Field of the Invention
This invention is directed to multilayer plastic articles, their properties and methods for making such articles More particularly the articles comprise a substrate or base layer of an injection molded, blow molded or extruded thermoplastic and a top and/or bottom layer of acycloahphatic polyester Background of the Invention
There is substantial commercial interest in the use of plastic materials in various product forms such as sheet, film, shaped products, thermoformed articles, packaging, and architectural products Many different plastics are used for such products in order to take advantage of particular phvsical, chemical, and mechanical properties Summary of the Invention
Thermoplastic resins are provided with a surface film which improves weatherabihty, and solvent resistance, and which can be used to modify the color and appearance of the thermoplastic material The surface film comprises a thm film of a cycloahphatic polyester which is applied to the thermoplastic substrate by lamination, coextrusion or bv an m-mold process known in the art as "m-mold decoration" in which the surface film is placed in the mold and the thermoplastic
melt, which forms the substrate or base layer, is injection molded to the exposed surface or surfaces of the film
The substrate or base layer can be any suitable thermoplastic resin including polycarbonates,
polyesters, acrylonitrile-butadiene-stvrene resins, referred to as ABS resins, acrylomtrile-styrene-acrylate resins , referred to as ASA resins, a polyphenylene ether or polyphenylene ether/polystyrene blend and blends comprising polycarbonate in a mixture with one or more ABS, ASA or polyester resins
In one embodiment of the invention a cycloahphatic polyester layer can be laminated or adhered to both sides, i e , top and bottom of the injection molded substrate, thereby making a three layer structure in which the substrate is protected on both sides by the same or different cycloahphatic polyester layers Various intermediate layers can be applied for decorative or functional purposes, or the cycloahphatic polyester resin itself can be colored or modified to be the decorative layer
The structures of this invention can be transparent, opaque, or non-transparent, or combinations of transparent and opaque layers as desired Transparent products are a preferred embodiments of this invention The composite multilayered structure or article can be stabilized by inclusion of ultra violet or infrared absorbing additives
The invention provides articles comprising a thermoplastic substrate or base, preferably a polycarbonate resin or polycarbonate blend with other resins, and at least one surface layer comprised of a cvcloahphatic polyester or a blend of polycarbonate and cycloahphatic polvester The substrate can have a surface layers on both sides The base and surface layers can be provided with compatible functional additives
Detailed Description
Polycarbonates (PC) for use in the production of the multilayered articles of the invention are thermoplastic, aromatic polymers and include homopolycarbonates, copolycarbonates and copolyestercarbonates and mixtures thereof which have average molecular weights of about 8,000 to more than 200,000, preferably of about 20,000 to 80,000 and an intrinsic viscosity (IV) of 0 40 to 1.5 dl/g as measured in methylene chloride at 25° C In one embodiment, the polycarbonates are derived from dihydnc phenols, or bisphenols, and carbonate precursors
Polycarbonates are a well known class of high impact resistant thermoplastic resins characterized by optical claritv and high ductility One of the most important engineering thermoplastics in use today are the polycarbonates Polycarbonates can be defined as polymers containing recurring carbonate groups (-O-CO-O-) m the mam chain Aromatic polycarbonates are of particular interest in the practice of this invention These polymers are known per se and are generally prepared by reacting a dihydnc phenol, or bisphenol, with a carbonate precursor, e g., phosgene, a halogen formate, or a carbonate ester
Aromatic polycarbonates comprise multiple structural units represented by the formula
(Formula Removed)
wherein A1 is a divalent aromatic hydrocarbon radical Suitable aromatic hydrocarbon radicals for inclusion as A1 include m-phenylene, p-phenylene, 4,4'-biphenylene, 4,4'-bi(3,5-dimethyl)-phenylene, 2,2-bis(4-phenylene)propane and similar radicals such as those which correspond to the dihvdroxy-substiruted aromatic hydrocarbons disclosed by name or formula in U S Patent 4,217,438

The Al radical preferably has the formula:
(Formula Removed)
wherein each of A2 and A3 is a mono cyclic divalent aromatic hydrocarbon radical and Y is a bridging hydrocarbon radical in which one or two atoms separate A2 from A3 The free valence bonds in formula 2 are usually in the
meta or para positions of A2 and A3 m relation to Y. Compounds in which A1 has formula 1 are bisphenols, and for the sake of brevity the term "bisphenol'' is sometimes used herein to designate the dihydroxy-substituted aromatic hydrocarbons, it should be understood, however, that non-bisphenol compounds of this type may also be employed as appropriate.
In formula 2, the A2 and A3 values may be unsubstituted phenylene or hydrocarbon-substituted derivatives thereof, illustrative substituents (one or more) being alkyl and alkenyl Unsubstituted phenylene radicals are preferred
JBoth A2 and A3 are preferably p-phenylene, although both may be o- or m-phenylene or one o- or m-phenylene and the other p-phenvlene
The bridging radical, Y, is one in which one or two atoms, preferably one,
separate A2 from A3 Illustrative radicals of this type are methylene,
cyclohexylmethylene, 2-[2.2.1]-bicycloheptylmethylene, ethylene,
isopropylidene, neopentylidene, cyclohexylidene, cyclopentadecylidene, cyclododecylidene and adamantylidene; gem-alkylene (alkylidene) radicals are preferred Also included, however, are unsaturated radicals. For reasons of availability and particular suitability for the purposes of this invention, the preferred bisphenol is 2,2-bis(4-hvdroxyphenyl)propane ("bisphenol A"), m
which Y is isopropylidene and A2 and A 3 are each p-phenvlene.
Cycloahphatic polyesters suitable for use m the present invention are those which are characterized by optical transparency, improved weatherablity
compared to the substrate alone, chemical resistance, and low water absorption The cycloahphatic polyester layers also have good melt compatibility with the substrate resins allowing easy recycling of the multilayer structures by simply re-melting the multilayer article and reforming one of the layers as a combination of the substrate layer and the cycloahphatic cap layer Other cap layers, for instance chlorinated polyolefms may react on re-melting causing degradation of the substrate resin particularly if the substrate resin is a high melting condensation polymer like polycarbonate This compatibility of the cap layer and the substrate of the multilayered articles of this invention allows recycling of scrap during manufacture or simple recovery of the resins after the useful lifetime of the article. This is especially beneficial in articles containing polycarbonate or polycarbonate blends.
Cycloahphatic polyesters useful m the practice of the invention are prepared by reaction of a diol with a dibasic acid or derivative
The diols useful in the preparation of Ihe cycloahphatic polyester resins for use as the surface films of the present invention are straight chain, branched, or cycloahphatic, preferably straight chain or branched alkane diols, and may contain from 2 to 12 carbon atoms Examples include, but are not limited to, ethylene glycol, propylene glycol, I e , 1,2- and 1,3-propvlene glycol, butane diol, l e , 1,3- and 1,4-butane diol, diethylene glycol, 2,2-dimethyl-l,3-propane diol, 2-ethyl, 2-methyl, 1,3-propane diol, 1,3- and 1,5-pentane diol, dipropylene glycol, 2-methyl-l,5-pentane diol, 1,6-hexane diol, 1,4-cyclohexane dimethanol and particularly its cis- and trans-isomers, triethylene glycol, 1,10-decane diol, and mixtures of any of the foregoing. Particularly preferred is dimethanol bicyclo octane, dimethanol decahn, a cycloahphatic diol or chemical equivalent thereof and particularly 1,4-cvciohexane dimethanol oi its chemical equivalents are to be used as the diol component, it is preferred that a mixture of cis- to trans-isomer thereof, ranging from 1 4 to 4.1, and preferably, a ratio of about 1 3 is used
Chemical equivalents to the diols include esters, such as dialkylesters, diaryl esters, and the like
The diacids useful in the preparation of the cycloahphatic polyester resins of the present invention are aliphatic diacids This is meant to include carboxvhc acids having two carboxyl groups each of which is attached to a saturated carbon in a saturated ring A preferred diacid is 1,4-cyclohexanedicarboxyhc acid and most preferred is trans-l,4-cyclohexanedicarboxyhc acid as further explained above Other cycloahphatic acids include decahvdro naphthalene dicarboxvhc acid, norbornene dicarboxylic acids, bicvcio octane dicarboxvhc acids Linear aliphatic diacids are also useful provided the polvester has at least one monomer containing a cycloahphatic ring Illustrative examples of linear aliphatic diacids are succinic acid, adipic acid, dimethyl succinic acid, and azelaic acid
Mixtures of diacid and diols mav also be used to make the cycloahphatic polyesters of the invention
Cyclohexanedicarboxyhc acids and their chemical equivalents can be prepared, for example, by the hydrogenation of cycloaromatic diacids and corresponding derivatives such as isophthalic acid, terephthalic acid of naphthalenic acid in a suitable solvent, water or acetic acid at room temperature and at atmospheric pressure using suitable catalvsts such as rhodium supported on a suitable carrier of carbon or alumina See, Fnefelder et al , Journal of Organic Chemistry, 31, 34-38 (1966), U.S. Patent Nos 2,675,390 and 4,754,064 They may also be prepared by the use of an inert liquid medium m which a acid is at least partially soluble under reaction conditions and a catalyst of palladium or ruthenium m carbon or silica See, U S Patent Nos 2,888,484 and 3,444,237
Typically, during hydrogenation, two or more isomers are obtained in which the carboxyhc acid groups are in cis- or trans-positions The cis- and trans-lsomers can be separated by crystallization with or without a solvent, tor example, n-heptane, or by distillation The cis-isomer tends to blend better,


however, the trans-isomer has higher melting and crystallization temperatures and is especially preferred Mixtures of the cis- and trans-isomers are useful herein as well, and preferably when such a mixture is used, the trans-isomer will comprise at least about 75 parts by weight and the cis-isomer will comprise the remainder based upon 100 parts bv weight of cis- and trans-isomers combined When a mixture of isomers or more than one diacid is used, a copolyester or a mixture of two polyesters may be used as the cycloahphatic polyester resin m the present invention
Chemical equivalents of these diacids include esters, alkyl esters, e g ,
dialkyl esters, diaryl esters, anhydrides, acid chlorides, acid bromides, and the
like The preferred chemical equivalents comprise the dialkyl esters of the
cycloahphatic diacids, and the most preferred chemical equivalent comprise the
dimethyl ester of the acid, particularh dimethyl-trans-1,4-
cyclohexanedicarboxylate
Dimethyl-l,4-cyclohexanedicarboxylate can be obtained by ring Irydrogenation of dimethvlterephthalate, and two isomers having the carboxyhc acid groups in the cis- and trans-positions are obtained The isomers can be separated, the trans-isomer being especially preferred Mixtures of the isomers are suitable as explained above and preferably m the ratios as explained above
The polyester resins of the present invention are typically obtained through the condensation or ester interchange polymerization of the diol or diol equivalent component with the diacid or diacid chemical equivalent component and having recurring units of the Formula 3
(Formula Removed)
wherein R13 represents an alkyl or cvcloalkvl radical containing 2 to 12 carbon atoms and which is the residue of a straight chain, branched, or cycloahphatic

alkane diol having 2 to 12 carbon atoms or chemical equivalents thereof, and R14 is an alkyl or a cycloahphatic radical which is the decarboxylated residue derived from a diacid, with the proviso that at least one of R13 or R14 is a cycloalkyl group
A preferred cycloahphatic polyester is pol)'(l,4-cyclohexane-dimethanol-1,4-cyclohexanedicarboxylate) (PCCD) having recurring units of formula 4
(Formula Removed)
wherein R13 is a cyclohexane ring, and wherein R:4 is a cyclohexane ring derived from cyclohexanedicarboxylate or a chemical equivalent thereof and is selected from the cis- or trans-isomer or a mixture of cis- and trans-isomers thereof
Cycloahphatic polyester resins of the instant invention can be generally
made following the teachings of, for example, U 5 Patent 2,465,319 The reaction
is generally run m the presence of a suitable catalyst such as a tetra(2-ethyl
' hexyl)titanate, in a suitable amount, typically about 50 to 400 ppm of titanium
based upon the final product.
Poly(l,4-cyclohexanedimethanol-l,4-cyclohexanedicarboxylate), herein abbreviated as PCCD, film shows excellent adhesion to polycarbonate resin substrates, including polycarbonate blends with other thermoplastics, without using a primer BPA polycarbonates are preferred substrate resins for use in this invention. Films comprising blends of PCCD and polvcarbonates also be used as the cap layers of this invention They exhibit excellent primerless adhesion to a polycarbonate substrate when the film is bonded to the polycarbonate by lamination, hot pressing, in mold decoration, melt extrusion of the polycarbonate on to a PCCD film, coextrusion of both resins, or any similar bonding or joining technique known to those in the art An In mold decoration process is described m "Modern Plastics " Feb 1998, p34
The cap layer of the invention may also comprise a blend of polycarbonate resm with cycloahphatic polyester resin Addition of the PC resm to the cycloaliphatic polyester allows retention of clarity and increases the heat distortion temperature (HDT) of the cap layer allowing it be used in a wider range of articles PC addition to the cycloahphatic cap layer resin may also beneficially alter its melt strength and crystallization behavior A preferred embodiment provides a blend of cycloahphatic polyester resin, and cycloahphatic polyesters with increased stiffness containing rigid segments such as adamantane, neopentyl or norbornene segments
A preferred embodiment provides a composition wherein the
polycarbonate is bisphenol-A polycarbonate, the cycloahphatic polyester resm is
derived from a cycloahphatic diol and a cycloahphatic diacid The preferred
cycloahphatic resin being poly (l,4-cyclohexanedimethanol-l,4-
cyclohexanedicarboxylate) (PCCD), and further, wherein the ratio of the polycarbonate to PCCD is from about 60 40 to about 75 25
Blends of polymers such as polycarbonate and cycloahphatic polyesters generally contain catalyst quenchers Catalyst quenchers are agents which inhibit activity of any catalysts which mav be present m the resins Catalyst quenchers are described in detail m U S Patent 5,441,997 It is critical to chose the correct quencher to avoid color formation and loss of clarity in the cap layer when it consists of a cycloaliphatic polyester blended with PC resin
A preferred class of quenchers are those which provide a transparent and colorless product Typically, such stabilizers are used at a level of 0 001-10 weight percent and preferably at a level of from 0 005-2 weight percent The preferred stabilizers include an effective amount of an acidic phosphate salt, an acid, alkyl, aryl or mixed phosphite having at least one acidic hydrogen, a Group IB or Group IIB metal phosphate salt, a phosphorus oxo acid, a metal acid pyrophosphate or a mixture thereof The suitability of a particular compound
for use as a stabilizer and the determination of how much is to be used as a stabilizer may be readily determined by preparing a mixture of the polyester resin component, and polycarbonate resin with and without the particular compound and determining the effect on melt viscosity, gas generation, color or the formation of interpolymer The acidic phosphate salts include sodium, dihydrogen phosphate, mono zinc phosphate, potassium hydrogen phosphate, calcium dihydrogen phosphate and the like The phosphites may be of the formula
(Formula Removed)
where R1, R2 and R1 are independently selected from the group consisting of hydrogen, alkyl and aryl with the proviso that at least one of R1, R2 and R3 is hydrogen.
The phosphate salts of a Group IB or Group IIB metals of the periodic table include zinc phosphate, copper phosphate and the like The phosphorus oxo acids include phosphorous acid, phosphoric acid, polyphosphoric acid or hypophosphorous acid.
The polyacid pyrophosphates may be of the formula
MzxHvPn03n+i
wherein M is a metal, x is a number ranging from 1 to 12 and y is a number ranging 1 to 12, n is a number from 2 to 10, z is a number from 1 to 5 and the sum of (xz) + y is equal to n + 2 The preferred M is an alkaline or alkaline earth metal
The most preferred quenchers are oxo acids of phosphorous or acidic organo phosphorus compounds Inorganic acidic phosphorus compounds may also be used as quenchers, however they may result in haze or loss of clarity Most preferred quenchers are phosphoric or phosphorous acid
Cycloahphatic polyester resins have been found to have better weatherabihty than polycarbonate alone Ultraviolet light absorbers are used to improve the polycarbonate light stability Inclusion of a light stabilizer in a cycloahphatic polyester layer on the polycarbonate surface has been found to provide additional light stability for the polycarbonate resin
The ultraviolet light absorbers (UVA) useful m the present invention are those which are generally compatible with polycarbonates Preferred are benzotriazole, benzophenone, triazine, cyanoacrylate, dibenzoylresorcmol, and oxanihde based UVA Incorporation of a light stabilizing additive in the PCCD composition, 1 e, cycloahphatic polyester alone or a polvcarbonate cycloahphatic polyester blend, provides additional benefits in weatherabihty
In addition to UV absorbers, hindered amine light stabilizers (HALS) also contribute to increased weatherabihty of the structure
Illustrative ultraviolet radiation absorbing compounds include 2-(benzotriazol-2-yI)-4-(l,l,3,3-terramethyIbutyl)phenol,
2-(benzotriazol-2-yI)-4-methylphenol, 2-hvdroxy-4-octvloxy benzophenone, 2-
hydroxy-4-methoxybenzophenone, ethvI-2,2-diphenvl-l-cyanoacrylate, 2-
ethylhexyl - 2, 2-diphenyl-l-cyanoacrylate, 2-(2'-hydroxy-4,-octyloxy) bis-4,6-(2',4'-dimethylphenyl) triazine, 2-ethvl- 2- ethoxy oxalamde, bis [ 2-hydroxyo-methyl-3- (benzotriazol-2-yl) phenyl ] - methane, bis[ 2 - hydroxy- 5 -t - octyl -3 - ( benzotriazol -2 -yl) phenyl] methane, 2,2' - ( 1,4 - phenvlene ) bis [ 4 H - 3, 1 -benzoxazin -4 - one], and 2 - ( 2' - hvdroxy-4-hexyloxy) - 4,6 - diphenyltriazine Light stabilizers are incorporated m the cycloahphatic polyester e g , PCCD, resin in amounts of about 0 05 to about 10 weight percent
Blends comprising polycarbonate and cycloahphatic polyester components form one class of resin compositions which can be used to form the multilayer articles of this invention Such blends generally contain various additives such as colorants , light stabilizers, ultraviolet absorbers, and the like,
m addition to quenchers In preferred examples, the polycarbonate and the cycloahphatic polyester resin, taken together, comprise (a) from about 70% to about 99 94% by weight of the total composition, the ratio of the polycarbonate to the cycloahphatic polyester resin being from about 50 50 to about 90.10, (b) the benzotriazole, benzophenone, triazme, cyanoacrylate, dibenzoylresorcmol, and oxamhde based UV absorber comprises from about 0.05% to about 10% by weight of the total composition, and (c) the catalyst quencher comprises from about 0.001% to about 3% by weight of the total composition
Other preferred embodiments of the instant invention provide a composition wherein the benzotriazole, benzophenone, triazme, cyanoacrylate, dibenzoylresorcmol, and oxamhde based UVA comprises from about 0 3% to about 10% by weight of the total composition of the film laver Another preferred embodiment provides a composition wherein the benzotriazole, benzophenone, triazme, cyanoacrylate, dibenzoylresorcmol, and oxamhde based UVA comprises from about 0 3% to about 1% by weight of the total composition Irhndered amine light stabilizers, which are well known in the art, may optionally be added at 0.01 to about 1% of the total composition
In another embodiment of the invention the support layer or substrate comprises an ABS type polymer or an ABS -PC blend In general, ABS type polymers contain two or more polvmeric parts of different compositions which are bonded chemically. The polymer is preferably prepared by polymerizing a conjugated diene, such as butadiene or a conjugated diene with a monomer copolymenzable therewith, such as stvrene, to provide a polymeric backbone After formation of the backbone, at least one grafting monomer, and preferably two, are polymerized in the presence of the prepolymenzed backbone to obtain the graft polymer These resins are prepared by methods well known m the art
Related ASA resins (Acrylonitrile-Styrene-Acrylate ) are made m a similar fashion in some cases by grafting acrvlonitrile, stvrene and an optionally an alkvl
acrylate to an acrylic rubber ASA may also be blended with polycarbonate to form a substrate resin
In ABS the backbone polymer, as mentioned, is preferably a conjugated diene polymer such as polybutadiene, polyisoprene, or a copolymer, such as butadiene-styrene, butadiene-acrylonitrile, or the like Examples of dienes that may be used are butadiene, isoprene, 1,3-heptadiene, methyl-l,3-pentadiene, 2,3-dimethyl-l,3-butadiene, 2-ethyl-l,3-pentadiene, 1,3- and 2,4-hexadienes, chloro and bromo substituted butadienes such as dichlorobutadiene, bromobutadiene, dibromobutadiene, mixtures thereof, and the like A preferred conjugated diene is butadiene
One monomer or group of monomers that may be polymerized m the presence of the prepolymerized backbone are monovinvlaromatic hydrocarbons Examples of the monovinylaromatic compounds and alkyl-, cycloalkyl-, aryl-, alkaryl-, aralkyl-, alkoxy-, aryloxy-, and other substituted vinylaromatic compounds include styrene, 3-methylstyrene, 3,5-diethylstyrene, 4-n-propylstyrene, alpha-methylstyrene, alpha-methyl vinyltoluene, alpha-chlorostyrene, alpha-bromostyrene, dichlorostvrene, dibromostyrene, tetra-chlorostyrene, mixtures thereof, and the like The preferred monovinvlaromatic hydrocarbons used are styrene and alpha -methylstyrene
A second group of monomers that mav be polvmenzed in the presence ot the prepolymerized backbone are acrylic monomers such as acrylonitrile, substituted acrylomtrile and/or acrylic acid esters, exemplified by acrylonitrile, and alkyl acrylates such as methyl methacrylate Examples of such monomers include acrylonitrile, ethacrylonitrile, methacrylomtrile, alpha chloroacrylonitrile, beta -chloroacrylonitrile, alpha -bromoacrylonitrile, and beta -bromoacrylomrrile, methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, propyl acrylate, isopropyl acrylate, and mixtures thereof The preferred

acryhc monomer; is acrylonitrile and the preferred acrylic acid esters are ethyl acrylate and methyl methacrylate
In the preparation of the graft polvmer, the conjugated diolefm polymer or copolymer exemplified by a 1,3-butadiene polymer or copolymer comprises about 50% by weight of the total graft polymer composition The monomers polymerized in the presence of the backbone, exemplified bv styrene and acrylonitrile, comprise from about 40 to about 95% by weight of the total graft polymer composition
The second group of grafting monomers, exemplified bv acrylonitrile, ethyl acrylate or methyl methacrvlate, of the gratt polvmer composition, preferably comprise from about 10% to about 40% by weight of the total graft copolymer composition. The monovmylaromatic hydrocarbon exemplified by styrene comprise from about 30 to about 70% bv weight of the total graft polymer composition.
In preparing the polymer, it is normal to have a certain percentage of the /polymerizing monomers that are grafted on the backbone combine with each other and occur as free copolymer If styrene is utilized as one of the grafting monomers and acrylonitrile as the second grafting monomer, a certain portion oi the composition will copolymenze as free stvrene-acrylorutrile copolymer In the case where alpha -methylstyrene (or other monomer) is substituted for the styrene in the composition used in preparing the graft polymer, a certain percentage of the composition mav be an alpha -methylstyrene-acrylonitrile copolymer. Also, there are occasions where a copolymer, such as alpha -methylstyrene-acrylonitrile, is added to the graft polymer copolymer blend When the graft as polymer-copolymer blend is referred to herein, it is meant optionally to include at least one copolymer blended with the graft polymer composition and which mav contain up to 90% of free copolymer
Optionally, the elastomeric backbone may be an acrylate rubber, such as one based on n-butyl acrylate, ethylacrylate, 2-ethylhexylacrylate, and the like Additionally, minor amounts of a diene may be copolvmerized in the acrvlate rubber backbone to yield improved grafting with the matrix polymer
The preferred ABS material for the support layer is Cycolac© resin available from the GE Plastics component of General Electric Company
Additional material for the support layer include polycarbonate and ABS blends The polycarbonate and ABS, respectively, are as before described with Lexan® resin and Cycolac® resin being available from GE Plastics component of General Electric Company The ABS/polycarbonate resin is also available from GE Plastics as Cvcoloy® resin Suitable blends contain about 15 to about 85 weight percent polycarbonate and about 15 to about 85 weight percent ABS resin
Other preferred substrate layers are polyester components include crystalline polyesters such as polyesters derived from aliphatic or cycloahphatic diols, or mixtures thereof, containing from 2 to about 12 carbon atoms and at least one aromatic dicarboxylic acid Preferred polyesters are derived from an aliphatic diol and an aromatic dicarboxylic acid having repeating units of the following general formula
(Formula Removed)
R wherein n is an integer of from 2 to 6 Ar is a C6-C20 aryl radical comprising a
decarboxylated residue derived from an aromatic dicarboxvlic acid
Examples of aromatic dicarboxvlic acids represented b\ the
decarboxylated residue Ar are isophthalic or terephthahc acid, l,2-di(p-
carboxyphenyl)ethane, 4,4'-dicarboxvdiphenvl ether, 4,4' bisbenzoic acid and
mixtures thereof All of these acids contain at least one aromatic nucleus Acids
containing fused rings can also be present, such as m 1,4- 1,5- or 2,6- naphthalene dicarboxylic acids The preferred dicarboxyhc acids are terephthahc acid, isophthahc acid, naphthalene dicarboxylic acid or mixtures thereof
The most preferred polyesters are poly(ethylene terephthalate) (PET), and poly(butylene terephthalate) (PBT), poly(ethylene naphthanoate) (PEN), poly(butylene naphthanoate) (PBN), poly(propylene terephthalate) (PPT), or mixtures of these resins
Also contemplated herein are the above polvesters with minor amounts, e g , from about 0.5 to about 15 percent by weight, ot units derived from aliphatic acids and/or aliphatic polvols to form copolvesters The aliphatic polvols include glycols, such as poly(ethylene glvcol) or poly(butvlene glvcol) Such polvesters can be made following the teachings of, for example, U S Pat Nos 2,465,319 and 3,047,539
The preferred poly(l,4-butylene terephthalate) resin used in this invention
is one obtained by polymerizing a glycol component at least 70 mol %, preferably
t at least 80 mol %, of which consists of tetramethvlene glvcol and an acid
component at least 70 mol %, preferably at least 80 mol %, of which consists of
terephthahc acid, and polvester-forming derivatives therefore
The polyesters used herein have an intrinsic viscosity of from about 0 4 to about 2 0 dl/gm measured in a 60 40 phenol/tetrachloroethane mixture or similar solvent at 23-30° C VALOX ®315 polvester is particularlv suitable tor this invention Preferably intrinsic viscosity is about 1 1 to about 1 4 dl/gm
Blends of polvesters may also be employed in the composition Preferred polyesters blends contain poly(ethvlene terephthalate) and poly(l,4-butylene terephthalate) When blends of these preferred components are emploved the polyester resin component can comprise from about 5 to about 50 parts by weight poly(ethylene terephthalate) and from about 95 to about 50 part by
weight poly(l,4-riutylene terephthalate) based on 100 parts by weight of both components combined
Also, blends ' of relatively low molecular weight polybutylene terephthalate resin may be used with a relatively high molecular weight polybutylene terephthalate as set forth in U.S patent 5,589,530 to Walsh The low molecular weight polybutylene terephthalate is a PBT resin having a melt viscosity of less than 600 poise at 250°C
The aromatic polyesters are the reaction products of aliphatic diols and aromatic dicarboxylic acids, or their derivatives Preferred diols are C2-C12 diols; especially preferred are ethylene glycol, propvlene glycol and butylene glycol Preferred dicarboxylic acid are derived from benzene or naphthalene rings. Most preferred diacids are iso and tere phthalic acid or naphthalene dicarboxylic acid, especially the 2, 6 naphthalene dicarboxylate
Blends of polycarbonate with polyesters are also preferred substrates As indicated earlier, the preferred polycarbonate is bisphenol-A polycarbonate When blends of these preferred components are employed the polyester resin component can comprise from about 1 to about 99 parts by weight polyester and from about 99 to about 1 part by weight polycarbonate based on 100 parts by weight of both components combined
These materials especially when further blended with rubbery impact modifiers provide resins with excellent impact and stiffness The preferred polycarbonate resins are as described previously with BPA-PC being most preferred Impact modifiers especiallv suitable for optional inclusion in the aromatic polyester polycarbonate blends are core shell modifiers such and MBS (methacrylate-butadiene-styrene)copolymers and methylmethacry late-butyl acrylate (acrylic rubber) core shell rubbers as well as acrylomtrile styrene gratt polybutadiene rubbers (ABS rubber)
Thermoplastic resins comprising a blend of polycarbonate and polyesters resin are available from General Electric Company Plastics Division under the trademark Xenoy®.
Articles of the invention may also use polyphenylene ether and polyphenylene ether/polystyrene blends as the substrate The polyphenylene either resins can be homopolymers or copolymers and are preferably derived from the polymerization of alkyl or aryl substituted phenols, 2,6 xylenol and 2,3,6 trimethyl phenol are especially preferred The polystyrene resins used m blends with the polyphenylene ethers can be alkyl, aryl or halogen substituted They may further be modified with rubber especially butadiene based rubber Most preferred are polystyrene, alpha-methyl polystyrene, para-methyi polystyrene and high impact modified polystyrene known as HIPS Polyphenylene ether polystyrene blends are sold by GE Plastics under the Noryl® trade name
The composite article comprising a base or substrate of a thermoplastic /resin such as a polycarbonate, polyester, or an ABS resin or a polycarbonate resin blend and an adherent layer of cycloaliphatic polyester film is preferably, optically transparent and has improved weather resistance when compared to the substrate, e g., polycarbonate, surface alone In addition to a transparency of greater than 87%, the polycarbonate cycloaliphatic polyester composite is characterized by other properties such as good impact strength, low water absorption, chemical resistance to methanol, ethyl acetate, and MEK, low shrinkage, good processabihty, printabihty, and curability
The substrate resin mav also contain other additives such as colorants, flame retardant chemicals, glass fibers, mineral fillers such as talc, clay, barium sulfate, mica, glass spheres as well as thermal stabilizers , lubricants and other processing aids
In a preferred method for forming the multilayer articles of this invention a surface layer is formed by coextruding polycarbonate and cycloahphatic as a composite film. The substrate is then injected onto the polycarbonate side of the composite during a subsequent molding operation The resulting multilayer article comprises a substrate (in this case PC), an intermediate film of the same material as the substrate, e.g , polycarbonate, and a top layer of a cycloahphatic polyester, such as PCCD. The composite film can be anv suitable and convenient thickness. For example the polycarbonate film can be about 10 mils thick and the PCCD film can be about 5 mils thick, the substrate can be thicker Any ink or decorative layer can be printed on the surface of the laminated polycarbonate or cycloahphatic polyester film
The articles of the invention can be formed by various processes for instance; compression molding, multilayer blow molding, coextrusion of sheet or film, injection over molding, insertion blow molding and other methods
The multilayer articles of the invention can have a variety of uses in business equipment, hand held communication devices, pagers, telephones, automobiles m applications such as body panels , interior and exterior trim and bumpers The articles can also be used , glazing, membrane switches, packaging, building and construction
The following examples are presented to illustrate the invention and should not be construed to limit the scope of the invention Example 1
A blend of 60% PCCD and 40 % PC film 13-15 mil thick was prepared with 0.05% [45%] aqueous phosphorous acid The extrusion conditions are listed in Table 1

(Table Removed)
The resulting 13-15 mil film was optically transparent with good appearance. Example 2:
A 10 mil optically transparent 100 % PCCD film was also prepared. Prior to extrusion the PCCD resin was dried at 200°F for 4-5 hours. The dry resin was then put into a 1.25" diameter single stage screw extruder with barrel settings set between 425°F and 450°F The L/D ratio was 24 and the screw had a compression ratio of 3.5, the screw speed was 55 RPMs and power was at 27 amps on a line moving at a
rate of 7 2 fpm, Short residence times were desirable to avoid thermal degradation The resulting film was optically transparent In Mold Decorating-
The PCCD film sample from the prior example was treated with Teflon tape on both sides for the first one inch along the width of a 4" x 6" film The film was then placed into the mold of an injection molding machine. Lexan 140 grade polycarbonate resin was then injected into the mold to form a layered composite of PC resm and PCCD film. The experimental conditions for the Nissei 160 ton press injection molder are shown in Table 2

(Table Removed)
Once the layered structure was made the adhesion could be tested. A one inch wide adhesion test sample was cut from the plaque and mounted in a screw driven model 6025 Instron running Acquihn software. The Teflon PTFE flap provided a flap which could be easily grasped by the Instron which was used to perform 90 degree peel tests. The rate of peel was 0.0067 in/sec
The adhesion test showed that the PCCD to PC adhesion was greater than 22 lb /m , before the film failed by breaking In addition, upon viewing the film under magnification a clean interface is observed which would indicate low distortion upon printing and thermoformmg Tear Strength
The tear strength of a 10 mil 100 % PCCD film was tested along with a PC film and a PC/PCCD blend all of the same thickness. It was found that the PCCD film showed a better tear strength of 69 g/mil than did PC film which had a tear strength of 42 g/mil. A blend of 90% PC and 10% PCCD film was also tested and found to have an intermediate tear strength of 48 g/mil. A 15 mil multilayer article of PCCD coextruded over PC also showed good tear resistance in practical tests Heat Deflection Temperature (HDT)
Since PCCD has a low heat deflection temperature of 125° F for a 10 mil film, it is shown that it can be blended with higher heat resistant materials to 'improve its HDT. Table 3 Shows PCCD being blended with polycarbonate resin to reach heat deflection temperatures of 250F with only 50 weight percent polycarbonate. Table 3 The HDT of PCCD Can be Improved with Small Amounts of PC Resin
(Table Removed)
Qxygen (Kb) Barner Performarce.
The amount of PCCD in the PCCD/PC blend formulation can be used to
control the rate of oxygen transmittance through the film, while maintaining
overall clarity and chemical resistance Table 4. Shows the relative performance
of PC film, PCCD film and a 90/10 PC/PCCD film to oxygen transmittance rates
Table 4. Oxygen Transmittance Rates of PCCD, PC and Blend Films
Film material
(Table Removed)
A 60 PCCD/ 40 PC blend film was screen printed with a black ink made by Nazdar Company (Black, 9624). No adhesion promoters or treatments were Aised. The print adhesion was then tested by a Crosshatch adhesion test (ASTM D3559) and was found to have a 5B rating.
The diecutting process involves stamping out the film into the shape of the mold. Failure is marked by hairline cracks along the edges or slivers ot polymer along the cut surface, often referred to as 'angel hair' by those skilled in the art. The film printed and cut according to acceptable standards. Example 4.
An ABS resin (Cycolac® GPM5500) and an ABS/PC (Cycoloy® C6200) blend made by the General Electric Company was used to in mold decorate a 60 % PCCD with 40 % 130 grade PC blend film (60/40 PCCD/PC). The 60/40 PCCD/PC film was thermoformed and diecut to fit within a three dimensional mold. In mold decorated samples were prepared with each the Cycolac GPM5500 and the Cycoloy C6200 resins. The resulting parts were laminated
parts containing the 60/40 PCCD/PC film on one side The final parts had an acceptable aesthetic appearance The conditions for m mold decorating the film are shown in table 5, below
Table 5 In Mold Decorating Conditions for Cycolac ABS and Cycoloy ABS/PC Resins
(Table Removed)
The samples were tested to determine the adhesion between the base resin and the film using a one-inch strip cut from the laminate and an Instron A 90 degree adhesion peel test showed that the Cycolac GPM 5500 resin with the 60/40 PCCD/PC film had an average adhesion of 1.2 lb/in while the Cycoloy C6200 had an average adhesion of 11 2 lb/in Example 5.
A 50% Polycarbonate (PC)/50% PCCD film blend and a 100 % PCCD film both containing benzotriazole stabilizer, Cyasorb UV 5411® as a UV light absorber (UVA) were prepared. The UVA was thoroughly mixed into the resin pellet with 0 05% phosphorous acid quencher and extruded under the conditions listed in table 6
Table 6 Composition and Extrusion Conditions for Making PCCD Film and 50/50 PC/PCCD Film

(Table Removed)
After the films were prepared the thickness, transmittance, YI, and haze were measured The results are shown in the table below The transmittance, YI and haze were measure using a Gardner Colorimeter m the transmittance mode Table 7 Film Thickness, Transmittance, YI and Haze of the PCCD and 50/50 PC/PCCD films prepared.
Tansmittance YI % Haze Thickness (mil)
PCCD Film 92.1 3.1 0 8 8.8
PC/PCCD Film 91.4 2.0 6.2 8.3
These film; samples were then in mold decorated with Lexan® 12o Resin (PC), Xenoy ® 1102 Resin (46/40/14 PC/Polybutylene terephthalate/MBS blend, Noryl PX1005® resin ( a polystyrene (PS) modified polyphenylene oxide (PPO)blend )) and Valox 315® resin (PBT) to make 4" x 6" x 0 0625" plaques A Nissei 160 ton press under the conditions shown m table 8 was used to make these samples
Table 8
(Table Removed)
The laminate samples produced from this experiment were tested for chemical resistance, mterlayer part adhesion and weatherabihty Chemical Resistance
The laminated plaque was tested for chemical resistance using a 50% Ethyl Acetate/50% Methanol mixture The test was performed by placing a saturated piece of filter paper approximately 1" in diameter on the plaque (film side) The sample was then covered with a watch glass to prevent evaporation After 5, 15, 30, 45 and 60 minutes the samples were checked for failure 1 e blistering or cracking The table below shows the results of each laminated plaques performance.
Table 9 Results of Chemical Resistance Testing using a 50% Ethyl Acetate/50%
(Table Removed)
An Instron 90 degree adhesion peel test was utilized to test the adhesion between the film and the injection molding resin An area of the plaque was masked before in mold decorating to provide a tab to grab for the adhesion tests
One inch strips were cut from the center of each plaque The samples was then mounted in the Instron and pulled apart at a rate of 0 016" per sec The adhesion was reported in pounds per linear inch. The following table shows the results of these adhesion tests Table 10 Results of 90 Degree Adhesion Tests
(Table Removed)
The xenon arc accelerated testing was performed on a Ci35a xenon arc Weather-ometer® using a modified SAE J1960 protocol The modification consisting of using a type S borosilicate filter as the inner and outer filters The irradiance level was 0 77 W/m2 at 340 nm, the black panel temperature was between 70-73° C, the dry bulb temperature was 45° C with a wet bulb depression of 10° C (50% relative humidity) The cycle was 160 mm light, 5
minutes dark, 16 minutes dark with water spray This cycle accumulates 2 46 KJ/m2 at 340 run per hour of operation Samples were exposed to 598 5 KJ/m2 under these conditions
The yellowness index (YI), haze and transmittance measurements were taken using a Gardner XL-835 colorimeter Gloss measurements were also collected at a 60 degree angle on the irradiante/cycloahphatic polvester side as per ASTM D523
The results of these tests are shown in table 11

Table 11 Weathering Results of Prepared Samples after 589 5 KJ/m2 Exposure in Xenon Arc
(Table Removed)
Sample
PC/PBT/MBS Control with PCCD laminate with PC/ PCCD laminate
PBT Control
with PCCD laminate
with PC/PCCD laminate
PPO/PS Control with PCCD laminate with PC/PCCD laminate
PC Control with PCCD laminate with PC/PCCD laminate Example6
A sheet was coexrruded having a 70 wt % PCCD/30 wt % 130 grade PC blend cap layer and a 100% 100 grade PC substrate The cap laver was 0 005 in thick and the PC substrate was 0 095 in thick The resulting sheet was transparent and colorless The layers showed excellent adhesion, good toughness and solvent resistance
Table 12 Coextfusion Conditions for 70/30 PCCD/PC Cap Laver Over 100 % PC Substrate
(Table Removed)
In a preferred embodiment of the invention a thin film of top layer material such as PCCD is coextruded with a thicker substrate material such as PC The bottom of the polycarbonate layer is imprinted with an ink image The decorative two layer composite is then placed in a mold and a layer of substrate material, in this case, the PC is injection molded to the printed side of what is now the layer of a four layer structure

What is Claimed:
1. A multilayer article which comprises a thermoplastic resin substrate
layer and an adherent layer comprising a cycloaliphatic polyester on at least
one surface of the substrate.
2. A multilayer article which comprises a substrate comprising a
thermoplastic resin layer and an adherent layer comprising a cycloaliphatic
polyester on at least one surface of the substrate wherein the cycloaliphatic
polyester surface layer shows a 60 degree gloss change of less than or equal to
50% after 600 KJ/m2 exposure to a J1960 weathering test using borosilicate
glass filtered xenon arc light.
3. A multilayer article which comprises a substrate comprising a
thermoplastic resin layer and an adherent layer comprising a cycloaliphatic
polyester on at least one surface of the substrate wherein the peel strength
between the layers is greater than or equal to 5 Ibs/in.
4. A multilayer article which comprises a substrate comprising a
' thermoplastic resin layer and an adherent layer comprising a cycloaliphatic
polyester on at least one surface of the substrate where in the cycloaliphatic polyester surface of the article resists cracking or blistering after 60 minutes exposure to a 1:1 mixture of ethyl acetate and rnethanol.
5. An article according to claim 1 in which the thermoplastic resin
substrate layer is a polycarbonate resin, an ABS resin, an ASA resin, a
polyester, a polyphenylene ether or polyphenylene ether/polystyrene blend,
or a blend comprising a polycarbonate resin with an ABS, ASA or aromatic
polyester resin.
6. An article according to claim 5 in which the substrate layer is
polycarbonate or a'polycarbonate containing blend.
7. An article according to claim 6 in which the substrate layer blend
comprises from about 15 to about 85 weight percent polycarbonate and from
about 15 to about 85 weight percent ABS, ASA or polyester resin.
8. An article according to claim 1 in which the substrate layer further
contains 1-50% of the cycloaliphatic polyester cap layer.
9. An article according to claim 1 where the adherent cap layer is a blend
of polycarbonate with cycloaliphatic polyester.
10. An article according to claim 1 in which the adherent cap layer is a
blend of polycarbonate and cycloaliphatic polyester derived from a
cycloaliphatic diol and a cycloaliphatic diacid.
11. An article according to claim 1 in which the cycloaliphatic polyester is
poly(l,4 - cyclohexane dimethanol -1,4 - cyclohexanedicarboxylate)
12. An article according to claim 9 in which the amount of polycarbonate
in the polycarbonate - cycloaliphatic poly ester blend of the adherent cap
layer is from about 1 to about 50 percent by weight of the blend.
13. An article according to claim 9 which further comprises an acidic
phosphorus quencher,
14. An article according to claim 13 wherein the acidic phosphorus
quencher is chosen form the following group: phosphorous acid, phosphoric
acid, acidic organo phosphates, and acidic organo phosphites.
15. An article of claim 1 wherein the substrate layer is a polycarbonate or a
blend of polycarbonate with ABS, ASA or a polyester resin.
16. An article according to claim 9 in which the blend comprises
polycarbonate, a cycloaliphatic polyester, and a UV absorber.
17. An article according to claim 16 in which the UV absorber is selected
from the group consisting of 2-(benzotriazol-2-yl)-4-(l,l,3,3-
tetramethylbutyl)phenol, 2-(benzotriazol-2-yl)-4-methylphenoI, 2-hydroxy-4-
ocryloxy benzophenone, 2-hydroxy-4-methoxybenzophenone, ethyl-2,2-
diphenyl-1-cyanoacrylate, 2'-ethylhexyl - 2, 2-dipheny 1-1-cyanoacry late, 2-(2'-hydroxy-4'-octyloxy) bis-4,6-(2',4'-dimethylphenyl) triazine, 2-ethyl- 2'- ethoxy oxalanide, bis [ 2-hydroxy-5-methyl-3- (benzotriazol-2-yl) phenyl ] - methane, bis[ 2 - hydroxy- 5 -t - octyl -3 - ( benzotriazol -2 -yl) phenyl] methane, 2,2' - ( 1,4 - phenylene ) bis [ 4 H - 3, 1 - benzoxazin -4 -one], and 2 - ( 2' - hydroxy) -4,6 - diphenyltriazine.
18. An article according to claim 16 in which the UV absorber is a
benzotriazole, a benzophenone, a triazine, a cyanoacrylate, a
dibenzoylresorcinol, or an oxanilide.
19. An article according to claim 16 in which the UV absorber is a
dibenzoylresorcinol.
20. An article according to claim 19 in which the dibenzoyl rescorcinol is
4,6-dibenzoylresorcinol, bis(2,6-dihydroxy-3,5-dibenzoylphenyl)methane, or
2-(3-triethoxysilyl propyI)-4,6-dibenzoyl resorcinol.
21. A multilayer plastic article according to claim 1 comprising an
intermediate decorative layer between the substrate and the cycloaliphatic
polyester layer.
22. An article according to claim 21 in which the intermediate layer is
printed on at least a portion of the inner surface of the cycloaliphatic polyester
layer.
23. An article according to claim 1 comprising an thermoplastics resin, a
first film of the same resin bonded to at least one surface of the substrate, and
a second film comprising a cycloaliphatic polyester bonded to the outer
surface of the first film.
24. An article according to claim 23 comprising a polycarbonate substrate,
a polycarbonate film bonded to at least one surface of the substrate, a
cycloaliphatic polyester surface film bonded to the outer surface of the
polycarbonate film.
25. An article according to claim 24 in which the surface film is a blend of
polycarbonate and a cycloaliphatic polyester.
26. An article according to claim 25 in which the cycloaliphatic polyester is
PCCD.
27. An article of claim 5 wherein the polycarbonate -aromatic polyester
substrate further contains a rubbery impact modifier.
28. An article of claim 27 wherein the rubbery substrate is chosen from the
group consisting of MBS, Acrylic rubber, ASA or ABS rubbers.
29. An article of claim 1 made by a blow molding, sheet, film or profile
extrusion, in mold decoration or injection molding process.
30. An article of claim 29, made by coextruding the substrate layer
material and the top layer material, decorating the bottom surface of the
substrate layer, and injection or blow molding another layer of substrate
material to the decorative surface of the substrate.
31. A multilayer article comprising a substrate comprising a thermoplastic
resin layer and an adherent layer comprising a cycloaliphatic polyester on at
least one surface of the substrate wherein the polyester layer has a tear
strength of 69 grams/mil.
32. A multilayer article substantially as herein described with reference to
and as illustrated by the foregoing examples.
33. A multilayer plastic article substantially as herein described with
reference to and as illustrated by the foregoing examples.
34. A method of manufacturing a multilayer article substantially as herein
described with reference to and as illustrated by the foregoing
examples.