Title of Invention

THERMOPLASTIC MOLDING COMPOSITIONS HAVING IMPROVED PLATEABILITY

Abstract A thermoplastic molding composition containing a major amount of polycarbonate and a lesser amount of butadiene based graft polymer is disclosed. The inventive composition is especially suited for the preparation of a molded article wherein at least some of its surface is metallized by an electroless plating process. The thus plated article is characterized in its improved heat resistance and excellent adhesion of its metal plating.
Full Text FORM 2
THE PATENTS ACT 1970
[39 OF 1970]
COMPLETE SPECIFICATION
[See Section 10]
"THERMOPLASTIC MOLDING COMPOSITIONS HAVING IMPROVED PLATEABILITY"
BAYER CORPORATION, of 100 Bayer Road, Pittsburgh, Pennsylvania 15205, United States of America,
The following specification particularly describes the nature of the invention and the manner in which it is to be performed:-
GRANTED
02-07-2004

THERMOPLASTIC MOLDING COMPOSITIONS HAVING IMPROVED PLATEABILITY
FIELD OF THE INVENTION
The invention is ducted to A uv^moplasilc maiding composition, which contains ABS and polycarbonate and to articles molded therefrom, and more particularly to metal plated articles molded therefrom.
SUMMARY OF INVENTION
A thermoplastic molding composition containing a major amount of polycarbonate and a lesser amount of butadiene based graft polymer is disclosed. The inventive composition is especially suited for the preparation of a molded article wherein at least some of its surface is metallized by #n electroless plating process. The thus plated article is characterized in its improved heat resistance and excellent adhesion of its
metal plating.
BACKGROUND OF INVENTION
Thermoplastic molding composition containing polycarbonates and ABS polymers have been known for some time, see for example DE-A 1 170 141 which describes the favorable processing properties of such molding compositions. Also relevant are U.S. Patents 3,130,177, 3,162,695 and 3,852,393 and British Patent No 1,253,226.
Also known are thermoplastic molding compositions containing polycarbonate and acrylate based plating modifiers (U.S. Patent 4,828,921) or ABS which are suitable for electroless metal plating. In general, the polycarbonate content in these compositions is kept low as it has long been recognized that the presence of polycarbonate in relatively high amounts is the cause of difficulties in electroless metal-plating (see U.S. Patents 5,198,096 and 5,087,524). On the other hand, the heat resistance of the composition is directly related to the polycarbonate level. Blends containing a higher content of polycarbonate feature better thermal

performance. The art has long sought a molding composition that would combine good heat resistance with good plating characteristics. The composition of the present invention addresses this goal. Special procc-aes i"r electroless plating of polycarbonate have been described in U.S. Patents 5,087,524 and 5,198,096.
Processes for electroless plating have been disclosed in U.S. Patent 4,125,649 and in the Encyclopedia of Polymer Science and Technology, Vol. 8, both incorporated by reference herein.
DETAILED DESCRIPTION OF THE INVENTION
The thermoplastic molding composition of the invention comprises.
A) 51 to 90 parts by weight of an aromatic polycarbonate;
B) a positive amount up to 30 parts by weight of a rubber free vinyl copolymer of 50 to 99 percent B.I and 1 to 50 percent B.2, the percents being relative to the weight of the copolymer, where B.1 is at least one member selected from the group consisting of styrene, a-methyl styrene, nucleus-substituted styrene, and methyl methacrylate and where B.2 is at least one member selected from the group consisting of acrylonitrile, methyl methacrylate, maleic anhydride, N-alkyl-substituted maleic imide and N-aryl-substituted maleic imide;
C) 5 to 30 parts by weight of a first graft polymer containing 10 to 90 percent of a first graft phase C.1 and 10 to 90 percent of a first graft base C 2, said percents relative to the weight of said first graft polymer, where said first graft phase C.1 comprise
C.1.1 50 to 99 percent relative to the weight of said first graft phase of at least one member selected from the group consisting of styrene, a-methyl styrene, nucleus-substituted styrene, d.8 alkyl methacrylate and C,.e alky! acrylate, and
C 1.2 1 to 50 percent relative to the weight of said first graft phase of at least one member selected from the group consisting of acrylonitrile, methacrylonitrile. C,.8 alkyl methacrylate, C,^

alky! acrylate, maleic anhydride, CiU alkyl substituted maleic and phenyl-N-substituted maleic imide, and where said first graft base ccniorjse a crosslinked, particulate elastomer selected from the group consisting of butadiene and copolymers of butadiene with other ethylenically unsaturated monomers having an average particle JiSwiieter (d50 value) of 0.05 to 0.5 microns;
1 to 15 parts by weight of a second graft polymer containing 78 to 95 percent of a second graft phase D.1 and 5 to 22 percent of a second graft base D.2, said percents relative to the weight of said second graft polymer, where said second graft phase D.1 comprise D.1.1 65 to 85 percent relative to the weight of said second graft " phase of at least one member selected from the group consisting of styrene, a-methyl styrene, nucleus-substituted styrene, Ci-a alkyl methacrylate and C^ alkyl acrylate, and D. 1.2 15 to 35 percent relative to the weight of said second graft phase of at least one member selected from the group consisting of acrylonitrile, methacrylonitrile, Ci_e alkyl methacrylate, C^.8 alkyl acrylate. maleic anhydride, C,^ alkyl substituted maleic imide and phenyl-N-substituted maleic imide, and where said second graft base comprise a non-crosslinked elastomer selected from the group consisting of polybutadiene and copolymers of butadiene with at least one member selected from the group consisting of styrene, isoprene and C4-8 alkyl acrylate having a weight average molecular weight of 50,000 to 250.000 g/mole and where the second graft polymer has a weight average particle diameter of 0.6 to 20 microns; where the sum of A) + B) + C) + D) totals 100 resin, and 0.1 to 4 parts per 100 resin of a wax containing at least one ester group having a weight average molecular weight of 300 to 5000 " g/Mol and a melting point below 400°C

In a preferred embodiment, the components of the inventive composition are present in the following amounts;
Component A - 55 to 85 parts by weight,
Component L! 2 io 20 pa^ bv weight,
Component C - 10 to 30 parlstoy weight,
Component D - 2 to 10 parts toy weight, and
G.2 to 3 parts of Component E. In a most preferred embodiment, the components of the inventive composition are present in the following amounts:
Component A - 65 to 80 parts by weight,
Component B - 2 to 5 parts by weight,
Component C - 10 to 25 parts by weight,
Component D - 2 to 10 parts by weight, and
0.2 to 3 parts of Component E. Preferably, the first graft polymer comprise 30 to 80 percent of C.1 and 70 to 20 percent of C.2.
In a yet additionally preferred embodiment, component D contains 94 to 80 percent of a second graft phase D.1, and 6 to 20 percent by weight of a second grift base D.2. Component A
Suitable polycarbonate resins for preparing the copolymer of the present invention are homopolycarbonates and copolycarbonates and mixtures thereof.
The polycarbonates generally have a weight average molecular weight of 10,000 to 200,000, preferably 20,000 to 80,000, and their melt flow rate, per ASTM D-1238 at 300°C, is about 1 to about 65 g/10 min., preferably about 2 to 15 g/10 min. They may be prepared, for example, by the known diphasic interface process from a carbonic acid derivative such as phosgene and dihydroxy compounds by polycondensation (see German Offenlegungsschriften 2,063,050; 2,063,052; 1,570,703; 2,211,956; 2,211,957 and 2,248,817; French Patent 1,561,518; and the monograph by H. Schnell, "Chemistry and Physics of Polycarbonates",

Interscience Publishers, New York, New York, 1964, all incorporated herein by reference).
In the present-context, dihydroxy compounds suitable for the preparation of the polycarbonates of the "on conform to the structural formulae (1) or (2).

wherein
A denotes an alkylene group with 1 to 8 carbon atoms, an alkylidene group with 2 to 8 carbon atoms, a cycloalkylene group with 5 to 15 carbon atoms, a cycloaikylidene group with 5 to 15 carbon atoms, a carbonyl group, an oxygen atom, a sulfur atom, -SO- or -S02 or a radical conforming to


■■~: and g both dorote the number 0;o1;
Z denotes F, CI, Br or (VC4 alkyl and if several Z radicals are
substituents in one aryl radical, they may be identical or different
from one another;
d " denotes an integer of from 0 to 4; and
f denotes an integer of from 0 to 3.
Among the dihydroxy compounds useful in the practice of the • invention are hydroquinone, resorcinol, bis-(hydroxyphenyl)-alkanes, bis-(hydroxyphenyl)-ethers, bis-(hydroxyphenyl)-ketones, bis-(hydroxyphenyl)-sulfoxides, bis-(hydroxyphenyl)-sulfides, bis-(hydroxypheny!)-sulfones, a,a-bis-(hydroxyphenyl)-diisopropyl-benzenes, as well as their nuclear-alkylated compounds and dihydroxydiphenyl cycloalkanes. These and further suitable aromatic dihydroxy compounds are described, for example, in U.S. Patents 5,227,458; 5,105,004; 5,126.428; 5,109,076; 5,104,723; 5,086,157; 3,028,356; 2,999,835; 3,148,172; 2.991,273; 3,271,367; and 2,999,846, all incorporated herein by reference.
Further examples of suitable bisphenols are 2,2-bis-(4-hydroxy-phenyl)-propane (bisphenol A), 2,4-bis-(4-hydroxyphenyl)-2-methyl-butane. 1,1-bis-(4-hydroxyphenyl)-cyclohexane, a,a"-bis-(4-hydroxy-pheny!)-p-diisopropylbenzene, 2,2-bis-(3-methyl-4-hydroxyphenyf)-propane. 2,2-bis-(3-chloro-4-hydroxyphenyl)-propane, bis-(3,5-dimethyl-4-hydroxyphenyl)-methane, 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane, bis-(3,5-dimethy!-4-hydroxyphenyl)-sulfide. bis-(3,5-dimethyl-4-hydroxy-phenyl)-sulfoxide, bis-(3,5-dimethyl-4-hydroxyphenyl)-sulfone, dihydroxy-benzophenone, 2,4-bis-(3,5-dimethyl-4-hydroxyphenyl)-cyclohexane, a.a"-

bis-(3,5-dimethyl-4-hydroxyphenyl)-p-diisopropylbenzene and 4.4"-sulfonyl diphenol.
Examples of particularly preferred aromatic bisphenols are 2,2-bis-(4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane, 1,1-bis-(4-hydroxypheny()-cyclohexane and 1,1-bis-(4-hydroxy-phenyl)-3,3,5-trimethylcyclohexane.
The most preferred bispheno! is 2.2-bis-(4-hydroxyohenyl)-propane (bispheno! A).
The polycarbonates of the invention may entail in their structure units derived from one or more of the suitable bisphenols.
Among the resins suitable in the practice of the invention are phenolphthalein-based polycarbonates, copolycarbonates and terpolycarbonates such as are described in U.S. Patents 3,036,036 and 4,210,741, both incorporated by reference herein.
The polycarbonates of the invention may also be branched by condensing therein small quantities, e.g., 0.05 to 2.0 mole % (relative to the bisphenols) of polyhydroxy compounds.
Polycarbonates of this type have been described, for example, in German Offeniegungsschriften 1,570,533: 2,116,974 and 2,113,374; British Patents 885,442 and 1,079,821 ana U.S. Patent 3,5^4,514. The following are some examples of poiyhydroxyl compounds which may be used for this purpose: phloroglucinol; 4,6-dimethyl-2,4,6-tri-(4-hydroxy-phenyl)-heptane; 1,3,5-tn-(4-hydroxyphenyl)-benzene; 1,1,1 -tn-(4-hydroxy-phenyl)-ethane; tri-(4-hydroxyphenyl)-phenylmethane; 2,2-bis-[4,4-(4,4"-dihydroxydiphenyl)]-cyclohexyl-propane; 2,4-bis-(4-hydroxy-1-isopropy-lidine)-phenol; 2,6-bis-(2"-dihydroxy-5"-methylbenzyl)-4-methyl-phenot; 2,4-dihydroxybenzoic acid: 2-(4-hydroxyphenyl)-2-(2,4-dihydroxy-phenyl)-propane and 1,4-bis-(4,4"-dihydroxytriphenylmethyl)-benzene. Some of the other polyfunctional compounds are 2,4-dihydroxy-benzoic acid, tnmesic acid, cyanuric chloride and 3,3-bis-(4-hydroxyphenyi)-2-oxo-2, 3-dihydroindole.

In addition to the polycondensation process mentioned above, other processes for the preparation of the polycarbonates of the invention are polycondensation in a homogeneous phase and transesterification. The suitable processes are disclosed in the incorporated herein by reference U.S. Patents 3,028,365; 2,999,846; 3.153,008 and 2,991,273.
The preferred process for the preparation of polycarbonates is the intenacial polycondensation process.
Other methods of synthesis in forming the polycarbonates of the
invention such as disclosed in U.S. Patent 3,912,688, incorporated herein
by reference, may be used. .
Suitable polycarbonate resins are available in commerce, for instance, Makrolon FCR, Makrolon 2600, Makrolon 2800 and Makrolon 3100, all of which are bisphenol based homopolycarbonate resins differing in terms of their respective molecular weights and characterized in that their melt flow indices (MFR) per ASTM D-1238 are about 16.5 to 24, 13 to 16, 7.5 to 13.0 and 3.5 to 6.5 g/10 min., respectively. These are products of Bayer Corporation of Pittsburgh, Pennsylvania.
A polycarbonate resin suitable in the practice of the invention is known and its structure and methods of preparation have been disclosed, for example, in U.S. Patents 3,030.331; 3.169.121; 3,395,119; 3,729,447; 4,255.556; 4.260.731; 4.369.303; 4,714.746 and 5,227,458. all of which are incorporated by reference herein Component B
The rubber-free, thermoplastic vinyl copolymer component B of the present invention, contains B.1) 50 to 99 percent relative to the weight of the copolymer of at least
one member selected from the group consisting of styrene, alpha-methyl styrene, nucleus-substituted styrene and methylmeth-
acrylate and B.2) 1 to 50 percent relative to the weight of the copolymer of at least
one member selected from the group consisting of acrylonitnle,

methyl methacrylate, maleic anhydride, N-alkyl-substituted maleic
imide and N-aryl-substituted maleic imide.
The weight average molecular weight (as determined by light scattering or sedimentation) of the copolymer of component B is in the range of 15,000 to 200,000.
Particularly preferred ratios by weight of the components making up the copolymer B are 60 to 95 percent of B.1 and 40 to 5 percent of B.2. Particularly preferred copolymers B include those of styrene with acrylonitrile, optionally with methyl methacrylate; copolymers of alpha.-methyl styrene with acrylonitrile, optionally with methyl methacrylate and copolymers of styrene and alpha.-methyl styrene with acrylonitrile, optionally with methyl methacrylate.
The copolymers of component B are known and the methods for their preparation, for instance, by radical polymerization, more particularly by emulsion, suspension, solution and bulk polymerization are also well documented in the literature. The source of B in the claimed composition may be the ungrafted portion of components C and/or D and/or specifically added copolymer. Component C
The first graft polymer contains 10 to 90 percent of a first graft phase C.1 and 10 to 90 percent of a first graft base C.2, said percents relative to the weight of said first graft polymer. The first graft phase C.1 comprises C. 1.1 50 to 99 percent relative to the weight of said first graft phase of at
least one member selected form the group consisting of styrene, a-
methyl styrene, nucleus-substituted styrene. CI-B alkyl methacrylate
and Ci-8 alkyl acrylate, and C.1.2 1 to 50 percent relative to the weight of said first graft phase of at
least one member selected from the group consisting of
acrylonitrile, methacrylonitrile, C,.8 alkyl methacrylate, d.8 alkyl
acrylate, maleic anhydride, Ci^ alkyl substituted maleic imide and
phenyl-N-substituted maleic imide.

The first graft base comprise a crosslinked, particulate elastomer
selected from the group consisting of butadiene and copolymers of
butadiene with other ethylenically unsaturated monomers having an
average particle diameter (d50 value) of 0.05 to 0.5 microns.
The first graft polymer of the inventive composition is well known in
the art and is commercially available. A general description of such graft polymers is included in "Methoden der Organischen Chemie" (Houben Weyl), Vol. 14/1, Georg Thieme Verlag, Stuttgart 1961, pages 393-406 and in C. B. Bucknall, "Toughened Plastics", Appl. Science Publishers, London, 1977, incorporated herein by reference. Suitable graft polymers have been disclosed in U.S. Patents 3,564,077; 3,644,574 and 3,919,353, which are incorporated herein by reference.
Particularly preferred first graft polymers C may be obtainable by grafting of at least one (meth)acrylate and/or acrylonitrile and/or styrene as the first grafted phase onto a first graft base containing butadiene polymer having a gel content of at least 50% by weight (as measured in toluene), the degree of grafting (the degree of grafting is the weight ratio of graft monomers grafted on to the graft base and the monomers which were not grafted and is dimc-nsionless) being between 0.15 and 10. In addition to butadiene units, the graft base may contain up to 50% by weight, based on the weight of the butadiene units, of other ethylenically unsaturated monomers, such as styrene, acrylonitrile, esters of acrylic or methacrylic acid containing 1 to 4 carbon atoms in the alcohol component (such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate), vinyl esters and/or vinyl ethers The preferred graft base contains only polybutadiene.
Since the graft monomers do not have to be completely grafted onto the graft base in the grafting reaction, the first graft polymer C in the context of the invention is also understood to include products which are obtained by polymerization of the graft monomers in the presence of the graft base.

The average particle sizes (d 50) is the diameter above which 50%
by weight of the particles and below which 50% by weight of the particles
lie. It may be determined by uitracentrifuge measurement (W. Scholtan, H.
Lange, Kolloid Z. und Z. Polymere 250 (1972), 782-796).
The gel content of the graft base may be determined in dimethyl
formamide. (M. Hoffmann, H. Kromer, R. Kuhn, Polymeranalytik I und II,
Georg Thieme-Verlag. Stuttgart, 1977).
The first graft polymer may be produced by known methods, such
as bulk, suspension, emulsion or bulk suspension polymerization,
preferably by emulsion polymerization.
The average particle size (d 50) of the first graft polymer component
C of the present invention is about 0.05 to 0.5 microns, preferably 0.1 to
0.4 microns.
Component D
Component D, a second graft polymer is present in an amount of 1
to 15 parts by weight.
It contains 78 to 95 percent of a graft phase D. 1 and 5 to 22 percent
of a graft base D.2, the percents being relative to the weight of the second
graft polymer. The graft phase D.1 comprise
D. 1.1 65 to 85 percent relative to the weight or the graft phase of at least one member selected from the group consisting of styrene. alpha-methyl styrene, nucleus-substituted styrene, Ci,8 alky! methacrylate and C,.s aikvl acrylate, and
D. 1.2 15 to 35 percent relative to the weight of the graft phase of at least one member selected from the group consisting of acrylonitrile, methacryionitrile, C,.8 alkyl methacrylate, Ci-s alkyl acrylate. maleic anhydride. C1-4 alkyl substituted maleic imide and phenyl-N-substituted maleic imide.
and where said second graft base comprise a non-crosslinked elastomer
selected from the group consisting of polybutadiene and copolymers of
butadiene with at least one member selected from the group consisting of
styrene, isoprene and C4-8 alkyl acrylate having a weight average

molecular weight of 50,000 to 250,000 g/mole and where the second graft polymer has a weight,average particle diameter of 0.6 to 20 microns;
in a preferred embodiment, the graft phase contains 80 to 94 percent of D. 1.1 and 6 to 20 percent of D.1.2. In a further preferred embodiment, the graft base D.2 is present at an amount of 8 to 18 percent relative to the weight of the second graft polymer.
The second graft polymer of the invention, Component D, is largely similar to component C with a few important differences as these are noted above. This second graft polymer is also well known in the art and is commercially available. This graft has been extensively described in the literature, for instance in, "Methoden der Organischen Chemie" (HouDenWeyl), Vol. 14/1, Georg Thieme Verlag, Stuttgart, 1961, which is incorporated herein by reference.
Particularly preferred second graft polymer D may be obtainable by grafting of at least one (meth)acrylate and/or acrylonitrile and/or styrene as the grafted phase onto a graft base containing butadiene polymer. In addition to butadiene units, the graft base of Component D may contain up to 50% by weight, based on the weight of the butadiene units, of other etnylenically unsaturated monomers, such as styrene, isoprene or C4_g alkyl acrylate. The preferred graft base contains only polybutadiene or poly (butadiene-styrene) copolymer.
Since the graft monomers do not have to be completely grafted onto the graft base in the grafting reaction, the graft polymer D is also understood to include products which are obtained by polymerization of the graft monomers in the presence of the graft base
The weight average particle size of the second graft polymer, component D, of the present invention is about 0.6 to 20.0 microns, preferably 0.6 to 5 microns, most preferably 0.6 to 1.6 microns
The second graft polymer may be produced by known methods, such as suspension, bulk or mass graft polymerization. A preferred method entails mass or suspension graft polymerization of the

comonomers of the grafted phase, for instance, styrene and acrylonitrile, in the presence of polybutadiene.
In a preferred embodiment, Component D contains 10 to 16% by weight of graft base, which contains only polybutadiene. The weight average molecular weight (GPC) of the free SAN in the styrene/-acrylonitrile graft polymer is in the range from 50,000 to 150,000 and the crafted polybuta j"-ne has a weigh- average partic: ; ;ize in the rang^ A from 0.6 to 1.6 microns. Component E
Component E of the inventive composition is a wax which melts below 400 °C Waxes suitable in the practice are well known and are available in commerce. Chemically, these are compounds which are esters of a high molecular weight fatty acid with a high molecular weight alcohol, including mixtures of such esters. The molecular weight, weight average, or, where applicable, formula of the suitable waxes is in the range of 300 to 5000 g/mole. The alcohol component of the ester group is selected from among aliphatic, linear or branched, mono, bi-, or polyfunctional alcohols with more than two carbon atoms, preferably 3 to 22 carbon atoms, the acid component being mono-, di-, or polyfunctional aliphatic acids with more than 3 carbon atoms, preferred more than 5 carbon atoms. These compounds are known and are widely used as additives to polymeric molding compositions for their release function. Preferred compounds are the reaction products of C4 to C8 alcohols and C1-8 to C1-8 acids. Examples of preferred type esters are butylstearate, butyladipate and dioctyladipate.
Component E is present in the inventive composition in an amount of 0.1 to 4 parts per 100 resin of the total of A, B, C and D.
In addition, the composition of the invention may advantageously contain other additives such as plasticizers, antioxidants, plating additives. silicone oil, stabilizers, flame-retardants, fibers, mineral fibers, mineral fillers, dyes, pigments and the like.

The preparation of the inventive composition follows conventional procedures which are well known in the art. Usually, however, they are extrusion blended or compounded in a high intensity blender such as a Banbury Mixer or twin-screw extruder.
The invention is now described with reference to the following examples which aie for the purples onlv and are not intended to imply any limitation on the scope of the invention.
EXAMPLES COMPONENTS USED:
Polycarbonate - A linear polycarbonate based on bisphenol A having a meit viscosity of 4.5 grams per 10 minutes at 300°C with 1.2 kg load;ASTMD 1238.
ABS-1 and ABS-2 - prepared by the graft emulsion polymerization of styrene and acrylonitrile in a weight ratio of S/AN of about 70:30 in the presence of polybutadiene. ABS-1 and ABS-2 contained, respectively, 60 and 38 percent by weight of polybutadiene. The weight average molecular weights of the ungrafted SAN polymer fraction (GPC per ASTM Method D 3536-76) were respectively 80,000 and 100,000 g/mole. The ABS poiymer is recovered from the emulsion by conventional coagulation, filtration and washing The grafted polybutadiene has an average particle size of 0.3 to 0.2 micrometer measured as a d50 value measured by Photon Correlation Spectroscopy using a Brookhaven Instrument Company BI-90 Particle Size.
ABS-3 — prepared by the graft suspension polymerization of styrene and acrylonitrile in a weight ratio of 72:28 in the presence of polybutadiene.
ABS-3 contains 14% by weight of polybutadiene. The weight average molecular weight determined by GPC of the free SAN in the styrene/acrylonitrile graft polymer was 110,000 g/mole and the grafted polybutadiene had an average particle size of 0.8 microns

SAN-1 — a copolymer of styrene and acrylonitrile made by continous polymerization. The copolymer contains 75.5 weight % styrene and 24.5 weight % ac"vlcnitrile.
Each of the exemplified compositions contained 0.2 parts of butyl stearate per 100 resin of the total of A, B, C and D.
An extrusion process physically blended the components of the polymer blends of each example This was carried out in a 34 mm Leistritz twin-screw extruder (24:1 L:D screw; 250 revolutions per minute; at 260° C). A commercial antioxidant having no criticality in the present context was included in the compositional makeup at a level of 0.1% by weight. The die temperature was 260°C. The extruded material is passed through a water bath and peiletized
The peiletized material is then injection molded into specimens for testing.
Electroless plating was carried out by the process described below : Specimens tested for peel strength were prepared in the following manner:
Chromic Acid/Sulfuric Acid Etching—10 minutes at 68°C
Dead Rinse 1 minute
Cold Water Rinse —- 2 minutes
Neutralizer-Shipley PM 954 4 minutes at 40°C
Cold Water Rinse 1 minute
Activator-MacDermid D-34 C 4 minutes at 40DC
Cold Water Rinse 1 minute
Accelerator-Shipley PM 964 2 minutes at 52°C
Cold Water Rinse 1 minute
Electroless Copper-Shipley 251 10 minutes at40°C
Cold Water Rinse

Copper Strike 3 minutes @ 1 volt at 28°C
3 minutes @ 2 volts
2 minutes @ 3 volts
Acid Copper 120 minutes @ 40
amps/square foot at 28°C
The plate adhesion was measured in accordance with ASTM method B533-85 and Vicat temperature was measured in accordance with the procedure described in ASTM standard 1525.
The examples shown below illustrate the plate adhesion and heat performance.
In Example 1 (control) (not according to the invention) the heat resistance, determined as Vicat Temperature, is very high, yet the plate adhesion is very poor. In Example 5 (control) (not according to the invention) the adhesion is very good, yet the heat resistance is unacceptable/ low. Examples 2 and 4 demonstrate the invention where both heat resistance and adhesion are improved.
12 3 4 5
Poly¬
carbonate 70 70 70 70 50
ABS-1 14
ABS-2 20 20 16 25
ABS-3 5 10 10 10
SAN-1 16 5 4 15
Plate Adhesion
(lbs/in) 0.26 6.2 4.5 6.0 5.8
Vicat Temperature
(°C) 140 141 140 141 129

Although the invention has been described in detail in the foregoing :or the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the nvention except as it may tie limited by the claim
WE CLAIM :
1. A thermoplastic molding composition comprising
A) 51 to 90 parts by weight of an aromatic polycarbonate;
B) 2 to 20 parts by weight of a rubber free vinyl copolymer of 50 to 99 percent B.l and 1 to 50 percent B.2, the percents being relative to the weight of the copolymer, where B.l is at least one member selected from the group consisting of styrene, a-methyl styrene, nucleus-substituted styrene, and methyl methacrylate and where B.2 is at least one member selected from the group consisting of acrylonitrile, methyl methacrylate, maleic anhydride, N-alkyl-substituted maleic imide and N-aryl-substituted maleic imide;
C) 5 to 30 parts by weight of a first graft polymer containing 10 to 90 percent of a first graft phase C.l and 10 to 90 percent of a first graft base C.2, said percents relative to the weight of said first graft polymer, where said first graft phase C. 1 comprise
C. 1.1 50 to 99 percent relative to the weight of said first graft phase of at
least one member selected form the group consisting of styrene, a-methyl styrene, nucleus-substituted styrene, C1-8 alkyl methacrylate and C1-8 alkyl acrylate, and
C.1.2 1 to 50 percent relative to the weight of said first graft phase of at
least one member selected from the group consisting of acrylonitrile, methacrylonitrile, C1-8 alkyl methacrylate, C1-8 alkyl acrylate, maleic anhydride,C1-8 alkyl substituted maleic imide and phenyl-N-substituted maleic imide,
and where said first graft base comprise a crosslinked, particulate elastomer selected from the group consisting of butadiene and copolymers of butadiene

with other ethylenically unsaturated monomers having an average particle diameter (d50 value) of 0.05 to 0.5 microns;
D) 1 to 15 parts by weight of a second graft polymer containing 78 to 95 percent of a second graft phase D. 1 and 5 to 22 percent of a second graft base D.2, said percents relative to the weight of said second graft polymer, where said second graft phase D.l comprise
D.l.l 65 to 85 percent relative to the weight of said second graft phase of at
least one member selected from the group consisting of styrene. a-methyl styrene, nucleus-substituted styrene, C1-8 alkyl methacrylate and C1-8 alkyl acrylate, and
D. 1.2 15 to 35 percent relative to the weight of said second graft phase of at
least one member selected from the group consisting of acrylonitrile, methacrylonitrile, C1-8 alkyl methacrylate, C1-8 alkyl acrylate, maleic anhydride, C1.4 alkyl substituted maleic imide and phenyl-N-substituted maleic imide,
and where said second graft base comprise a non-crosslinked elastomer selected from the group consisting of polybutadiene and copolymers of butadiene with at least one member selected from the group consisting of styrene, isoprene and, C1-8 alkyl acrylate having a weight average molecular weight of 50,000 to 250,000 g/mole and where the second graft polymer has a weight average particle diameter of 0.6 to 20 microns; where the sum of A) + B) + C) + D) totals 100 resin, and
E) 0.1 to 4 parts per 100 resin of a wax containing at least one ester group having a weight average molecular weight of 300 to 5000 g/Mol and a melting point below 400°C.
The thermoplastic molding composition as claimed in claim 1 where
Component A is present in an amount of 55 to 85 parts by weight, and Component B is present in an amount of 2 to 20 parts by weight, and Component C is present in an amount of 10 to 30 parts by weight, and Component D is present in an amount of 2 to 10 parts by weight, and Component E is present in an amount of 0.2 to 3 parts.
3. The thermoplastic molding composition as claimed in claim 1 where the components are present in the following amounts : Component A - 65 to 80 parts by weight, Component B - 2 to 5 parts by weight, Component C - 10 to 25 parts by weight, Component D - 2 to 10 parts by weight, and 0.2 to 3 parts of Component E.
4. The thermoplastic molding composition as claimed in claim 1 where the average particle size (d 50) of component C is about 0.1 to 0.4 microns.
5. The thermoplastic molding composition as claimed in claim 1 where the weight average particle size of component D is 0.6 to 5 microns.
6. The thermoplastic molding composition as claimed in claim 1 where the weight average particle size of component D is 0.6 to 1.6 microns.
7. A thermoplastically molded article comprising the composition as claimed in claim 1, at least some of its surface is coated with an electrolessly deposited metal.
Dated 8th day of December, 2000.
[NALINIKRISHNAMUR 77]
OF REMFRY & SAGAR
ATTORNEY FOR THE APPLICANTS
-21-

Documents:

in-pct-2000-714-mum-claims(granted-(2-7-2004).doc

in-pct-2000-714-mum-claims(granted-(2-7-2004).pdf

in-pct-2000-714-mum-correspondence(3-7-2004).pdf

in-pct-2000-714-mum-correspondence(ipo)-(6-10-2006).pdf

in-pct-2000-714-mum-form 1(26-1-2001).pdf

in-pct-2000-714-mum-form 1a(2-7-2004).pdf

in-pct-2000-714-mum-form 1a(24-6-2004).pdf

in-pct-2000-714-mum-form 2(granted)-(2-7-2004).doc

in-pct-2000-714-mum-form 2(granted)-(2-7-2004).pdf

in-pct-2000-714-mum-form 3(13-7-2004).pdf

in-pct-2000-714-mum-form 3(24-6-2004).pdf

in-pct-2000-714-mum-form 4(25-3-2004).pdf

in-pct-2000-714-mum-form 5(8-12-2000).pdf

in-pct-2000-714-mum-petition under rule137(24-6-2004).pdf

in-pct-2000-714-mum-petition under rule138(24-6-2004).pdf

in-pct-2000-714-mum-power of authority(19-1-2001).pdf

in-pct-2000-714-mum-power of authority(24-6-2004).pdf


Patent Number 211334
Indian Patent Application Number IN/PCT/2000/00714/MUM
PG Journal Number 45/2007
Publication Date 09-Nov-2007
Grant Date 25-Oct-2007
Date of Filing 08-Dec-2000
Name of Patentee BAYER CORPORATION
Applicant Address 100 BAYER ROAD, PITTSBURGH, PENNSYLVANIA 15205,
Inventors:
# Inventor's Name Inventor's Address
1 VENTKATARAYALOO JANARTHANAN 15 GREEN PARK SOCIETY, TANDALJA RD, VADODARA 390 020,
2 ROLAND PETER BRASSARD A US CITIZEN OF 225 COOPER ST. AGAWAN, MASSACHUSETTS 01001-2165
3 KARL-ERWIN PIEJKO A GERMAN CITIZEN OF 129 GERRNHILL ROAD, LONGAMEADOW, MASSACHUSETTS 01106-2929
4 SARA DIANE GRAHAM A US CITIZEN OF 264 FLORIDA AVENUE, AMSTERDAM, NEW YORK 12010
PCT International Classification Number CO8L69/00
PCT International Application Number PCT/US99/13469
PCT International Filing date 1999-06-15
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 09/098,817 1998-06-17 U.S.A.