USOO7767738B2

(12) United States Patent (10) Patent No.: US 7,767,738 B2

Gaggar et al. (45) Date of Patent: *Aug. 3, 2010
(54) TRANSPARENT POLYCARBONATE 2.999,835 A 9/1961 Goldberg
POLYESTER COMPOSITION AND PROCESS 3,038,365 A 6, 1962 Schnell et al.
3,047,539 A 7/1962 Pengilly
(75) Inventors: Satish Kumar Gaggar, Parkersburg, 3,153,008 A
3,334,154 A
10,8, 1964 Fox
1967 Kim
WV (US); Johannes Jacobus de Moor, 3,444,237 A 5, 1969 Jaffe
Halsteren (NL); Paul Honigfort, 3,635,895 A 1, 1972 Krae
Gaithersburg, MD (US); Gabrie 4,001,184 A 1, 1977 Scott
Hoogland, Breda (NL); Mark van 4,083,896 A * 4, 1978 Moran et al. .................. 525,84
Heeringen, Bergen op Zoom (NL); 4,123,436 A 10/1978 Holub et al.
Eelco M. S. van Hamersveld, 4,125,572 A 11, 1978 Scott
Raamsdonksveer (NL) 4,131,575 A 12/1978 Adelmann et al.
4,188,314 A 2f1980 Fox et al.
(73) Assignee: Sabic Innovative Plastics IP B.V., 4.264,487 A 4, 1981 Fromuth et al.
Bergen op Zoom (NL) 4,292.233 A 9, 1981 Binsacket al.
4,391,954 A 7, 1983 Scott
(*) Notice: Subject to any disclaimer, the term of this 4,754,064 A
4,786,692 A
6, 1988 Lillwitz
11/1988 Allen et al.
patent is extended or adjusted under 35 4,897.453 A 1/1990 Flora et all
U.S.C. 154(b) by 795 days. 5,091,010 A 2/1992 Souma et al.
5,132,360 A 7, 1992 Machado et al.
This patent is Subject to a terminal dis- 5,302.646 A 4/1994 Vilasagar et al.
claimer. 5,321,056 A 6/1994 Carson et al.
5,367,016 A * 1 1/1994 Miyama et al. ............. 524,537
(21) Appl. No.: 11/245,462 5,409,967 A 4/1995 Carson et al.
5,441,997 A 8, 1995 Walsh et al.
(22) Filed: Oct. 5, 2005 5,478,896 A 12, 1995 Scott
5,494,969 A 2f1996 Abe et al.
(65) Prior Publication Data 5,510,398 A 4/1996 Clark et al.
5,512,631 A 4/1996 Jalbert et al.
US 2006/0205895A1 Sep. 14, 2006 5,614,589 A 3, 1997 Niznik et al.
5,718,753 A 2f1998 Suzuki et al.
Related U.S. Application Data 5,731,380 A * 3/1998 Golder ........................ 525,64
5,814,712 A 9, 1998 Gallucci et al.
(63) Continuation of application No. 10/373,547, filed O 5,859,119 A 1/1999 GN a
Feb. 24, 2003, now Pat. No. 6,989,190, which is a 5,891.962 A 4/1999 OtSuzuki et al.
continuation-in-part of application No. 09/891,731, 6,040,382 A 3/2000 Hanes
filed on Jun. 26, 2001, now abandoned, and a continu- 6,136,441 A 10/2000 MacGregor et al.
ation-in-part of application No. 09/690,341, filed on
Oct. 17, 2000, now abandoned, and a continuation-in- FOREIGN PATENT DOCUMENTS
part of application No. 09/690,342, filed on Oct. 17, EP O426466 5, 1991
2000, now abandoned. WO WO99/O2594 1, 1999
WO WO-99.63OO2 12/1999
(51) Int. Cl. k .
COSL 69/00 (2006.01) cited by examiner
COL 67/02 (2006.01) Primary Examiner David Buttner
(52) U.S. Cl. ......................... 524/88: 524/439; 524/440; (74) Attorney, Agent, or Firm—Larson & Anderson, LLC
524/441:524/449; 525/67: 525/133
(58) Field of Classification Search ....................... None (57) ABSTRACT
See application file for complete search history.
(56) References Cited Disclosed is a transparent/translucent molding composition
and process for making prepared from an impact modifier and
U.S. PATENT DOCUMENTS a resin blend of polycarbonate and a cycloaliphatic polyester
2.465,319 A 3, 1949 Rex et al. having a matching index of refraction.
2,675,390 A 4, 1954 Rosenblatt
2,888.484 A 5, 1959 Dehmet al. 11 Claims, No Drawings
 US 7,767,738 B2
1. 2
TRANSPARENT POLYCARBONATE styrene and alkyl(methyl)acrylate) to match the RI of a rub
POLYESTER COMPOSITION AND PROCESS bery component. It’s also possible to modify the rubbery
component to match the RI of the polymer matrix, like in U.S.
This application is a continuation of U.S. patent applica Pat. Nos. 5,321,056 and 5,409,967 assigned to Rohm and
tion Ser. No. 10/373,547, filed on Feb. 24, 2003, now U.S. Pat. Haas. The focus of all these patents is to chemically modify
No. 6,989,190, which was continuation-in-part of U.S. patent the ingredients to match RI to achieve transparency. Matching
application Ser. Nos. 09/891,731, filed Jun. 26, 2001 and now RI to achieve transparency is as such not a novelty.
abandoned; 09/690,341, filed Oct. 17, 2000 and now aban U.S. Pat. No. 5,859,119 to Hoefflin relates to reinforced,
doned; and 09/690,342, filed Oct. 17, 2000 and now aban molding compositions with desirable ductility and melt flow
doned, all of which are incorporated herein by reference. 10 properties. The composition contains a cyclo aliphatic poly
ester resin, an impact modifying amorphous resin which
FIELD OF THE INVENTION increases the ductility of the polyester resin but reduces the
melt flow properties thereof, and a high molecular weight
This invention relates to transparent or translucent thermo polyetherester polymer which increases the melt flow prop
plastic molding compositions, optionally containing visual 15 erties of the polyester polymer without reducing the ductility
effect colorants and other additives and processes for produc thereof, and a glass filler to reinforce and stiffen the compo
ing Such compositions. sition and form a reinforced molding composition. This
invention is focussed on opaque PC blends, rather than trans
BACKGROUND OF THE INVENTION parent blends.
U.S. Pat. No. 4,188.314 describes shaped articles (such as
Polycarbonate (PC) is a high-performance plastic with sheet and helmets) of blends of 25-98 parts by weight (pbw)
good impact strength. In addition to ductility (impact of an aromatic polycarbonate and 2-75pbw of a poly cyclo
strength), general-purpose PC has high transparency, good hexane dimethanol phthalate where the phthalate is from
dimensional stability, low water absorption, good stain resis 5-95% isophthalate and 95-10% terephthalate. Articles with
tance and a wide range of colorability. A weak area for PC is 25 enhanced solvent resistance and comparable optical proper
its relatively limited range of chemical resistance, which ties and impact to the base polycarbonate resin and Superior
necessitates careful appraisal of applications involving con optical properties to an article shaped from a polycarbonate
tact with certain organic solvents, some detergents, strong and an aromatic polyester, such as polyalkylene terephtha
alkali, certain fats, oils and greases. Also, another weak area late, are disclosed.
of PC is that it has a high melt viscosity which makes it 30 There are other patents that deal with polycarbonate poly
difficult to mold. Medium to high flow PC grades suffer from cyclohexane dimethanol phthalate blends for example: U.S.
the fact that the low temperature ductility is sacrificed for a Pat. Nos. 4,125,572; 4,391,954; 4,786,692; 4,897,453 and
better flow. Finally, PC formulations with visual-effect addi 5,478,896. U.S. Pat. No. 5,478,896 relates to transparent
tives like metallic type pigments or mineral flakes are in polycarbonate blends with 10-99% polyester of CHDM with
general very brittle at room temperature. This invention deals 35 Some minor amount of aliphatic diol and iso and terephthalic
with these shortcomings and as Such proposes a material that acid. U.S. Pat. No. 4,786,692 relates to a 2-98% aromatic
has an unique property profile in terms of transparency, polycarbonate blend with a polyester made of cyclohexane
improved chemical resistance, higher flow and low, tempera dimethanol (CHDM) and ethylene glycol (EG) in a 1:1 to 4:1
ture ductility at -20 to -40° C., even with special-effect ratio with iso and terephthalic acid. U.S. Pat. No. 4.391.954
colorants. 40 describes compatible compositions of non halogen polycar
A widely used method to increase low temperature impact bonate (PC) and amorphous polyesters of CHDM and a spe
resistance, is the addition of impact modifiers to the PC com cific iso?tere phthalate mixture. U.S. Pat. No. 4,125,572
positions. Adding minor amounts of methylacrylate-butadi relates to a blend of 40-95% PC, 5-60% polybutylene tereph
ene-styrene (MBS) rubbers or Acrylonitrile-butadiene (ABS) thalate (PBT) 1-60% and 1-60% an aliphatic/cycloaliphatic
rubbers results in lower D/B transition temperatures. The 45 iso?terephthalate resin. U.S. Pat. No. 4,897,453 describes
major drawback of these modifications is that, even with only blends of 10-90% PC, 10-90% of a polyester of 0.8-1.5IV.
1% addition levels, the transparency decreases, taking away comprised of 1,4-cyclohexane dicarboxylic acid, 70% trans
one of the key properties of PC. isomer, CHDM and 15-50 wt.% poly oxytetramethylene
This opaqueness is caused by the relatively high refractive glycol with 0-1.5 mole % branching agent. Also claimed are
index (RI) of the aromatic PC (1.58) compared to the more 50 molded or extruded articles of the composition.
aliphatic rubbery and/or siloxane components, which have R
values in the range 1.48-1.56. SUMMARY OF THE INVENTION
U.S. Pat. No. 6,040,382 describes how optical clarity of a
blend of 2 transparent, immiscible, polymers can be improved The present invention provides compositions with
by addition of a third polymer which is selectively miscible 55 improved ductility and melt flow properties, and good base
with one of the two original immiscible polymers. The con line transparency, which can then be reduced if and as desired
cept is based on matching refractive indexes. This patent is for a specific application by the addition of visual-effects
directed to compositions of monovinyl aromatic-conjugated additives. The composition comprises a uniform blend of:
diene copolymers (like styrene-butadiene block co-poly (a) a miscible resin blend of a polycarbonate resin and a
mers), Styrene-maleic anhydride copolymers (SMA) and 60 cycloaliphatic polyester resin, said cycloaliphatic poly
poly (alpha-methylstyrene). ester resin comprising the reaction product of an ali
U.S. Pat. Nos. 5,891,962; 5,494,969; and 5,614,589: phatic C-C diol or chemical equivalent and a C-C,
respectively, describe specific formulations of rubber modi aliphatic diacid or chemical equivalent, said
fied styrene; cycloolefin polymer composites; and methacry cycloaliphatic polyester resin containing at least about
late-acrylonitrile-butadiene-styrene copolymers with ure 65 80% by weight of a cycloaliphatic dicarboxylic acid, or
thane copolymer. In these compositions, polymers are being chemical equivalent, and/or of a cycloaliphatic diol or
replaced by co-polymers (fi. polystyrene by a co-polymer of chemical equivalent;
 US 7,767,738 B2
3 4
(b) an impact modifying amorphous resin having a refrac carbon radical containing from 1 to about 15 carbon atoms;
tive index from about 1.51 to about 1.58 for increasing each X is independently selected from the group consisting of
the low temperature ductility of the resin molding com hydrogen, halogen, and a monovalent hydrocarbon radical
position; Such as an alkyl group of from 1 to about 8 carbon atoms, an
wherein the proportions in the blend of polycarbonate and the aryl group of from 6 to about 18 carbon atoms, an arylalkyl
cycloaliphatic polyester resin are selected so that the index of group of from 7 to about 14 carbon atoms, analkoxy group of
refraction substantially matches the index of refraction of from 1 to about 8 carbon atoms; and m is 0 or 1 and n is an
said impact modifier. integer of from 0 to about 5. Ar" may be a single aromatic ring
In one embodiment, transparent and low temperature duc like hydroquinone or resorcinol, or a multiple aromatic ring
tile polycarbonate (PC) blends are obtained via the addition 10 like biphenol or bisphenol A.
of poly(cyclohexane dimethanol cyclohexane dicarboxylate) The dihydric phenols employed are known, and the reac
(PCCD) and an impact modifier. The complete miscibility of tive groups are thought to be the phenolic hydroxyl groups.
PC and PCCD permits the matching of refractive index (RI) Typical of some of the dihydric phenols employed are bis
of the impact modifier with the RI of the PC/PCCD blend, by phenols such as bis(4-hydroxyphenyl)methane, 2.2-bis(4-hy
adjusting the PC/PCCD ratio. Examples of such impact modi 15 droxyphenyl)propane (also known as bisphenol-A), 2.2-bis
fiers are MBS/ABS type of rubbers with a particle size range (4-hydroxy-3,5-dibromo-phenyl)propane; dihydric phenol
from 50-1000 nm, the rubber being butadiene or styrene ethers such as bis(4-hydroxyphenyl)ether, bis(3,5-dichloro
butadiene with styrene content of up to 40%. Styrene to 4-hydroxyphenyl)ether; p.p'-dihydroxydiphenyl and 3,3'-
acrylonitrile ratio in ABS rubbers can be between 100/0 and dichloro-4,4'-dihydroxydiphenyl; dihydroxyaryl sulfones
50/50 with a preferred ratio of 80/20 to 70/30. Typical such as bis(4-hydroxyphenyl)sulfone, bis(3,5-dimethyl-4-
examples are ABS 415 (RI=1.542) and ABS 336 (RI=1.546), hydroxyphenyl)sulfone, dihydroxybenzenes such as resorci
both produced by GE Plastics and BTA702, BTA736, being nol, hydroquinone, halo- and alkyl-substituted dihydroxy
MBS materials and produced by Rohm & Haas. All these benzenes such as 1,4-dihydroxy-2,5-dichlorobenzene, 1,4-
rubbers are used in the PVC market as impact modifiers to dihydroxy-3-methylbenzene; and dihydroxydiphenyl
improve the toughness of PVC without loosing the transpar 25 sulfides and sulfoxides such as bis(4-hydroxyphenyl)sulfide,
ency. bis(4-hydroxy-phenyl)sulfoxide and bis(3,5-dibromo-4-hy
The application further provides a method for the produc droxyphenyl)sulfoxide. A variety of additional dihydric phe
tion of compositions with improved ductility and melt flow nols are available and are disclosed in U.S. Pat. Nos. 2,999,
properties, and good baseline transparency, which can then be 835, 3,028,365 and 3,153,008; all of which are incorporated
reduced if and as desired for a specific application by the 30 herein by reference. It is, of course, possible to employ two or
addition of visual-effects additives. In accordance with one more different dihydric phenols or a combination of a dihy
embodiment of the method of the invention, a miscible resin dric phenol with a glycol.
blend of a polycarbonate resin and a cycloaliphatic polyester The carbonate precursors are typically a carbonylhalide, a
resin is prepared. The proportions of the polycarbonate resin diarylcarbonate, or a bishaloformate. The carbonyl halides
and the cycloaliphatic polyester resin are selected Such that 35 include, for example, carbonyl bromide, carbonyl chloride,
the blend has a refractive index that is intermediate between and mixtures thereof. The bishaloformates include the bisha
the refractive indices of the two components, and that sub loformates of dihydric phenols such as bischloroformates of
stantially matches the refractive index of an impact modifier 2.2-bis(4-hydroxyphenyl)-propane, hydroquinone, and the
which is added to form the final composition. like, or bishaloformates of glycol, and the like. While all of
40 the above carbonate precursors are useful, carbonyl chloride,
DETAILED DESCRIPTION OF THE INVENTION also known as phosgene, and diphenyl carbonate are pre
ferred.
The composition of the present invention comprise mis The aromatic polycarbonates can be manufactured by any
cible resinblend of a polycarbonate resin and a cycloaliphatic processes Such as by reacting a dihydric phenol with a car
polyester resin, said cycloaliphatic polyester resin compris 45 bonate precursor, Such as phosgene, a haloformate or carbon
ing the reaction product of an aliphatic C-C diol or chemi ate ester in melt or solution. U.S. Pat. No. 4,123,436 describes
cal equivalent and a C-C aliphatic diacid or chemical reaction with phosgene and U.S. Pat. No. 3,153,008 describes
equivalent, said cycloaliphatic polyester resin containing at a transesterification process.
least about 80% by weight of a cycloaliphatic dicarboxylic Preferred polycarbonate will be made of dihydric phenols
acid, or chemical equivalent, and/or of a cycloaliphatic diolor 50 that result in resins having low birefringence for example
chemical equivalent. dihydric phenols having pendant aryl or cup shaped aryl
Polycarbonate Resin groups like:
Polycarbonates useful in the invention comprise the diva Phenyl-di(4-hydroxyphenyl)ethane(acetophenone bisphe
lent residue of dihydric phenols, Ar", bonded through a car nol):
bonate linkage and are preferably represented by the general 55 Diphenyl-di(4-hydroxyphenyl)methane(benzophenone
formula III: bisphenol):
2.2-bis(3-phenyl-4-hydroxyphenyl)propane
2.2-bis-(3,5-diphenyl-4-hydroxyphenyl)propane;
60
bis-(2-phenyl-3-methyl-4-hydroxyphenyl)propane;
2,2'-bis(hydroxyphenyl)fluorene:

(C) oil-(C) pi

65
1,1-bis(5-phenyl-4-hydroxyphenyl)cyclohexane:
3,3'-diphenyl-4,4'-dihydroxy diphenyl ether;
2.2-bis(4-hydroxyphenyl)-4,4-diphenylbutane;
1,1-bis(4-hydroxyphenyl)-2-phenyl ethane;
wherein A is a divalent hydrocarbon radical containing from 2.2-bis(3-methyl-4-hydroxyphenyl)-1-phenylpropane;
1 to about 15 carbon atoms or a substituted divalent hydro 6,6'-dihdyroxy-3,3,3',3'-tetra methyl-1,1'-spiro (bis)indane;
 US 7,767,738 B2
5 6
(hereinafter “SBI), or dihydric phenols derived from spiro 50 mole% of cyclic diacid and/or cyclic diol components, the
bindane of formula IV: remainder, if any, being linear aliphatic diacids and/or diols.
The cyclic components assist by imparting good rigidity, to
the polyester and to allow the formation of transparent blends
R CH due to favorable interaction with the polycarbonate resin.
(R)p
The polyester resins are typically obtained through the
(R)
Co 10
condensation or ester interchange polymerization of the diol
ordiol equivalent component with the diacid or diacid chemi
cal equivalent component. Two types of cycloaliphatic poly
esters can be used with BPA-based polycarbonate to give the
compositions and articles of this invention. The most pre
CH R2 ferred polyester molecules are derived from cycloaliphatic
diol and cycloaliphatic diacid compounds, for example poly
Units derived from SBI and its 5-methyl homologue are 15 cyclohexane dimethanol cyclohexyl dicarboxylate (PCCD).
preferred, with SBI being most preferred. Polyesters having only one cyclic unit may also be useful. An
extra advantage of adding these aliphatic polyesters to PC is
Other dihydric phenols which are typically used in the that their low glass transition temperature (Tg) improves the
preparation of the polycarbonates are disclosed in U.S. Pat. flow of PC (or impact modified PC) significantly, resulting in
Nos. 2,999,835, 3,038,365, 3,334,154 and 4,131,575. an overall very favorable flow/impact balance. Another
Branched polycarbonates are also useful. Such as those advantage is that the polyester improves the overall chemical
described in U.S. Pat. Nos. 3,635,895 and 4,001,184. Poly resistance towards various chemicals that are very aggressive
carbonate blends include blends of linear polycarbonate and towards straight PC. Examples of these chemicals are
branched polycarbonate. acetone, coppertone, gasoline, toluene etc.
It is also possible to employ two or more different dihydric 25 Rand R1 are preferably cycloalkyl radicals independently
phenols or a copolymer of a dihydric phenol with an aliphatic selected from the following formula:
dicarboxylic acids like; dimer acids, dodecane dicarboxylic
acid, adipic acid, azelaic acid in the event a carbonate copoly
mer or interpolymer rather thana homopolymer is desired for
use in the preparation of the polycarbonate mixtures of the 30
invention. Most preferred are aliphatic C5 to C12 diacid
copolymers.
The preferred polycarbonates are preferably high molecular
weight aromatic carbonate polymers have an intrinsic viscos
35
---O)-cis-cis- s
ity (as measured in methylene chloride at 25°C.) ranging
from about 0.30 to about 1.00 d1/gm. Polycarbonates may be
branched or unbranched and generally will have a weight
average molecular weight of from about 10,000 to about
200,000, preferably from about 20,000 to about 100,000 as
measured by gel permeation chromatography. It is contem
plated that the polycarbonate may have various known end
40 --O)-cis-O)-cis- s
t
groups.
Cycloaliphatic Polyester Resin
The cycloaliphatic polyester resin comprises a polyester 45
--O--O)-cis CH
CH3
having repeating units of the formula I:

O O
( ) C

CH
( ) s

50
--O-R-O-C-R1-C--

where at least one R or R1 is a cycloalkyl containing radical.

The polyester is a condensation product where R is the
residue of an aryl, alkane or cycloalkane containing diol
having 6 to 20 carbon atoms or chemical equivalent thereof,
55 -O-O-
and R1 is the decarboxylated residue derived from an aryl,
aliphatic or cycloalkane containing diacid of 6 to 20 carbon
atoms or chemical equivalent thereof with the proviso that at 60
least one R or R1 is cycloaliphatic. Preferred polyesters of the The preferred cycloaliphatic radical R1 is derived from the
invention will have both R and R1 cycloaliphatic. 1,4-cyclohexyl diacids and most preferably greater than 70
The present cycloaliphatic polyesters are condensation mole % thereof in the form of the trans isomer. The preferred
products of aliphatic diacids, or chemical equivalents and cycloaliphatic radical R is derived from the 14-cyclohexyl
aliphatic diols, or chemical equivalents. The present 65 primary diols such as 1,4-cyclohexyl dimethanol, most pref
cycloaliphatic polyesters may be formed from mixtures of erably more than 70 mole % thereof in the form of the trans
aliphatic diacids and aliphatic diols but must contain at least isomer.
 US 7,767,738 B2
7 8
Other diols useful in the preparation of the polyester resins diacids, and the most favored chemical equivalent comprises
of the present invention are straight chain, branched, or the dimethyl ester of the acid, particularly dimethyl-1,4-cy
cycloaliphatic alkane diols and may contain from 2 to 12 clohexane-dicarboxylate.
carbon atoms. Examples of Such diols include but are not A preferred cycloaliphatic polyester is poly(cyclohexane
limited to ethylene glycol; propylene glycol, i.e., 1.2- and 5 1,4-dimethylene cyclohexane-1,4-dicarboxylate) also
1,3-propylene glycol; 2.2-dimethyl-1,3-propane diol; referred to as poly(1,4-cyclohexane-dimethanol-1,4-dicar
2-ethyl, 2-methyl, 1,3-propane diol; 1.3- and 1,5-pentane boxylate) (PCCD) which has recurring units of formula II:

-()- ci-O)-cis--O- ci-O)-col pi

diol, dipropylene glycol, 2-methyl-1,5-pentanediol; 1.6-hex With reference to the previously set forth general formula,
ane diol; dimethanol decalin, dimethanol bicyclooctane; 1,4- for PCCD, R is derived from 1.4 cyclohexane dimethanol:
cyclohexane dimethanol and particularly its cis- and trans and R1 is a cyclohexane ring derived from cyclohexanedicar
isomers; 2,2,4,4-tetramethyl-1,3-cyclobutanediol boxylate or a chemical equivalent thereof. The favored PCCD
(TMCBD), triethylene glycol; 1,10-decane diol; and mix has a cis/trans formula.
tures of any of the foregoing. Preferably a cycloaliphatic diol The polyester polymerization reaction is generally run in
or chemical equivalent thereof and particularly 1.4-cyclohex the melt in the presence of a Suitable catalyst Such as a tetrakis
ane dimethanol or its chemical equivalents are used as the diol 25 (2-ethylhexyl) titanate, in a Suitable amount, typically about
component.
Chemical equivalents to the diols include esters, such as 50 to 200 ppm of titanium based upon the final product.
dialkylesters, diaryl esters and the like. The preferred aliphatic polyesters used in the present trans
The diacids useful in the preparation of the aliphatic poly parent molding compositions have a glass transition tempera
ester resins of the present invention preferably are 30
ture (Tg) which is above 50° C., more preferably above 80° C.
cycloaliphatic diacids. This is meant to include carboxylic and most preferably above about 100° C.
acids having two carboxyl groups each of which is attached to Also contemplated herein are the above polyesters with
a saturated carbon. Preferred diacids are cyclo or bicyclo from about 1 to about 50 percent by weight, of units derived
aliphatic acids, for example, decahydro naphthalene dicar from polymeric aliphatic acids and/or polymeric aliphatic
boxylic acids, norbornene dicarboxylic acids, bicyclooctane polyols to form copolyesters. The aliphatic polyols include
dicarboxylic acids, 1,4-cyclohexanedicarboxylic acid or 35
chemical equivalents, and most preferred is trans-1,4-cyclo glycols. Such as poly(ethylene glycol) or poly(butylene gly
hexanedicarboxylic acid or chemical equivalent. Linear col. Such polyesters can be made following the teachings of
dicarboxylic acids like adipic acid, azelaic acid, dicarboxyl for example, U.S. Pat. Nos. 2,465,319 and 3,047,539.
dodecanoic acid and Succinic acid may also be useful. 40
Miscible Resin Blend
Cyclohexanedicarboxylic acids and their chemical equiva
lents can be prepared, for example, by the hydrogenation of In the miscible resin blend of the invention, the preferred
cycloaromatic diacids and corresponding derivatives Such as polycarbonate will be composed of units of BPA, SBI bisphe
isophthalic acid, terephthalic acid or naphthalenic acid in a nol, aryl Substituted bisphenols, cycloaliphatic bisphenols
Suitable solvent such as water or acetic acid using a suitable 45
and mixtures thereof. The most preferred materials will be
catalysts such as rhodium Supported on a carrier Such as blends where the polyester has both cycloaliphatic diacid and
carbon or alumina. See, Friefelder et al., Journal of Organic cycloaliphatic diol components specifically polycyclohexane
Chemistry, 31, 3438 (1966); U.S. Pat. Nos. 2,675,390 and dimethanol cyclohexyl dicarboxylate (PCCD).
4,754.064. They may also be prepared by the use of an inert In the miscible resin blends, a ratio of cycloaliphatic poly
liquid medium in which a phthalic acid is at least partially 50 ester to polycarbonate in the range of 80:20 to 5:95% by
soluble under reaction conditions and with a catalyst of pal weight of the entire mixture is preferred. Blends from 70:30
ladium or ruthenium on carbon or silica. See, U.S. Pat. Nos. to 40:60 are most preferred.
2,888,484 and 3,444,237. The refractive index of the miscible resin blend is deter
Typically, in the hydrogenation, two isomers are obtained
in which the carboxylic acid groups are in cis- or trans mined by the components and the amounts of each. The
positions. The cis- and trans-isomers can be separated by 55 refractive index of pure polycarbonate (PC) is 1.586 while
crystallization with or without a solvent, for example, n-hep that of PCCD is 1.516. In a mixture of polycarbonate and poly
tane, or by distillation. The cis-isomer tends to blend better; (1,4-cyclohexanedimethanol-1,4-cyclohexanedicarboxylate
however, the trans-isomer has higher melting and crystalliza the refractive index of the mixture, y, varies as the function
tion temperatures and may be preferred. Mixtures of the cis -0.0007 (weight percent poly (1,4-cyclohexanedimethanol
and trans-isomers are useful herein as well. 60 1,4-cyclohexanedicarboxylate)+1.586 with a regression R
When the mixture of isomers or more than one diacid or squared coefficient of 0.998. Similarly, resorcinol diphos
diol is used, a copolyester or a mixture of two polyesters may phate (RDP) has a refractive index of 1.5673. A mixture
be used as the present cycloaliphatic polyester resin. having 25 weight percent RDP in PC would result in a calcu
Chemical equivalents of these diacids include esters, alkyl late refractive index of 0.25(1.5673)+0.75(1.586)=1.581.
esters, e.g., dialkyl esters, diaryl esters, anhydrides, salts, acid 65 Thus the refractive index of the mixture of the two compo
chlorides, acid bromides, and the like. The preferred chemical nents may be controlled between the upper and low lower
equivalents comprise the dialkyl esters of the cycloaliphatic limits of their respective indices of refraction.
 US 7,767,738 B2
9
Impact Modifier
The compositions of the invention further comprise a sub
stantially amorphous impact modifier copolymer resin that is
added to the miscible resinblend in an amount between about
1 and 30% by weight. The impact modifier may comprise one
of several different rubbery modifiers such as graft or core
shell rubbers or combinations of two or more of these modi
fiers. Suitable are the groups of modifiers known as acrylic where R is selected from the group consisting of hydrogen,
rubbers, ASA rubbers, diene rubbers, organosiloxane rub 10 alkyl groups of from 1 to 5 carbon atoms, bromine and chlo
bers, EPDM rubbers, SBS or SEBS rubbers, ABS rubbers, rine. Examples of vinyl cyanide monomers include acryloni
MBS rubbers and glycidyl ester impact modifiers. trile, methacrylonitrile, ethacrylonitrile, (-chloroacrylonitrile
The term acrylic rubber modifier can refer to multi-stage, and (-bromoacrylonitrile. The di-olefins utilized in the
core-shell, interpolymer modifiers having a cross-linked or 15
present invention are herein defined by the following struc
partially crosslinked (meth)acrylate rubbery core phase, pref tural formula:
erably butyl acrylate. Associated with this cross-linked
acrylic ester core is an outer shell of an acrylic or styrenic
resin, preferably methyl methacrylate or styrene, which inter Q H H Q,
penetrates the rubbery core phase. Incorporation of Small | | /
CEC-CFC
amounts of other monomers such as acrylonitrile or (meth) Q Q
acrylonitrile within the resin shell also provides suitable
impact modifiers. The interpenetrating network is provided
when the monomers forming the resin phase are polymerized 25 where each Q is independently selected from the group con
and cross-linked in the presence of the previously polymer sisting of hydrogen, alkyl groups of from 1 to 5 carbonatoms,
ized and cross-linked (meth)acrylate rubbery phase. bromine and chlorine. Examples of di-olefins includebutadi
Preferred rubbers are graft or core shell structures with a ene, isoprene, 13-heptadiene, methyl-1,3-pentadiene, 2.3-
rubbery component with a Tg below 0° C., preferably dimethylbutadiene, 2-ethyl-1,3-pentadiene, 1,3-hexadiene,
between about -40° to -80°C., composed of poly alkylacry 30
2,4-hexadiene, chlorobutadiene, bromobutadiene, dichlorob
lates or polyolefins grafted with PMMA or SAN. Preferably utadiene, dibromobutadiene and mixtures thereof. Vinyl aro
the rubber content is at least 40 wt %, most preferably matic monomers are herein defined by the following struc
between about 60-90 wt %. tural formula:
Especially suitable rubbers are the butadiene core-shell 35
polymers of the type available from Rohm & Haas, for X R
example Paraloid R EXL2600. Most preferably, the impact
modifier will comprise a two stage polymer having an buta X CFCH2,
diene based rubbery core and a second stage polymerized
40
from methylmethacrylate alone or in combination with sty
rene. Surprisingly, with opaque impact modifiers like MBS X X
EXL2600, the effect of adding PCCD to these PC/impact X
modifier compositions had very similar results; high trans
missions and low haze values were obtained with modifiers, 45
each modifier having a unique PC/PCCD ratio to match the RI where each X is independently selected from the group con
of thermoplastic blend to the RI of the impact modifier. sisting of hydrogen, alkyl groups of from 1 to 5 carbonatoms,
Other suitable rubbers are the ABS types Blendex.R. 336 cycloalkyl, aryl, alkaryl, aralkyl, alkoxy, aryloxy and halogen
and 415, available from GE Specialty Chemicals. Both rub and where R is independently selected from the group con
bers are based on impact modifier resin of SBR rubber. 50
sisting of hydrogen, alkyl groups of from 1 to 5 carbonatoms,
Although the mentioned rubbers appear to be very suitable, bromine and chlorine. The phrase independently selected
there are many more rubbers which can be used. Actually any means that co-polymers, terpolymers, or other interpolymers
rubber which has a reasonable clarity and which has an RI of these vinyl cyanide monomers may have an independently
between the RI of the components of the miscible resin blend
can be used, for example between 1.51 and 1.58 when the 55 selected R for the vinyl cyanide relative to the R selected for
blend is PC and PCCD can be used to the present invention. the vinyl aromatic monomer. Examples of substituted vinyl
The ABS type thermoplastic resins utilized by the present aromatic monomers include styrene, 4-methylstyrene, vinyl
invention are graft copolymers of vinyl cyanide monomers, Xylene, 3,5-diethylstyrene, p-tert-butyl-styrene, 4-n-propyl
di-olefins, vinyl aromatic monomers and vinyl carboxylic styrene, (-methyl-styrene (-ethyl-styrene, (-methyl-p-me
60
acid ester monomers. Thus applicants define herein the thyl-styrene, p-hydroxy-styrene, methoxy-styrenes, chloro
phrase ABS type or acrylonitrile-butadiene styrene type to styrene, 2-methyl-4-chloro-styrene, bromo-styrene,
include the group of polymers derived from vinyl cyanide (-chloro-styrene, (-bromo-S styrene, dichloro-styrene, 2.6-
monomers, di-olefins, vinyl aromatic monomers and vinyl dichloro-4-methyl-styrene, dibromo-styrene, tetrachloro
carboxylic acids ester monomers as hereinafter defined. Vinyl 65 styrene and mixtures thereof. Vinyl carboxylic acid ester
cyanide monomers are herein defined by the following struc monomers (esters of alpha-, beta-u unsaturated carboxylic
tural formula: acids) are herein defined by the following structural formula:
 US 7,767,738 B2
11 12
The acrylonitrile-butadiene-styrene type (ABS) thermo
plastic resin is preferably based on a SBR high rubber graft
with a SAN free rigid phase. Rubber amounts between about
V || 20 percent and about 45 percent are preferred. This ABS
composition preferably comprises: a) a free rigid phase
derived from a vinyl aromatic monomer and a vinyl carboxy
lic acid ester monomer, wherein the free rigid phase is present
where J is selected from the group consisting of hydrogen at a weight percent level of from about 30 to about 70 percent
by weight based on the total weight of the composition, more
and alkyl groups of from 1 to 8 carbonatoms and A is selected 10 preferably from about 35 to about 50 percent by weight
from the group consisting of alkyl groups of from 1 to 5 thereof, and most preferably from about 38 to about 47 per
carbonatoms. Examples of vinyl carboxylic acid ester mono cent by weight thereof; b) a graft copolymer (graft phase)
mers include methyl methacrylate, methyl acrylate, ethyl comprising a Substrate copolymer and a Superstrate copoly
methacrylate, ethyl acrylate, butyl methacrylate, butyl acry mer wherein the Substrate copolymer comprises a copolymer
late, propyl methacrylate, propyl acrylate, 2-ethylhexylacry 15 derived from a vinyl aromatic monomer and a di-olefin and is
late, 2-ethylhexyl methacrylate, methyl ethacrylate and mix wherein the Superstrate copolymer comprises a copolymer
tures thereof. derived from an aromatic monomer wherein the graft copoly
It will be understood that by the use of “monomers' are mer is present at a level of from about 30 to about 70 weight
included all of the polymerizable species of monomers and percent of the total weight of the composition, more prefer
copolymers tropically utilized in polymerization reactions, ably from about 50 to about 65 percent by weight thereof, and
including by way of example monomers, homopolymers of most preferably from about 53 to about 62 percent by weight
primarily a single monomer, copolymers of two or more thereof; and c) wherein the refractive index of the free rigid
monomers, terpolymers of three monomers and physical phase and the calculated refractive index of the graft phase are
mixtures thereof. For example, a mixture of polymethyl approximately the same (that is, matched to within about
methacrylate (PMMA) homopolymer and styrene-acryloni 25 0.005 or less). The refractive index of the phases may be
readily calculated based on the weight percentage of the
trile (SAN) copolymer may be utilized to form the “free rigid components and their refractive indices, for example:
phase', or alternatively a methylmethacrylate-styrene-acry The refractive indices of butadiene, styrene, acrylonitrile
lonitrile (MMASAN) terpolymer may be utilized. and methyl methacrylate homo-polymers are 1.515, 1.591,
Various monomers may be further utilized in addition to or 30 1.515 and 1.491 respectively. A butadiene/styrene ratio of
in place of those listed above to further modify various prop 85:15 gives a calculated refractive index of (0.85x1.515)+
erties of the compositions disclosed herein. In general, the (0.15x1591)=-1.526.
components of the present invention may be compounded The grafted SAN having a styrene to acrylonitrile ratio of
warmth a copolymerizable monomer or monomers within a 80:20 gives a calculated refractive index of (0.80x1.591)+
range not damaging the objectives and advantages of this 35 (0.20x1.515)=-1.576.
invention. For example, in addition to or in place of SBR, the
rubber phase may be comprised of polybutadiene, butadiene A graft copolymer of 65% styrene-butadiene rubber (buta
acrylonitrile copolymers, polyisoprene. EPM and EPR rub diene:styrene=85:15) and 35% grafted SAN (styrene:acry
bers (ethylene/propylene rubbers), EPDM rubbers (ethylene/ lonitrile=80:20) gives a calculated refractive index of (0.65x
propylene/non-conjugated diene rubbers) and crosslinked 40 1.526)+(0.35x1.576)=-1.544.
alkylacrylate rubbers based on C-C alkylacrylates, in par In the example above, the free rigid phase must have approxi
ticular ethyl, butyl and ethylhexylacrylates, either alone or as mately the same refractive index as the graft rubber phase
a mixture of two or more kinds. Furthermore, the rubber may within +0.005. A free rigid phase of 60% PMMA and 40
comprise either a block or random copolymer. In addition to percent SAN of 75% styrene and 25% acrylonitrile has a
or in place of Styrene and acrylonitrile monomer used in the 45 refractive index of approximately 1.539, thereby matching
graft or free rigid phase, monomers including vinyl carboxy the graft phase refractive index to within 0.005.
lic acids such as acrylic acid, methacrylic acid and itaconic The free rigid phase is preferably derived from styrene
acid, acrylamides such as acrylamide, methacrylamide and acrylonitrile (SAN). The ratio of styrene to acrylonitrile is
n-butyl acrylamide, alpha-, beta-unsaturated dicarboxylic preferably from 1.5 to 15 (that is, preferably from about 60
anhydrides such as maleic anhydride and itaconic anhydride, 50 percent to about 94 percent styrene) and from about 6 percent
imides of alpha-, beta-unsaturated dicarboxylic acids such as to about 40 percent acrylonitrile by weight based on the total
maleimide, N-methylmaleimide, N-ethylmaleimide, N-Aryl weight of the free rigid phase, more preferably from about 4
maleimide and the halo substituted N-alkyl N-aryl maleim to 12 (from about 80 percent to about 92 percent styrene) and
ides, imidized polymethyl methacrylates (polyglutarimides), from about 8 percent to about 20 percent acrylonitrile by
unsaturated ketones such as vinyl methyl ketone and methyl 55 weight based on the total weight of the free rigid phase and
isopropenylketone, alpha-olefins such as ethylene and pro most preferably from about 6 to 9 (from about 85 percent to
pylene, vinyl esters such as vinyl acetate and vinyl Stearate, about 90 percent styrene) and from about 10 percent to about
vinyl and vinylidene halides such as the vinyl and vinylidene 15 percent acrylonitrile by weight based on the total weight of
chlorides and bromides, vinyl-substituted condensed aro the free rigid phase. The graft copolymer is preferably derived
matic ring structures such as vinyl naphthalene and vinyl 60 from a vinyl aromatic-di-olefin rubber substrate copolymer.
anthracene and pyridine monomers may be used, either alone The graft copolymer preferably comprises from about 40
or as a mixture of two or more kinds. percent to about 90 percent of a substrate copolymer and from
Preferred impact modifiers are of the type disclosed in U.S. about 10 percent to about 60 percent of a superstrate copoly
Pat. No. 4,292.233, incorporated by reference. These impact mer based on the total weight of the graft copolymer, more
modifiers comprise, generally, a relatively high content of a 65 preferably from about 55 percent to about 75 percent of a
cross-linked butadiene polymer grafted base having grafted substrate copolymer and from about 25 percent to 45 percent
thereon acrylonitrile and styrene. of a Superstrate copolymer by weight thereof, and most pref
 US 7,767,738 B2
13 14
erably about 65 percent by weight of a substrate copolymer improve the appearance, special effect additives have been
and 35 percent by weight of a superstrate copolymer. The utilized as colorants. U.S. Pat. No. 5,510,398 to Clark et al
Substrate copolymer preferably comprises a vinyl aromatic relates to a highly filled, extruded polyalkylene terephthalate
component level of from slightly greater than about 0 percent resin, a polycarbonate resin, a filler, a stabilizer, and a non
to about 30 percent by weight based on the total weight of the dispersing pigment to give the extruded thermoplastic mate
substrate copolymer, more preferably from 10 to 20 percent rial a speckled Surface appearance. Column 5. lines 35 to
by weight thereof and most preferably 15 percent by weight column 6, line 61, describes impact modifiers. U.S. Pat. No.
thereof, and a di-olefin component level of from about 70 5,441.997 to Walsh etal describes the use of impact modifiers
percent to about 100 percent of a di-olefin by weight based on 10 in conjunction with polycarbonate/polyester compositions
the total weight of the substrate copolymer, more preferably having a barium sulfate, strontium sulfate, Zirconium oxide,
from about 80 to about 90 percent by weight thereof, and most or zinc sulfate filler. U.S. Pat. No. 5,814,712 to Gallucci etal
preferably about 85 percent by weight hereof. The superstrate describes a glycidyl ester as an impact modifier, and option
may optionally contain a vinyl carboxylic acid ester compo ally other impact modifiers, for a polycarbonate/polyester
nent such as methyl methacrylate. The graft phase preferably 15
has a weight average particle size of less than 2400 angstroms resin. U.S. Pat. No. 4,264,487 to Fromuth et al describes
(0.24 microns), more preferably less than 1600 angstroms aromatic polycarbonate, acrylate-based core-shell polymer,
(0.16 microns) and most preferably less than 1200 angstroms and aromatic polyester.
(0.12 microns). Generally, the particle size of the rubber has Visual-Effect Additives
an effect upon the optimum grafting level for the graft copoly
mer. As a given weight percentage of Smaller size rubber In the compositions of the invention, one or more visual
particles will provide greater Surface area for grafting than the effects additives of various types may be added as desired.
equivalent weight of a larger rubber particle size, the density Glitter Type of Materials
of grafting may be varied accordingly. In general, Smaller
rubber particles preferably utilize a higher superstrate/sub 25 As the glitter material, it is Suitable to use one or more kinds
strate ratio than larger size particles to give generally compa selected from the group consisting of mica, pearl mica, glass
rable results. flake, aluminum powder, stainless powder, brass powder,
The graft phase may be coagulated, blended and colloided metallic plating powder, metallic coating powder, aluminum
with the free rigid phase homopolymers, copolymers and/or 30 flake, aluminum foil, zinc, and bronze powder. This leads to
terpolymers by the various blending processes that are well an advantage of an excellent glitter feeling. It is particularly
known in the art to form the ASA polymer polyblend. preferable to use a glitter material having a high transmittance
Preferred Compositions of the Invention with respect to a visible ray Such as mica; pearl mica, glass
The preferred impact-modified, cycloaliphatic polymer 35
flake, or the like. These materials further improve the glitter
compositions of the present invention comprise: and color depth of a skin layer, and moreover, provide a color
(A) from 20 to 80% by weight of a blend of polycarbonate tone with high gloss, depth and glitter feel to the glitter resin
and cyclo aliphatic polyester resin, where the ratio of poly molded material by light that has transmitted through the skin
carbonate to cyclo aliphatic polyester resin is from 20/80 to layer and reflected on the surface of a core layer which is
95/5, preferable from 30/70 to 60/40, the cyclo aliphatic 40
colored with a coloring pigment.
polyester comprises the reaction product of
(a) at least one straight chain, branched, or cycloaliphatic The coloring pigment contained in the skin layer and the
C-C alkane diol, most preferably a C-C cycloaliphatic core layer is Suitably one or more kinds selected from a group
diol, or chemical equivalent thereof, and of organic pigments such as phthalocyanine blue, cyanine
45 green, indanthrene, azo, anthraquinone, perylene, pery none,
(b) at least one cycloaliphatic diacid, most preferably a quinacridone, isoindolinone, thioindigo, dioxazine; a group
C-C diacid, or chemical equivalent thereof, and of inorganic pigments such as titanium oxide, titanium yel
(B) from 1 to 30%, preferably from 5 to 20% by weight of low, red iron oxide, burned pigment, carbon black; and a
an impact modifier comprising a substantially amorphous group of dyes such as phthalocyanine, anthraquinone,
resin comprising one of several different modifiers or combi 50
perylene, perynone.
nations of t-o or more of these modifiers. Suitable are the
groups of modifiers known as ABS modifiers ASA modifiers, Granite Type of Additives
MBS modifiers, EPDM graft SAN modifiers, acrylic rubber Many large opaque particles can be used to make the simu
modifiers. lated granite. These particles can be colored or uncolored.
55
The method of blending the compositions can be carried Typical mineral particles that can be used are calcined talc,
out by conventional techniques. Preferably the polyester and magnetite, siderite, ilmenite, goethite, galena, graphite,
polycarbonate are pre-blended in amount selected to match anthracite and bituminous coal, chalcopyrite, pyrite, hema
the refractive index of the modifier. The ingredients are typi tite, limonite; pyroxenes Such as augite; amphiboles Such as
cally in provider or granular form, extruding the blend and 60 hornblende; biotite, sphalerite, anatase, corunbum, diamond,
comminuting into pellets or other Suitable shapes. The ingre carborundum, anhydrite, chalk, diurite, rutile, sandstone,
dients are combined in any usual manner, e.g., by dry mixing shale, Slate, sparite, Vermiculite, natural granite, peat and
or by mixing in the melted State in an extruder, or in other basalt. Other useful materials are chips of brick, charcoal,
mixers. concrete, plaster, porcelain, sawdust, seashells, slag, wood
Impact modified polycarbonate resins as outlined above 65 and the like, various filled or pigmented chips of insoluble or
are excellent materials for applications requiring high impact, crosslinked polymers such as ABS resins, cellulose esters,
chemical resistance, and appealing aesthetic. In order to cellulose ethers, epoxy resins, polyethylene, ethylene copoly
 US 7,767,738 B2
15 16
mers, melamine resins, phenolic resins, polyacetals, poly the range of about 20° to 50° C. provided that the initiator
acrylics, polydienes, polyesters, polyisobutylenes, polypro system is not added until ready to cast.
pylenes, polystyrenes, urea/form-aldehyde resins, polyureas,
polyurethanes, polyvinyl chloride, polyvinylidene chloride, Colored Pigments
polyvinyl esters and the like. 5 In general, the effect pigment is a metallic-effect pigment,
Useful large translucent and transparent particles are natu a metal oxide-coated metal pigment, a platelike graphite pig
ral or synthetic minerals or materials such as agate, alabaster, ment, a platelike molybdenumdisulfide pigment, a pearles
albite, calcite, chalcedony, chert, feldspar, flint quartz, glass, cent mica pigment, a metal oxide-coated mica pigment, an
malachite, marble, mica, obsidian, opal, quartz, quartzite, organic effect pigment, a layered light interference pigment,
rock gypsum, sand, silica, travertine, wollastonite and the 10
a polymeric holographic pigment or a liquid crystal interfer
like; and moderately filed or unfilled, pigmented or dyed, ence pigment. Preferably, the effect pigment is a metal effect
insoluble or crosslinked chips of polymers referred to in the pigment selected from the group consisting of aluminum,
last paragraph. gold, brass and copper metal effect pigments; especially alu
The large opaque, translucent and/or transparent particles minum metal effect pigments. Alternatively, preferred effect
15
are present in the stimulated granite at a concentration of pigments are pearlescent mica pigments or a large particle
about 0.1-50% by volume, preferably about 1-35% by vol size, preferably platelet type, organic effect pigment selected
ume. The opaque particles are most preferably at a concen from the group consisting of copper phthalocyanine blue,
tration of about 5-25% by volume while the concentration of copper phthalocyanine green, carbazole dioxazine, diketopy
the translucent or transparent particles is most preferably
about 5-30% by volume. rrolopyrrole, iminoisoindoline, irninoisoindolinone, azo and
Additional additives can be included in the stimulated quinacridone effect pigments.
granite article to give it decorative effects or to color the Suitable colored pigments especially include organic pig
matrix background. These additives can be incorporated at a ments selected from the group consisting of azo, azomethine,
concentration up to about 10% by volume; however, when methine, anthraquinone, phthalocyanine, perinone, perylene,
dyes or pigments are used to color the matrix, the color diketopyrrolopyrrole, quinacridone, flavanthrone, indan
concentration cannot be so great as to hide the large opaque, throne, anthrapyrimidine and quinacridone, flavanthrone,
translucent and transparent particles. The optical density of a indanthrone, anthrapyrimidine and quinophthalone pig
0.05 inch thick wafer must be less than 3.0 and the surface ments, or a mixture or Solid solution thereof, especially a
must exhibit a granite-like pattern. 30 dioxazine, diketopyrrolopyrrole, quinacridone, phthalocya
The surface patterns of a number of different natural gran nine, indanthrone or iminoisoindolinone pigment, or a mix
ites have been defined by IMANCOR Quantimet 720 image ture or solid solution thereof.
analysis. These patterns have about 0.1 to 40% area detect Colored organic pigments of particularinterest include C.I.
able at densitometric level 820, about 0 to 30% additional area Pigment Red 202, C.I. Pigment Red 122, C.I. Pigment Red
detectable at level 860, about 0.1 to 25% additional area 35 179, C.I. Pigment Red 170, C.I. Pigment Red 144, C.I. Pig
detectable at level900, about 0 to 25% additional area detect ment Red 177, C.I. Pigment Red 254, C.I. Pigment Red 255,
able at level 950 and about 15 to 95% additional area detect
able at a level greater than 950. It is preferred that the simu C.I. Pigment Red 264, C.I. Pigment Brown 23, C.I. Pigment
lated granite have essentially the same Surface pattern. Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow
In addition to dyes and pigments, other useful decorative 147, C.I. Pigment Orange 61, C.I. Pigment Orange 71, C.I.
40
additives are metallic fibers, dusts, flakes, chips or shavings Pigment Orange 73, C.I. Pigment Orange 48, C.I. Pigment
Such as aluminum, copper, bronze, brass, chromium, nickel, Orange 49, C.I. Pigment Blue 15, C.I. Pigment Blue 60, C.I.
gold, iron, steel, platinum, silver, tin, titanium, tungsten, Zinc Pigment Violet 23, C.I. Pigment Violet 37, C.I. Pigment Vio
and the like; non-metallic chips or flakes such as titanium let 19, C.I. Pigment Green 7, C.I. Pigment Green 36, or a
nitride, nickel sulfide, cobalt sulfide, anhydrous chromic 45
mixture or solid solution thereof.
chloride and magnesium sulfide; and natural or colored flocks Suitable colored pigments also include inorganic pig
or chopped fibers such as asbestos, rayon, cotton, nylon, flax, ments; especially those selected from the group consisting of
polyester, glass, hair, hemp, paper pulp, polyacrylonitrile, metal oxides, antimony yellow, lead chromate, lead chromate
polyethylene, polypropylene, protein, rock wool, wood fiber, sulfate, lead molybdate, ultramarine blue, cobalt blue, man
wool and the like. 50 ganese blue, chrome oxide green hydrated chrome oxide
The simulated granite is prepared by first preparing a green, cobalt green and metal Sulfides, such as cerium or
castable composition. This composition can be made by pre cadmium Sulfide, cadmium Sulfoselenides, Zinc ferrite, bis
paring a mixture of the large opaque particles, the large trans muth Vanadate and mixed metal oxides.
parent and/or translucent particles and, if desired, any of the Most preferably, the colored pigment is a transparent
Solid optional ingredients such as the decorative particles. 55
organic pigment. Pigment compositions wherein the colored
The matrix for the composition is prepared by mixing the pigment is a transparent organic pigment having a particle
polymerizable constituent, a viscosity control constituent, an size range of below 0.2 um, preferably below 0.1 um, are
initiating amount of an initiator System for the polymerizable particularly interesting. For example, inventive pigment com
constituent, the Small filler particles and any other optional positions containing, as transparent organic pigment, the
ingredients such as a cross-linking or coloring agent. These 60
two mixtures are mixed at a ratio which will give the desired transparent quinacridones in their magenta and red colors, the
visual effect in the final product and then this final mixture, transparent yellow pigments, like the isoindolinones or the
called the castable composition is poured onto a Surface yellow quinacridone?quinacridonequinone solid solutions,
which takes the form of the final article, e.g. a flat surface for transparent copperphthalocyanine blue and halogenated cop
simulated granite sheets or a mold for simulated granite 65 per phthalocyanine green, or the highly-Saturated transparent
shaped articles. The poured mixture is then cured autogeni diketopyrrolopyrrole or dioxazine pigments are particularly
cally. The matrix mixing can be conducted at a temperature in interesting.
 US 7,767,738 B2
17 18
Adding a fluorescent dyestuff generates Striking visual be added to the compositions of the present invention. These
effects for the article. Suitable fluorescent dyestuffs include additives may be introduced in a mixing or molding process,
Permanent PinkR (Color Index Pigment Red 181, from Clari provided the properties of the composition are not damaged.
ant Corporation), Hostasol Red 5B (Color Index #73300, Suitable antistatic agents include, but are not limited to,
CAS # 522-75-8, from Clariant Corporation) and Macrolex phosphonium salts, polyalkylene glycols, Sulfonium salts and
Fluorescent Yellow 10GN (Color Index Solvent Yellow 160:
1, from Bayer Corporation). Among these, Permanent Pink R alkyl and aryl ammonium salts.
is preferred. Suitable mold release agents include, but are not limited to,
Typically the pigment composition is prepared by blending pentaerythritol tetracarboxylate, glycerol monocarboxylates,
the pigment with the filler by known dry or wet mixing 10 glycerol b-carboxylates, polyolefins, alkyl waxes and amides.
techniques. For example, the components are wet mixed in In the thermoplastic compositions which contain a
the end step of a pigment preparatory process, or by blending cycloaliphatic polyester resin and a polycarbonate resin it is
the filer into an aqueous pigment slurry, the slurry mixture is
then filtered, dried and micropulverized. preferable to use a stabilizer or quencher material. Catalyst
In a preferred method, the pigment is dry blended with the 15 quenchers are agents which inhibit activity of any catalysts
filler in any suitable device which yields a nearly homog which may be present in the resins. Catalyst quenchers are
enous mixture of the pigment and the filler. Such devices are, described in detail in U.S. Pat. No. 5,441,997. It is desirable
for example, containers like flasks or drums which are Sub to select the correct quencher to avoid color formation and
mitted to rolling or shaking, or specific blending equipment loss of clarity to the polyester polycarbonate blend.
like for example the TURBULA mixer from W. Bachofen, A preferred class of stabilizers including quenchers are
CH-4002 Basel, or the P-K TWIN-SHELL INTENSIFIER those which provide a transparent and colorless product.
BLENDER from Patterson-Kelley Division, East Strouds Typically, such stabilizers are used at a level of 0.001-10
burg, Pa. 18301. weight percent and preferably at a level of from 0.005-2
The pigment compositions are generally used in the form weight percent. The favored stabilizers include an effective
of a powder which is incorporated into a high-molecular 25
amount of an acidic phosphate salt; an acid alkyl, aryl or
weight organic composition, Such as a coating composition, mixed phosphitehaving at least one acidic hydrogen; a Group
to be pigmented.
The pigment composition consists of or consists essen IB or Group IIB metal phosphate salt; a phosphorus oxoacid,
tially of the filler and colored pigment, as well as customary a metal acid pyrophosphate or a mixture thereof. The Suit
additives for pigment compositions. Such customary addi 30 ability of a particular compound for use as a stabilizer and the
tives include texture-improving agents and/or antiflocculat determination of how much is to be used as a stabilizer may be
ing agents. readily determined by preparing a mixture of the polyester
The following patents relate to metallic type pigments. WO resin component and the polycarbonate and determining the
99/02594 which describes the use of rectangular aluminum effect on melt viscosity, gas generation or color stability or the
flakes in Nylon compositions. U.S. Pat. No. 5,091,010 and EP 35 formation of interpolymer. The acidic phosphate salts include
0.426 446 relate to the aesthetics of molded articles contain Sodium dihydrogen phosphate, mono Zinc phosphate, potas
ing flakes. These references do not address mechanical per sium hydrogen phosphate, calcium dihydrogen phosphate
formance concerns which are addressed by the present inven and the like. The phosphites may be of the formula V:
tion.
40
Among the problems to be solved when utilizing polycar
bonate resins and particles and pigments to produce special RO-P-OR2
color effects are those related to composition coloring and OR3
those related to producing a very bright, metallic reflective
sparkle appearance in the molded articles while retaining 45
impact strength and transparency. For most visual effects, it is
desirable to have a completely transparent matrix in order to where R1, R2 and R3 are independently selected from the
obtain the deepest color effect. The use of modifiers in com group consisting of hydrogen, alkyl and aryl with the proviso
bination various colorant additives may to be detrimental to that at least one of R1,R2 and R3 is hydrogen.
physical properties such as notched Izod impact. Although The phosphate salts of a Group IB or Group IIB metal
50
various impact modifiers are known in the prior art, the prior include Zinc phosphate and the like. The phosphorus oxo
art is deficient in addressing the problem of enhancing the acids include phosphorous acid, phosphoric acid, polyphos
impact properties of polycarbonate (alloys) having special phoric acid or hypophosphorous acid.
effect colorants, while maintaining the transparency. The The polyacid pyrophosphates may be of the formula VI:
blend compositions as described in this invention combine 55
appealing aesthetics, chemical resistance, and high impact
properties and will be useful in molded article applications
where this combination of properties is desirable. wherein M is a metal, X is a number ranging from 1 to 12 and
Other Additives y is a number ranging 1 to 12, n is a number from 2 to 10, Z is
Additionally, additives such as antioxidants, heat resisting 60
a number from 1 to 5 and the Sum of (XZ)+y is equal to n+2.
agents, anti-weathering agents, mold release agents, lubri The preferred M is an alkaline or alkaline earth metal.
cants, nucleating agents, plasticizers, flow-improving agents The most preferred quenchers are oxoacids of phosphorus
and anti-statics, quenchers, minerals such as talc, clay, mica, or acidic organo phosphorus compounds. Inorganic acidic
barite, wollastonite and other stabilizers including but not phosphorus compounds may also be used as quenchers, how
limited to UV stabilizers, such as benzotriazole, supplemen 65 ever they may result in haze or loss of clarity. Most preferred
tal reinforcing fillers such as flaked or milled glass, and the quenchers are phosphoric acid, phosphorous acid or their
like, flame retardants, pigments or combinations thereof may partial esters.
 US 7,767,738 B2
19 20
The glass transition temperature of the preferred blend will (such as coated Al and glass flakes), which are normally
be from 60 to 150° C. with the range of 90-150° C. most negatively affecting the mechanical properties of Polycar
preferred. bonate, to this PC/PCCD/ABS blend to enhance required
A flexural modulus (as measured by ASTM method D790) Impact properties. These films can be used in direct film
at room temperature of greater than or equal to 150.00 psi is applications but also in processes like IMD (In Mould Deco
preferred, with a flexural modulus of greater than or equal to ration).
250,000 psi being more preferred.
The yellowness index (YI) will be less than 10, preferably EXAMPLES
less than 5 as measured by ASTM method D1925.
Haze, as measured by ASTM method D1003, will be below 10
The following examples serve to illustrate the invention but
5% in the preferred composition, however in some cases are not intended to limit the scope of the invention. Blends
higher haze levels (5-60%) are preferred in cases where the were prepared by tumbling all ingredients together for 1-5
highest heat resistance is needed.
Above described materials have also been tested in GE min at room temperature followed by extrusion at 250-300
Structured Products applications like film and coextruded 15 C. on a co-rotating 30 mm vacuum vented twin screw
solid sheet materials. In film advantages like “cold forming extruder. Blends were run at 300 rpm. The output was cooled
(the low Tg of the material enables the operator to use lower as a strand in a water bath and pelletized.
temperatures to thermoform the film), improved tensile The resultant materials were dried at 100-120° C. for 3-6 h
impact and chemical resistance were seen. These products and injection molded in discs or sections of discs (fans) for
will perfectly Suit in applications like eg. transparent keypads evaluation of optical properties.
for mobile phones, where customers require the possibility to
form these films at low temperatures (below 100° C.) and Blends of PCCD with BPA-PC and various impact modi
further require an improved punch ductility and chemical fiers were prepared and various stabilizers were added to give
resistance. Other typical applications of Such films are auto good color and melt stability. The samples were compounded
motive trim, automotive interior parts, portable telecommu 25 on a twill screw extruder and injection-molded at Standard
conditions.
nications and appliance fronts. Another advantage in film
applications is the possibility to add Visual effects pigments Example 1

MVR
PC PCCD (cc/10")
105 4000 Impact PC/PCCD Transmission (300° C. D/B
Batch # grade % poise % stabilizers % Modifier% ratio 2 mm 90 1.2 kg) o C.

1 99.8 O.2 91.4 S.1 -10

2 69.6 30 0.4 70.30 90.4 16.8 O

3 28.4 66.2 0.4 5% MBS 30, 70 89.5 31.6 -20

4 25.4 59.2 0.4 15% MBS 30, 70 88.5 14.3 -32

5 30.6 S4 0.4 15% clear 3664 89.6 22.2 -6

ABS

6 47.3 47.3 0.4 10% ABS 415 50/50 89.8 7.4 -22

7 46.6 38.1 0.4 15% ABS 336 45.50 88.1 6.7 -33

8 67.2 22.4 0.4 10% ABS 336 25.75 77.1 4.8 -32
 US 7,767,738 B2
21 22
From the data batch 1-7 it is clear that adding PCCD to PC
gives a significant improvement in flow. Adding impact modi -continued
fiers not only gives an improvement in flow, but also improves
low temperature ductility, while obtaining high transparen Film sample 2 Film sample 3
Film sample 1 45.45.10% 40.60%
cies in the same range as PC. 5 Test name: 100% PC PCPCCD ABS PCPCCD
In some cases lower amounts of PCCD are desired, than the
Taber Abrasion ASTM 27 24 19
ones mentioned in batch 2-7. This can be from a cost perspec D104425 Rotations
tive or that for applications more heat is required. Although Haze 96
this will result in lower transmission values (the 100% match
of RI is no longer present in the blend), in many cases these 10
values are still high enough to allow for adding special/visual From this example it is apparent that impact properties of
effects like glass or metal flakes and in Some cases some film material made from PC/PCCD mixtures is improved
translucency is even desired. A typical example is given in the significantly compared to PC alone, either with or without
table for latch 8. adding impact modifiers. Also the chemical resistance
15 towards artificial Sweat has improved.
Example 2
Example 4
These property enhancements are further illustrated in the
next table, in which some typical comparisons are made The polyester PCCD (with low RI RI of PCCD-1.525)
between PC formulated with special effects and blends of that is fully miscible with PC can be used to lower the RI of
PC/PCCD and impact modifier, formulated with the same the PC phase (phase 1) to the RI of a clear ABS (that has RI of
type of special effects. SAN and Rubber phases already matched). This results in

PC PCCD (cc/10")
105 2OOO Impact (265° C. D/B
batch # grade % poise % stabilizers % Modifier % Special Effect 5 kg) o C.
9 98.3 O.S 1.2% glassisilver 10.1 >25
flakes
10 41.7 41.7 0.4 15% ABS 1.2% glass/silver 12.8 -22
415 flakes
11 99.3 O.S 0.2% variochr. red 10.4 >25
(AngularMetameric)
12 41.7 41.7 0.4 15% ABS 0.2% variochr. red 12.8 -18
415 (AngularMetameric)

It is obvious from the data that typical effects like glass and transparent PC/SAN/rubber blend. Mixtures of PC/PCCD
metal flakes turn PC into very brittle blends. However with 40 resulted in linear RI going from 1.525 to 1.577 when using
the correct PCCD and impact modifier loading, the visual 100% PCCD to 100% PC respectively. The Clear ABS that
effect was very similar to the PC sample, but the blend was was utilized in this example had a RI of 1.548. In order to
still ductile at lower than 0°C. and even had an improved flow. match this a PC/PCCD ratio of 54 to 31 was prepared and
This remarkable achievement of highly ductile, transparent mixed with 15 wt.% of clear ABS. The results of samples
45 from this blend were as follows:
materials with special effects like Angular Metamerism, Dia
mond, Diffusion and Pearl effects is not restricted to the ones
mentioned in the examples.
Transmission (%, 3.2 mm) 85
Haze (ASTM9125) 15
Example 3 50

The refractive index of pure polycarbonate (PC) is 1.586

Film material with a thickness of 220 microns was pro while that of PCCD is 1.516. In a mixture of polycarbonate
duced from a 45/45/10% ratio PC/PCCD/ABS blend and and poly (1,4-cyclohexanedimethanol-1,4-cyclohexanedi
tested with 100% PC film as a reference material. Following 55 carboxylate the refractive index of the mixture, y, varies as the
results were obtained: function -0.0007 (weight percent poly (1,4-cyclohex
anedimethanol-1,4-cyclohexanedicarboxylate)+1.586 with a
regression R squared coefficient of 0.998. Thus the refractive
Film sample 2 Film sample 3
index of the mixture of the two components may be controlled
Film sample 1 45.45.10% 40.60% 60 between the upper and lower limits of their respective indices
Test name: 100% PC PCPCCDABS PCPCCD of refraction.
What is claimed is:
Tensile Impact Kj/m2 961 1129 1147 1. A composition comprising a blend of:
Elongation to br. % 75.2 98.3 87.5
After stress cracking 102.8 126.4 1546 (a) a resin blend of a polycarbonate resin and a
“Sweat’ test: Tensile 65 cycloaliphatic polyester resin, said cycloaliphatic poly
Strain at max% ester resin comprising the reaction product of an ali
phatic C-C diol or chemical equivalent and a C-C,
 US 7,767,738 B2
23 24
aliphatic diacid or chemical equivalent, said 5. The composition of claim 1, wherein the amorphous
cycloaliphatic polyester resin containing at least about resin is selected from the group consisting of ABS impact
80% by weight of a cycloaliphatic dicarboxylic acid, or modifiers, ASA impact modifiers, EPDM graft SAN impact
chemical equivalent, and/or of a cycloaliphatic diol or modifiers and acrylic rubber impact modifiers.
chemical equivalent; 6. The composition of claim 5, wherein polycarbonate is
(b) from 1 to 30% by weight of an impact modifying present in an amount of from 20 to 95% by weight of the entire
component comprising an amorphous resin having a composition.
refractive index from about 1.51 to about 1.58, said 7. The composition of claim 5, wherein polycarbonate is
impact modifier enhancing the impact strength of present in an amount of from 30 to 60% by weight of the entire
molded composition as compared to a molding compo 10 composition.
sition absent said impact modifier, and 8. The composition of claim 5, wherein the composition
(c) from 0.0001 to 7 percent by weight of mica flakes for Surrounding the flakes is transparent.
imparting a desired visual effect, 9. The composition according to claim 1 wherein the flakes
wherein the composition is a miscible blend and comprises comprise from about 0.05 to about 5.0 weight percent of the
the polycarbonate and the cycloaliphatic polyester resin 15 resin composition.
in amounts such that the index of refraction of the blend 10. The composition according to claim 1 further compris
matches the index of refraction of said impact modifier ing a background colorant having a different coloration than
to produce a transparent or translucent composition Sur said flakes.
rounding said flakes. 11. The composition according to claim 1 wherein said
2. The composition of claim 1, wherein polycarbonate is colorant is selected from the group consisting of carbon
present in the resin blend in an amount of from 20 to 95% by black, phthalocyanine blues, phthalocyanine greens,
weight. anthraquinone dyes, Scarlet 3b Lake, azo compounds, acid
aZo pigments, quinacridones, chromophthalocyanine pyrrols,
3. The composition of claim 1, wherein polycarbonate is halogenated phthalocyanines, quinolines, heterocyclic dyes,
present in the resin blend in an amount of from 30 to 60% by 25 perinone dyes, anthracenedione dyes, thioxanthene dyes,
weight. parazolone dyes and polymethine pigments.
4. The composition of claim 1, wherein the composition
Surrounding the flakes is transparent. k k k k k