was measured according to JAPAN
oxidant, etc., as deemed appropriate, in order to adjust the TAPPI No. 49-1, or specifically by dripping wetting agent, or
property and improve the performance if necessary. 25 distilled water, onto the paper, causing the wet paper Surface
Here, plasticizer and pressure-sensitive adhesiveness add to contact electrodes and waiting for 2 minutes, and then
ing agent are preferably water-soluble or water-dispersible. reading the pH value.
Examples of plasticizer include Sugar alcohol and other poly 5)Yellowing Level
hydric alcohols, and polyether polyol, rosin oxidize and other A test piece of 25x25 cm square was prepared according to
alkanol amine salts, among others. Examples of pressure 30 JIS K 7103 and its yellowness was measured using Suga
sensitive adhesiveness adding agent include rosin, dispropor Tester's SM Color Computer, after which the test piece was
tionating rosin, hydrogenated rosin and other alkali metal stored for 7 days in a dark place at 23° C. and 50% RH.
salts, ammonium salt, and polyether ester, among others. Thereafter, yellowness was measured and the yellowness
Any such pressure-sensitive adhesive agent can be directly before storage was subtracted from the yellowness after stor
coated onto the non-coated Surface of the base material to 35 age, to obtain the yellowing level.
provide a pressure-sensitive adhesive layer. Alternately, pres Evaluation Standards
Sure-sensitive adhesive can be applied onto the release-agent O: If the yellowing level was less than 1, “O'” was given to
coated Surface of a backing sheet to provide a pressure-sen indicate that no yellowing occurred.
sitive adhesive layer, after which the layer can be pressured x: If the yellowing level was 1 or greater, “X” was given to
and thus transferred onto the non-coated surface. Whichever 40 indicate that yellowing occurred.
method is used, the pressure-sensitive adhesive layer can have 6) Printability (Text-Specific)
a backing sheet attached to it, so that the backing sheet is 6-1)Thermo-Sensitive Recording Paper (Evaluation Using
removed as desired for use, so as to prevent unnecessary a Thermo-Sensitive Printer)
adhesion when the layer is not in use. Zebra’s “Barcode Printer 140Xill” was used to print on the
The coating amount of the pressure-sensitive adhesive 45 water-dispersible coated papers produced per Examples 13
layer provided on the base material is 3 to 60 g/m, or pref through 22, 25 and Comparative Examples 5 through 9.
The reflective densitometer “Macbeth RD-918 was used
erably 10 to 50 g/m or so, in solid content. If the coating to measure the Surface texture of printed and unprinted areas
amount of pressure-sensitive adhesive is less than 5 g/m, the of the sample printed with the thermal head energy of 0.2 m.J.
pressure-sensitive adhesive sheet will not exhibit enough Evaluation Standards
adhesion performance. If the coating amount of pressure 50
sensitive adhesive exceeds 60 g/m, on the other hand, pres O: If the measured values of printed areas were high,
Sure-sensitive adhesive will easily run off during the manu indicating excellent color development sensitivity,
facturing of pressure-sensitive adhesive sheet or in the while the measured values of unprinted areas were low,
Subsequent processing steps, which is not desirable. indicating minimal Surface coverage and excellent ther
55 mal printability (text-specific), “O'” was given.
EXAMPLES x: If the measured values of surface texture were low in
printed areas and high in unprinted areas, “X” was given
The present invention is explained specifically below using to indicate poor thermal printability (text-specific).
examples. It should be noted, however, that the present inven 6-2) Inkjet Recording Paper (Evaluation Using an Inkjet
tion is not limited to those examples in any way. The evalu 60 Printer)
ation methods used in the examples are described below. Epson’s “PM-970C was used to perform solid printing
These methods were used in all examples. (black) on the water-dispersible coated paper produced per
1) Water Dispersion Time Example 23, and printing density was measured using the
Five test pieces, each of 3x3 cm square, were prepared. reflective densitometer “Macbeth RD-918.” The same printer
Next, 300 ml of deionized water was put in a 300-ml beaker 65 was used to print “fi (a Chinese character) in font 8, and ink
and one of the test pieces was introduced while agitating the seepage was visually evaluated according to the standards
water with a stirrer at 650 rpm. A stopwatch was used to below.
 US 9,388,532 B2
25 26
Evaluation Standards lose by 85.6 percent) and 40 percent by weight of purified
O: If ink was little seeped in the printed area or seeped pulp being needle-leaved mercerized pulp (containing C-cel
slightly but the character could be discriminated without lulose by 97.5 percent, water retention level 138 percent at
problem, “O'” was given to indicate excellent inkjet 450 ml CSF) were blended together and then mixed and
printability. beaten to a freeness of 641 ml CSF to obtain a papermaking
x: If ink seeped in the printed area and there was problem material, to which polyamine resin (Arkofix. 159 manufac
discriminating the character, “X” was given to indicate tured by Ciba Specialty Chemicals) was added as cationic
poor inkjet printability. fixer by 0.9 percent by weight relative to the material in
6-3) Printability equivalent Solid content, along with aqueous solution of car
Solid printing was performed using a flexo-press (KPrint 10 boxylmethyl cellulose sodium salt (hereinafter referred to as
ing Proofer manufactured by Matsuo Sangyo) and the condi “CMC'; Sunrose manufactured by Nippon Paper Industries
tion of paper surface was evaluated in terms of lint and fiber Chemical Division) as water-soluble polymeric electrolyte
detachment. For the ink, alcohol flexo-ink (FB King X manu salt by 2.0 percent by weight in equivalent solid content, after
factured by Toyo Ink) was used. which the mixture was used to manually make a water dis
Evaluation Standards 15 persion paper of 60 g/m in weight. Table 1 shows the mea
O: Good solid-printing result Sured results of water dispersion time, tensile strength, print
A: Paper surface had lint ability and paper Surface pH of this water dispersion paper.
x: Fibers attached to the rubber printing roll
7) Pressure-Sensitive Adhesion Strength EXAMPLE 2
Pressure-sensitive adhesive was coated on the unprinted
(text-specific) side or unprinted side of the base material and A water dispersion paper was produced in the same manner
the coated base material was processed into a pressure-sen as in Example 1, except that the blending amounts of NBKP
sitive adhesive sheet or label, and its pressure-sensitive adhe and mercerized pulp were changed as shown in Table 1.
sion strength was evaluated as described below.
7-1) Preparation of Test Piece 25
Anapplicator bar was used to coat pressure-sensitive adhe EXAMPLE 3
sive (Riki-Dyne manufactured by VIGte(Qnos) onto a sili
cone-coated side of the silicone-coated backing paper (manu A water dispersion paper was produced in the same manner
factured by Lintec) to a dry weight of 30 g/m, after which the as in Example 1, except that the blending amounts of NBKP
adhesive was dried to form a pressure-sensitive adhesive 30 and mercerized pulp were changed as shown in Table 1.
layer.
After aligning the pressure-sensitive adhesive-coated side EXAMPLE 4
of the backing paper with the unprinted (text) side of the base
material, a rubber roller weighing 3 kg was rolled back and A water dispersion paper was produced in the same manner
forth over them twice to pressure-bond, after which the 35
as in Example 1, except that the blending amounts of NBKP
obtained piece was stored for 60 days in a room at 23°C. and and mercerized pulp were changed as shown in Table 1.
50% RH.
7-2) Pressure-Sensitive Adhesion Strength Test
Pressure-sensitive adhesive was coated according to JIS Z EXAMPLE 5
0237 and on day 60 thereafter, three test pieces, each of 25 40
mm in width and 170 mm in length, were cut out. After A water dispersion paper was produced in the same manner
removing the backing paper, each test piece was placed on a as in Example 1, except that, instead of mercerized pulp.
stainless sheet (100x150 mm) with the adhesive-coated side broad-leaved dissolving pulp obtained by Sulfite cooking
contacting the stainless sheet, and then a rubber roller weigh (containing C-cellulose by 92.0 percent, water retention level
ing 3 kg was rolled back and forth over it twice to pressure 45 58 percent at 450 ml CSF) was blended in as purified pulp.
bond the test piece.
The stainless sheet was clamped with the bottom chuck of EXAMPLE 6
the tensile tester and one side of the test piece was clamped
with the top chuck, and then pull-off test was conducted at a A water dispersion paper was produced in the same manner
pulling speed of 300 mm/min, after which pressure-sensitive 50
adhesion strength was measured. as in Example 1, except that, instead of mercerized pulp.
Evaluation Standards broad-leaved dissolving pulp obtained by Sulfite cooking
O: If the pressure-sensitive adhesion strength was 200 (containing C-cellulose by 89.0 percent, water retention level
g/m2 or more, "O" was given to indicate minimal drop 120 percent at 450 ml CSF) was blended in as purified pulp.
in pressure-sensitive adhesion strength over time, mak 55
ing the paper usable as a pressure-sensitive adhesive EXAMPLE 7
sheet.
x: If the pressure-sensitive adhesion strength was less than A water dispersion paper was produced in the same manner
200 g/m2, “O'” was given to indicate significant drop in as in Example 1, except that the amount of CMC added to the
pressure-sensitive adhesion strength over time, making 60
papermaking material was changed to 6.0 percent by weight.
the paper not practically usable as a pressure-sensitive
adhesive sheet.
EXAMPLE 8
EXAMPLE1
65 A water dispersion paper was produced in the same manner
Sixty percent by weight of needle-leaved bleached kraft as in Example 1, except that the blending amount of cationic
pulp (hereinafter referred to as “NBKP containing C-cellu fixer was changed as shown in Table 1.
 US 9,388,532 B2
27 28
EXAMPLE 9 Although the paper surface pH was neutral at 6.8 and water
dispersion property was good, the printability test found
A water dispersion paper was produced in the same manner printability problems caused by detachment of regenerated
as in Example 1, except that the blending amount of cationic cellulose fibers. The regenerated cellulose fibers were highly
fixer was changed as shown in Table 1. purified and C-cellulose content was high, but the fiber sur
face was smooth and did not fibrillate easily, which led to poor
EXAMPLE 10 inter-fiber bonding and behaviors different from what are
normally expected from pulp fibers. Accordingly, the prob
A water dispersion paper was produced in the same manner lem is that fibers produced lint and detached often.
10
as in Example 1, except that the blending amount of cationic Example 1A
fixer was changed as shown in Table 1.
A water-soluble polymer constituted by a solution contain
EXAMPLE 11 ing 4 percent by weight of CMC (Sunrose manufactured by
Nippon Paper Industries Chemical Division, 5 mPa's viscos
A water dispersion paper was produced in the same manner 15 ity in 2 weight-percentaqueous solution at 20°C.) was coated
as in Example 2, except that the blending amounts of cationic onto the water dispersion paper (base paper) produced in
fixer and polymeric electrolyte salt were changed as shown in Example 1 by 9.3 percent by weight (5.6 g/m) relative to the
Table 1. base paper, using the sizing press method, to produce a water
dispersion paper of Example 1A.
EXAMPLE 12 Table 2 shows the measured results of water dispersion
time, tensile strength, printability and paper Surface pH of this
A water dispersion paper was produced in the same manner water dispersion paper.
as in Example 2, except that the blending amounts of cationic The water dispersion paper obtained in Example 1A was
fixer and polymeric electrolyte salt were changed as shown in superior in terms of floc water dispersion time and fiber water
25 dispersion time.
Table 1.
Example 1B
Comparative Example 1
A water dispersion paper was produced in the same manner
A water dispersion paper was produced in the same manner 30
as in Example 1A with the water dispersion paper produced in
as in Example 1, except that only NBKP (containing C-cel Example 1 being used as the base paper, except that additive
lulose by 85.6 percent by weight) was used, with no purified ratio of water-soluble polymer was changed as shown in
pulp blended into the papermaking material. Table 2.
As no purified pulp was blended in, inter-fiber bonding of
paper material fibers was too strong, which made the fiber 35
Example 2A
water dispersion time too long and consequently the obtained
water dispersion paper did not have excellent water disper A water dispersion paper was produced in the same manner
sion property. as in Example 1A, except that the water dispersion paper
produced in Example 2 was used as the base paper and addi
Comparative Example 2 tive ratio of water-soluble polymer was changed as shown in
40
Table 2.
A water dispersion paper was produced in the same manner
as in Example 1, except that only needle-leaved mercerized Example 3A
pulp (containing C-cellulose by 97.5 percent by weight, water
retention level 138 percent at 450 ml CSF) was used, with no A water dispersion paper was produced in the same manner
papermaking fibers blended into the papermaking material. 45
as in Example 1A, except that the water dispersion paper
As the papermaking material only contained purified pulp, produced in Example 3 was used as the base paper.
inter-fiber bonding of paper material fibers was weak and
Sufficient paper strength was not obtained, resulting in low Example 4A
printability.
50 A water dispersion paper was produced in the same manner
Comparative Example 3 as in Example 1A, except that the water dispersion paper
produced in Example 4 was used as the base paper and addi
Forty percent by weight of NBKP (containing C-cellulose tive ratio of water-soluble polymer was changed as shown in
by 85.6 percent) and 60 percent by weight of fiber carboxy Table 2.
lmethyl cellulose Nasalt pulp (substitution degree 0.28) were 55
blended together and then mixed and beaten to a freeness of Example 5A
648 ml CSF, and the obtained papermaking material was used
to manually make a base paper of 60 g/m in weight. A water dispersion paper was produced in the same manner
The sheet had a neutral paper surface pH of 6.9, but its floc as in Example 1A, except that the water dispersion paper
water dispersion time was 264 seconds, which was too long to 60 produced in Example 5 was used as the base paper and addi
call the paper “water dispersion paper.” tive ratio of water-soluble polymer was changed as shown in
Table 2.
Comparative Example 4
Example 6A
A water dispersion paper was produced in the same manner 65
as in Example 1, except that regenerated cellulose fiber (3.3 A water dispersion paper was produced in the same manner
dtexx5 mm) was blended in instead of mercerized pulp. as in Example 1A, except that the water dispersion paper
 US 9,388,532 B2
29 30
produced in Example 6 was used as the base paper and addi produced in Example 12 was used as the base paper and
tive ratio of water-soluble polymer was changed as shown in additive ratio of water-soluble polymer was changed as
Table 2. shown in Table 2.
Example 7A
Comparative Example 1A
A water dispersion paper was produced in the same manner
as in Example 1A, except that the water dispersion paper
produced in Example 7 was used as the base paper. A water dispersion paper was produced in the same manner
Example 1 1A as in Example 1A, except that the water dispersion paper
10 produced in Comparative Example 1 was used as the base
A water dispersion paper was produced in the same manner paper and additive ratio of water-soluble polymer was
as in Example 1A, except that the water dispersion paper changed as shown in Table 2.
produced in Example 11 was used as the base paper and
additive ratio of water-soluble polymer was changed as Comparative Example 2A
shown in Table 2.
Example 12A An attempt was made to coat the water dispersion paper
produced in Comparative Example 2 in the same manner as in
A water dispersion paper was produced in the same manner Example 1A, but the base paper tore in the sizing press pro
as in Example 1A, except that the water dispersion paper cess and water dispersion paper could not be obtained.
TABLE 1.
Examples
1 2 3 4 5 6 7 8

NBKP blending ratio 9% 60 40 8O 10 60 60 60 60

Blending ratio of high C-cellulose 40 60 2O 90 40 40 40 40
pulp %
C-cellulose content of high 97.5 97.5 97.5 97.5 92.0 89.0 97.5 97.5
C-cellulose pulp %
Freeness of blended pulp mlCSF 641 641 635 645 633 636 641 641
Additive ratio of cationic fixer 96 O.9 O.9 O.9 O.9 O.9 O.9 O.9 2
Additive ratio of polymeric 2.O 2 2 2 2 2 6 2
electrolyte salt %
Tensile strength of base paper kN/m 2.55 1.73 3.38 O.S6 2.49 3.09 2.48 2.18
Wet tensile strength of base paper O.O39 O.O26 0.055 O.O14 O.061 O.O68 0.055 O.O3O
kNm
Floc dispersion time sec 22 9 23 4 11 19 10 7
Fiber dispersion time sec 297 192 3OO 28 277 3OO 124 62
Paper surface pH 6.4 6.8 6.7 6.9 7.0 6.9 6.8 6.8
Printability O O (3) O-A O (3) O O
Examples Comparative Examples
9 10 11 12 1 2 3 4

NBKP blending ratio 9% 60 60 40 40 100 O 40 40

Blending ratio of high C-cellulose 40 40 60 60 O 1OO CMC-NA Regenerated
pulp % Salt cellulose
60 60
C-cellulose content of high 97.5 97.5 97.5 97.5 97.5
C-cellulose pulp %
Freeness of blended pulp mlCSF 655 655 641 641 640 700 648 655
Additive ratio of cationic fixer 96 O 5 O O.9 O.9 O.9 O.9 O.9
Additive ratio of polymeric 2 2 5 O 2 2 2 2
electrolyte salt %
Tensile strength of base paper kN/m 1.38 2.26 1.34 1.26 4.87 O.04 4.06 1.76
Wet tensile strength of base paper O.043 O.O29 O.O73 O.OOO O.O68 O.044
kNm
Floc dispersion time sec 13 25 14 11 39 2 264 6
Fiber dispersion time sec 115 3OO 142 215 300s 14 300s 45
Paper surface pH 6.7 6.7 6.6 6.9 6.5 6.8 6.9 6.8
Printability O O O O (3) X O X

TABLE 2
Examples
1B 2A 3A 4A SA

Type of base paper Example 1 Example 1 Example 2 Example 3 Example 4 Example 5

Additive ratio of water-soluble 1.O 5.7 S.6 3.0 6.1
polymer g/m·
 US 9,388,532 B2
31 32
TABLE 2-continued
Additive ratio of water-soluble 9.3 1.7 9.5 9.3 5.2 10.2
polymer%
Tensile strength of water dispersion 4.06 2.78 3.19 4.94 O.61 4.98
paper kN/m
Floc dispersion time of water 2.8 9.0 2.2 4.2 4.0 3.3
dispersion paper Sec
Fiber dispersion time of water 15.2 63.0 9.8 38.6 19.3 18.7
dispersion paper Sec
Paper surface pH 6.8 6.4 6.9 7.0 6.8 7.0
Printability (3) O (3) (3) O-A (3)

Comparative
Examples Examples
6A 7B 11A 12A 1A 2A

Type of base paper Example 6 Example 7 Example1 1 Example 12 Comparative Comparative

Examples 1 Examples 2
Additive ratio of water-soluble 5.7 S.6 6.3 7.1 5.5 Could not be
polymer g/m· coated.
Additive ratio of water-soluble 9.5 9.3 1O.S 11.6 9.2 Could not be
polymer% coated.
Tensile strength of water dispersion 4.39 4.24 3.13 3.64 6.03
paper kN/m
Floc dispersion time of water 5.7 3.1 3.8 3.2 9.2
dispersion paper Sec
Fiber dispersion time of water 56.3 19.4 7.4 21.3 82.3
dispersion paper Sec
Paper surface pH 6.8 6.9 6.5 7.1 6.7
Printability (3) (3) (3) (3) (3)

EXAMPLE 13 (Coating of Under Layer)

30
In this Example, the coating solution for under layer to be
Sixty percent by weight of needle-leaved bleached kraft coated on top of the sealer layer which is coated on one side
pulp (hereinafter referred to as “NBKP containing C-cellu of the base material of the water-dispersible coated paper
lose by 85.6 percent) and 40 percent by weight of needle consists of 100 parts of sintered kaolin (XCI 300 manufac
leaved mercerized pulp (containing C-cellulose by 97.5 per 35
tured by FECC, oil absorption amount 70 ml/100g), 0.2 part
cent, water retention level 138 percent at 450 ml CSF) were of dispersant, 80 parts of 10% PVA solution, and 50 parts of
blended together and then mixed and beaten to a freeness of water. This under layer coating Solution was coated using a
641 ml CSF to obtain a papermaking material, to which Meyer bar to a dry weight of 6 g/m, after which the solution
polyamine resin (Arkofix 159 manufactured by Ciba Spe was dried to form an under layer.
cialty Chemicals) was added as cationic fixer by 0.9 percent 40 (Coating of Thermo-Sensitive Recording Layer)
by weight relative to the material in equivalent Solid content, Next, athermo-sensitive recording layer was formed on top
along with aqueous Solution of carboxylmethyl cellulose of the aforementioned under layer. Composition-wise, the
sodium salt (hereinafter referred to as "CMC': Sunrose coating solution for thermo-sensitive recording layer con
manufactured by Nippon Paper Industries Chemical Divi sisted of 36.0 parts of color developer dispersant, 9.2 parts of
sion) as water-soluble polymeric electrolyte salt by 2.0 per 45 dye dispersant, 12.0 parts of sensitizer dispersant, and 12.0
cent by weight in equivalent solid content. Then, this mixture parts of calcium carbonate (Brilliant-15 manufactured by
was used to produce a handmade paper of 60 g/m in weight. Shiraishi Kogyo, average particle size 0.20-50% dispersant).
A water-soluble polymer constituted by a solution containing This thermo-sensitive recording layer coating Solution was
4 percent by weight of CMC (Sunrose manufactured by Nip coated using a Meyer bar to a dry weight of 5 g/m, after
pon Paper Industries Chemical Division, 5 mPa is viscosity in 50
which the solution was dried (at 50° C.) to form a thermo
2 weight-percent aqueous solution at 20°C.) was coated onto sensitive recording layer. The color developer dispersant, dye
this handmade paper, using the sizing press method, by 9.3 dispersant and sensitizer dispersant used were prepared,
percent by weight (5.6 g/m) relative to the handmade paper, respectively, as follows:
to produce a base material for water-dispersible coated paper. 1 Color developer dispersant: Dispersion of 18.8 parts of
A sealer layer was coated onto the obtained base material, 55
10% PVA aqueous solution, 6.0 parts of 4-hydroxy-4-isopro
and a coating layer was provided on top of the sealer layer. An poxy diphenyl Sulfone and 11.2 parts of water was crushed
under layer and thermo-sensitive recording layer were into particles of 1 um in average particle size using a sand
coated, as the coating layer, and then dried to produce a grinder.
water-dispersible coated paper of Example 13.
(Coating of Sealer Layer) 60 2 Dye dispersant: Dispersion of 2.0 parts of 3-di-n-butyl
A sealer layer was formed on one side of the base material. amino-6-methyl-7-anilinofluoran, 4.6 parts of 10% PVA
Composition-wise, the sealer layer coating solution consisted aqueous Solution and 2.6 parts of water was crushed into
of 53 parts by weight of silica powder (Carplex Powder manu particles of 1 Lim in average particle size using a sand grinder.
factured by DSL. Japan) and 433 parts by weight of 12% PVA 3 Sensitizer dispersant: Dispersion of 4.0 parts of 4-bi
aqueous solution. This sealer layer coating solution was 65 phenyl p-tolyl ether, 5.0 parts of 10% PVA aqueous solution
coated using a Meyer bar to a dry weight of 7 g/m, after and 3.0 parts of water was crushed into particles of 1 um in
which the solution was dried to form a sealer layer. average particle size using a sand grinder.
 US 9,388,532 B2
33 34
A water-dispersible coated paper (thermo-sensitive record EXAMPLE 21
ing paper) was obtained as above.
The obtained water-dispersible coated paper was passed A water-dispersible coated paper was produced in the same
through a mini-Super calender tester (manufactured by Yuri manner as in Example 15, except that the blending amounts of
Roll Machine) at a line pressure of 25 kg/m and paper-passing cationic fixer and polymeric electrolyte salt and additive ratio
speed of 5 m/min, with the coating layer contacting the or water-soluble polymer were changed as shown in Table 4.
chilled roll (room temperature), after which a smoothing pro
cess was applied until the Oken-type Smoothness fell in a EXAMPLE 22
range of 200 to 500 seconds. 10
Table 3 shows the measured results of water dispersion A water-dispersible coated paper was produced in the same
time, yellowing level, printability and paper surface pH of this manner as in Example 15, except that the blending amounts of
water-dispersible coated paper. cationic fixer and polymeric electrolyte salt and additive ratio
or water-soluble polymer were changed as shown in Table 4.
EXAMPLE 1.4
15
EXAMPLE 23
A water-dispersible coated paper was produced in the same
manner as in Example 13, except that the additive ratio of A water-dispersible coated paper was produced in the same
water-soluble polymer was changed as shown in Table 3. manner as in Example 13, except that the thermo-sensitive
recording layer was changed to the inkjet recording layer as
EXAMPLE 1.5 shown in Table 4.

A water-dispersible coated paper was produced in the same EXAMPLE 24

manner as in Example 13, except that the blending amounts of
NBKP and mercerized pulp were changed as shown in Table 25 A water-dispersible coated paper was produced in the same
3. manner as in Example 13, except that the thermo-sensitive
recording layer was changed to the coating layer for general
EXAMPLE 16 printing as shown in Table 4.
A water-dispersible coated paper was produced in the same 30 EXAMPLE 25
manner as in Example 13, except that the blending amounts of
NBKP and mercerized pulp were changed as shown in Table A water-dispersible coated paper was produced in the same
3. manner as in Example 13, except that a sealer layer was
coated onto the opposite side of the base material (non
EXAMPLE 17 35 thermo-sensitive recording layer) with no under layer pro
vided on the base material and no sealer layer provided on the
A water-dispersible coated paper was produced in the same thermo-sensitive recording layer side.
manner as in Example 13, except that the blending amounts of
NBKP and mercerized pulp and additive ratio of water Comparative Example 5
40
soluble polymer were changed as shown in Table 3.
A water-dispersible coated paper was produced in the same
EXAMPLE 1.8 manner as in Example 13, except that only NBKP (containing
C.-cellulose by 85.6 percent) was used without blending any
A water-dispersible coated paper was produced in the same purified pulp into the papermaking material and the additive
manner as in Example 13, except that broad-leaved dissolv 45 ratio of water-soluble polymer was changed as shown in
ing pulp obtained by Sulfite cooking (containing C-cellulose Table 4.
by 92.0 percent, water retention level 59 percent at 450 ml
CSF) was blended in as purified pulp instead of mercerized Comparative Example 6
pulp and the additive ratio of water-soluble polymer was
changed as shown in Table 3. 50 An attempt was made to produce a water-dispersible
coated paper in the same manner as in Example 13, except
EXAMPLE19 that only needle-leaved mercerized pulp (containing C-cellu
lose by 97.5 percent, water retention level 138 percent at 450
A water-dispersible coated paper was produced in the same ml CSF) was used without blending any papermaking fibers
manner as in Example 13, except that broad-leaved dissolv 55 into the papermaking material, but base material for water
ing pulp obtained by Sulfite cooking (containing C-cellulose dispersible coated paper could not be obtained as the base
by 89.0 percent, water retention level 120 percent at 450 ml material tore when the water-soluble polymer was coated.
CSF) was blended in as purified pulp instead of mercerized
pulp and the additive ratio of water-soluble polymer was Comparative Example 7
changed as shown in Table 4. 60
A water-dispersible coated paper was produced in the same
EXAMPLE 20 manner as in Example 13, except that 40 percent by weight of
NBKP and 60 percent by weight of fiber carboxylmethyl
A water-dispersible coated paper was produced in the same cellulose Nasalt pulp (substitution degree 0.28) were blended
manner as in Example 13, except that the blending amount of 65 together and then mixed and beaten to a freeness of 648 ml
water-soluble polymeric electrolyte salt added to the paper CSF, and the obtained papermaking material was used. The
making material was changed as shown in Table 4. sheet had a neutral paper surface pH of 6.9, but its floc water
 US 9,388,532 B2
35 36
dispersion time was 300 seconds or more, which was too long A sealer layer, under layer and thermo-sensitive recording
to call the paper “water dispersion paper.” layer were coated onto one side of the obtained handmade
paper and then dried in the same manner as in Example 13,
Comparative Example 8 after which aqueous sodium carbonate solution of 18 percent
by weight in concentration was coated, as alkalization agent,
A water-dispersible coated paper was produced in the same onto the handmade paper from the non-sensitive recording
manner as in Example 13, except that regenerated cellulose layer side to a dry weight of 5.0gm. Then, water-dispersible
fibers (3.3 dtexx5mm) were blended in instead of mercerized coated paper was produced by turning the water-insoluble
pulp. The paper surface pH was neutral at 6.8 and water handmade paper into the one soluble in water. The obtained
dispersion property was good, but the thermo-sensitive print 10 water-dispersible coated paper was passed through a mini
ability (text-specific) test found that printed areas were faded super calender tester (manufactured by Yuri Roll Machine) at
due to insufficient Smoothness and the paper was not suitable a line pressure of 25 kg/m and paper-passing speed of 5
for thermo-sensitive printing applications. m/min, with the coating layer contacting the chilled roll
(room temperature), after which a smoothing process was
Comparative Example 9 15 applied until the Oken-type smoothness fell in a range of 100
to 200 seconds.
A handmade paper of 55 g/m in weight was produced by Since Sodium carbonate of approx. twice the neutralization
using a papermaking material prepared by blending together equivalent of acid-type fiber carboxylmethyl cellulose was
65 percent by weight of NBKP with a freeness of 600 ml CSF coated, the sheet had an alkaline paper surface pH of 10.5 and
and 35 percent by weight of fiber carboxylmethyl cellulose its floc water dispersion time was 27 seconds, indicating
pulp (Substitution degree 0.43). This handmade paper con appropriate water dispersion property, but the paper turned
tained water-insoluble fiber carboxylmethyl cellulose and yellow significantly over time and was not suitable for
therefore did not have water dispersion property. thermo-sensitive printing applications.
TABLE 3
Examples
13 14 15 16 17 18 19 2O 21

NBKP blending ratio 9% 60 60 40 8O 10 60 60 60 40

Blending ratio of high C-cellulose pulp 90 40 40 60 2O 90 40 40 40 60
Ci-cellulose content% 97.5 97.5 97.5 97.5 97.5 92.0 89.0 97.5 97.5
FreenessmlCSF 641 641 641 635 645 633 636 641 641
Additive ratio of cationic fixer 96 O.9 O.9 O.9 O.9 O.9 O.9 O.9 O.9 O
Additive ratio of polymeric electrolyte salt % 2.0 2.0 2 2 2 2 2 6 5
Additive ratio of water-soluble polymerg?m S.6 1.O 5.7 S.6 3.0 6.1 5.7 S.6 6.3
Additive ratio of water-soluble polymer% 9.3 1.7 9.5 9.3 5.2 10.2 9.5 9.3 1O.S
Attached amount of alkalization agent g/m O O O O O O O O O
Coating layer Thermo- Thermo- Thermo- Thermo- Thermo- Thermo- Thermo- Thermo- Thermo
sensitive sensitive sensitive sensitive sensitive sensitive sensitive sensitive sensitive
Sealer layer One side One side One side One side One side One side One side One side One side
Floc dispersion time 15.7 29.6 13.2 23.0 23.2 20.1 27.3 18.2 14.8
Fiber dispersion time 59.3 79.0 40.3 57.5 48.2 44.9 70.3 46.6 33.3
Yellowing level O O O O O O O O O
Paper surface pH 7.1 6.8 7.0 7.0 6.9 7.1 6.9 6.9 6.8
Suitability for thermo-sensitive printing O O O O O O O O O
Suitability for inkjet printing
General printability
Pressure-sensitive adhesion strength O O O O O O O O O

TABLE 4
Examples Comparative Examples
22 23 24 25 5 6 7 8 9

NBKP blending ratio 9% 40 60 60 60 1OO O 40 40 65

Blending ratio of high C-cellulose pulp 90 60 40 40 40 O 1OO CMC-NA Regenerated Acid-type
Salt cellulose CMC
60 60 35
C-cellulose content of high a-cellulose pulp 90 97.5 97.5 97.5 97.5 97.5
Freeness of blended pulp mlCSF 641 641 641 641 640 700 648 655 600
Additive ratio of cationic fixer 96 O.9 O.9 O.9 O.9 O.9 O.9 O.9 O.9 O
Additive ratio of polymeric electrolyte salt % O 2.0 2O 2.0 2 2 2.0 2.O O
Additive ratio of water-soluble polymerg?m 7.1 S.6 S.6 S.6 5.5 Could not S.6 S.6 O
be coated.
Additive ratio of water-soluble polymer% 11.6 9.3 9.3 9.3 9.2 Could not 9.3 9.3 O
be coated.
Attached amount of alkalization agent g/m’ O O O O O O O O S.O
Coating layer Thermo- IJ General Thermo- Thermo- Thermo- Thermo- Thermo
sensitive sensitive sensitive sensitive sensitive sensitive
Sealer layer One side One side One side One side One side One side One side One side
Floc dispersion time 19.5 11.2 10.1 16.1 42.9 249 17.4 27.0
 US 9,388,532 B2
37 38
TABLE 4-continued
Examples Comparative Examples
22 23 24 25 5 6 7 8 9

Fiber dispersion time SS.4 36.5 33.4 60.3 3OO< 3OO< 22.9 79.8
Yellowing level O O O O O O O X
Paper surface pH 7.0 6.9 6.9 7.0 7.1 6.9 6.8 1O.S
Suitability for thermo-sensitive printing O O O O X O
Suitability for inkjet printing O
General printability O
Pressure-sensitive adhesion strength O O O O O O O O

We claim: contain a hydroxyl group, hydroxymethyl group,

1. A water dispersion paper made of wood pulp and/or 15 hydroxyethyl group, or other substitution group,
non-wood pulp, wherein said water dispersion paper is char wherein the above Substitution groups are not counted
acterized in that purified pulp containing C-cellulose by 88 toward the carbon number, and n represents a positive
percent by weight or more accounts for 15 to 95 percent by integer.
weight of all pulp, and the water dispersion paper contains a 9. A water dispersion paper according to claim 1, charac
water-soluble polymeric electrolyte salt. terized in that it does not contain regenerated cellulose fibers,
2. A water dispersion paper made of wood pulp and/or fiber carboxylmethyl cellulose or fiber carboxylmethyl cellu
non-wood pulp, wherein purified pulp containing hemi-cel lose Nasalt.
lulose by less than 12 percent by weight accounts for 15 to 95 10. A water dispersion paper according to claim 1, charac
percent by weight of all pulp, and the water dispersion paper terized in that its paper surface pH is 6 to 8.
contains a water-soluble polymeric electrolyte salt. 25
11. A water dispersion paper according to claim 1, charac
3. A water dispersion paper according to claim 2, charac
terized in that it does not contain regenerated cellulose fibers, terized in that its floc water dispersion time, defined as the
fiber carboxylmethyl cellulose, or fiber carboxylmethyl cel time until a test piece of 3x3 cm square, put in a beaker
lulose Nasalt. containing water, tears into two or more pieces when agitated
4. A water dispersion paper according to claim 2, charac 30 with a stirrer at 650 rpm, is within 30 seconds.
terized in that its paper surface pH is 6 to 8. 12. A water dispersion paper according to claim 1, wherein
5. A water dispersion paper according to claim 2, charac the water-soluble polymeric electrolyte salt is at least one
terized in that its floc water dispersion time, defined as the selected from the group consisting of carboxymethyl cellu
time until a test piece of 3x3 cm square, put in a beaker lose salt, alginate, carboxymethylated Starch, polyacrylate,
containing water, tears into two or more pieces when agitated 35 polymethacrylate, anionic polyacrylamide, and amphoteric
with a stirrer at 650 rpm, is within 30 seconds. polyacrylamide.
6. A water dispersion paper according to claim 2, wherein 13. A water dispersion paper according to claim 1, further
the water-soluble polymeric electrolyte salt is at least one containing a cationic fixer.
selected from the group consisting of carboxymethyl cellu 14. A water dispersion paper according to claim 13,
lose salt, alginate, carboxymethylated Starch, polyacrylate, 40 wherein the cationic fixer is a polyamine resin expressed by
polymethacrylate, anionic polyacrylamide, and amphoteric General Formula (1) below:
polyacrylamide.
7. A water dispersion paper according to claim 2, further (1)
containing a cationic fixer. R
8. A water dispersion paper according to claim 7, wherein 45
the cationic fixer is a polyamine resin expressed by General CH-CH-CH-N"
Formula (1) below: OH
| Cr
R. '"

(1) 50 wherein R represents an alkyl group with 1 to 10 carbons

R that may include a hydroxyl group, hydroxymethyl
CH-CH-CH-N" group, hydroxyethyl group, or other Substitution group,
C wherein the above Substitution groups are not counted
OH R. '" toward the carbon number; R represents a hydrogen
55 atom or alkyl group with 1 to 10 carbons that may
wherein R represents an alkyl group with 1 to 10 carbons contain a hydroxyl group, hydroxymethyl group,
that may include a hydroxyl group, hydroxymethyl hydroxyethyl group, or other substitution group,
group, hydroxyethyl group, or other Substitution group, wherein the above Substitution groups are not counted
wherein the above Substitution groups are not counted toward the carbon number, and n represents a positive
toward the carbon number, R represents a hydrogen 60 integer.
atom or alkyl group with 1 to 10 carbons that may