TW200520948A - A formable thermoplastic multi-layer laminate, a formed multi-layer laminate, an article, and a method of making an article - Google Patents

Abstract

Disclosed is a formable thermoplastic multi-layer laminate (10) comprising an outer layer (2) comprising a polymer comprising resorcinol arylate polyester chain members, a middle layer (4) comprising a thermoplastic polymer, an inner-tie layer (6) comprising a thermoplastic polymer comprising a carbonate polymer and an acrylonitrile-styrene graft copolymer comprising at least one of an acrylonitrile-styrene-acrylate graft copolymer (ASA) or an acrylonitrile-butadiene-styrene graft copolymer (ABS), the middle layer (4) being between the outer layer (2) and the inner-tie layer (6) and being in contact with both the outer layer (2) and the inner-tie layer(6). Also disclosed are a formed multi-layer laminate (10) and an article comprising the multi-layer laminate (10) bonded to a substrate (8). A method of making the article is also disclosed.

Description

200520948 ⑴ 玖, description of the invention [Technical field to which the invention belongs] The present invention relates to formable multilayer thermoplastic laminates, which have good adhesion to substrates, especially foam substrates. [Prior art] Mold many automotive components and body panels of vehicles with thermoformable compositions (such as thermosetting polymer compositions). However, the automotive industry generally requires that all surfaces seen by consumers have, grade A, surface quality. The minimum is that all surfaces must be smooth, shiny and wind-meltable. Components made from thermoformable compositions often require extensive surface products and are coated with a curable coating to provide an acceptable quality and appearance surface. The steps required to prepare such a surface can be too expensive and time consuming, and can affect the mechanical properties of thermoset materials. Although the surface quality of the moldable components made of thermoformable components is continuously improved, surface defects often occur due to exposed glass fibers, see-through glass fibers, and the like. These surface defects may further cause defects in the coatings applied to these surfaces. Defects in the surface of the thermoformable composition and the cured coating applied to the surface of the thermoformable composition may result in paint blasts, long-term and short-term ripples, peeling of orange peel, variation in gloss, or similar defects. A number of techniques have been proposed to provide thermoformable surfaces of acceptable appearance and quality. For example, an overmolded thin preformed coating film can provide the required Class A surface. However, this overmolding is often only applicable to those components that can provide 200520948-(2) primary molding surfaces that do not require any secondary surface preparation operations. Although the surface quality of ‘therefore molded’ is improved, the surface of the component being molded therefore requires continuous sanding, especially at the edges, followed by sealing and priming before painting. These operations can be eliminated by in-mold coating, but only at the expense of significantly increasing cycle time and cost. These processes use expensive painting systems that can be applied to the surface of the part, while the model is slightly reopened and then sealed to dispense and cure the coating. Surface improvement has also been achieved with the addition of low-distribution additives. These additives reduce 'transparency' on the surface, cause small internal voids due to high stress, and provide a smoother surface. If voids occur on the surface, they can cause defects in the finished product. Voids are also used as stress concentrators, which can cause premature failure under additional stress, or appear on the surface during ordinary sandpaper sanding and leave pits that cannot be hidden by the painting process. Thermoformable multilayer laminates are known in vehicle technology because they provide acceptable surface products when coated on various automotive components without compromising the quality of the underlying surface or substrate. However, it has been known that the laminates of the prior art exhibit inter-layer or intra-layer separation phenomena, including separation from the substrate bonded to the laminate. However, the layers of various multilayer laminates may be unevenly adhered to each other and / or to the surface or substrate to which they are applied. This may cause unacceptable surface quality in finished automotive parts. Multi-layer laminates have traditionally been formed in a variety of methods, including co-injection molding, 'overmolding, multi-shot injection molding, sheet molding, co-extrusion, and coatings that are replaced on the substrate sheet Material film and similar methods-6-200520948 (3). It is particularly desirable to use a common extrusion method. The multi-layer laminate formed by the co-extrusion method has economic benefits and generally exhibits adhesion and adhesion improvement effects relative to various layers made of the multilayer laminate. However, some multilayer laminate compositions are not easily formed by coextrusion. Therefore, it is not easy to provide a moldable multilayer laminate having a characteristic balance regarding adhesion to a substrate and surface quality, but a stomach & coextrusion. Therefore, there is a continuing need for thermoformable multilayer laminate compositions that adhere more effectively to the substrate surface and provide the desired 'A-grade, surface quality. There is a further need in the art for these thermoformable multilayer laminate compositions that can be made by coextrusion. [Summary of the Invention] The present invention is focused on a formable thermoplastic multilayer laminate comprising an outer layer 'which contains a polymer containing members of a resorcinol arylate polyester chain; a middle layer' which contains a thermoplastic polymer; and an inner link A layer comprising an acrylonitrile-benzene containing a carbonate polymer and an acrylonitrile-styrene-acrylate graft copolymer (ASA) or an acrylonitrile-butadiene-styrene graft copolymer (ABS) The middle layer of the thermoplastic polymer of the ethylene graft copolymer is interposed between the outer layer and the inner connecting layer, and is in contact with both the outer layer and the inner connecting layer. In one embodiment, a shaped multilayer laminate is provided. A multilayered body suitable for forming can be produced by a thermoforming method such as vacuum forming or a method such as compression forming. In an exemplary embodiment, a formed multilayer laminate is formed by a thermoforming method. 200520948 * (4) The present invention also focuses on an article containing a multilayer laminate as described above, in which the multilayer laminate is adhered to a substrate. In a specific embodiment, the substrate can be any of a variety of suitable materials, including thermoset materials, thermoplastic materials, foamed materials (such as foamed polyurethane materials), and the like. Articles are used to prepare outer body panels for automobiles. In one embodiment, a multilayer laminate formed by a multilayer laminate system bonded to a substrate is formed. A method of making an article is also disclosed that includes providing a multilayer laminate including an outer layer including a secondary layer containing a resorcinol arylate polyester chain member; a middle layer including a thermoplastic polymer; and an inner linking layer that Contains a carbonate polymer and an acrylonitrile-styrene graft containing one of the acrylonitrile-styrene-acrylate graft copolymers (ASA) or acrylonitrile-butadiene-styrene graft copolymers (ABS) The thermoplastic polymer of the branch copolymer is interposed between the outer layer and the inner connecting layer, and is in contact with both the outer layer and the inner connecting layer. The multilayer laminate is placed in the model, so a hollow body is formed after the multilayer laminate; and The substrate is injected into the hollow body after the multilayer laminate, and the inner connecting layer of the multilayer laminate is bonded to the substrate to provide an object. In another embodiment, a multilayer laminate formed by a multilayer laminate system placed in a model. In an exemplary embodiment, the model includes a shape or hollow body that substantially conforms to the formed multilayer laminate. In another embodiment, the method further includes cooling the object and removing the object from the model. [Embodiment] In a specific embodiment, a multilayer laminate having improved adhesion to a substrate is disclosed. In another specific embodiment, the disclosure also provides a multilayer laminate having an A-level surface, particularly in a formed multilayer laminate or in a formed article. As used herein, the 'Grade A surface' term provides a general meaning known in the art and refers to a surface that is substantially free of visual defects such as hairline, pinholes, and similar defects. In a specific embodiment, the Class A surface includes a gloss of greater than 100 units at 20 or 60 degrees, a wave scan of less than 5 units (long and short waves), and an image difference (DOI) of greater than 95 units. . Once applied to the substrate, the multilayer laminate maintains the surface quality of the substrate and provides objects with the required surface appearance and quality. In a specific embodiment, the outer layer, the middle layer and the inner connecting layer of the multilayer laminate are composed of a thermostabilizing material, and they have a viscosity and a molecular weight that can be extruded together into a thermoformable multilayer laminate. . Compositions suitable for extrusion processing typically have a higher weight average molecular weight, higher melt strength, and higher viscosity than compositions intended to be processed via injection-molding equipment. Now turn to FIG. 1 which is a cross-sectional illustration of a multi-layer laminate 10 that is unveiled. The multilayer laminate 10 includes an outer layer 2, an inner connection layer 6 opposite to the outer layer 2, and a middle layer 4 disposed between the outer layer 2 and the inner connection layer 6. In an exemplary embodiment, the outer layer 2 comprises a polymer containing a resorcinol polyacetate chain member 'middle 4 contains a carbonate polymer containing a thermoplastic polymer' and a tie layer 6 (also referred to herein as the "inner The tie layer ") contains acrylic acid containing a carbonate polymer, at least one of acrylonitrile-styrene-acrylate graft copolymer (ASA) or acrylonitrile-butane disulfide_ 200520948 (6) Graft copolymer (ABS) A thermoplastic polymer of calcined nitrile-phenethyl graft copolymer. In a specific embodiment, the outer layer 2 of the multilayer laminate 10 comprises at least one polymer containing a member of the resorcinol arylate polyester chain. "Resorcinol arylate polyester chain member" as used herein refers to a compound comprising at least one combination with at least one aromatic diphenol residue (which is combined with at least one aromatic diresidue acid residue) Chain members of residues. The preferred diphenol residue as exemplified by formula I is derived from a 1,3-dihydroxybenzene moiety and is often referred to throughout the specification as a resorcinol or resorcinol moiety. It should be understood that as used herein, resorcinol or resorcinol moiety includes both unsubstituted 1,3-dihydroxybenzene and substituted 1,3-dihydroxybenzene, unless otherwise clearly stated .

Wherein R is at least one of C 12 alkyl or halogen, and η is 0.3. Suitable dicarboxylic acid residues include aromatic di # acid residues (preferably isophthalic acid, terephthalic acid, or mixtures thereof) derived from monocyclic moieties or aromatic dicarboxylic acids of polycyclic moieties. Residues (including diphenyl dicarboxylic acid, diphenyl ether dicarboxylic acid, naphthalenedicarboxylic acid (such as naphthalene-2: 6-dicarboxylic acid), and morphthalene dicarboxylic acid (such as morphthalene-2; 6-dicarboxylic acid )). In a specific embodiment, the dicarboxylic acid residue used is a cyclohexanedicarboxylic acid residue. In an exemplary embodiment, the aromatic dicarboxylic acid residue is derived from -10- 200520948 (7) a mixture of isophthalic acid and / or terephthalic acid, as exemplified by Formula II.

In an exemplary embodiment, the outer layer 2 will comprise a polymer as exemplified by Formula II, where R and n are as previously defined:

In an exemplary embodiment, the outer layer 2 comprises a polymer having a member of the resorcinol arylate polyester chain, which does not substantially have an anhydride bond as illustrated in Figure IV:

In an exemplary embodiment, the outer layer 2 comprises a polymer containing members of a resorcinol arylate polyester chain produced by an interfacial method, the method comprising combining at least one resorcinol moiety with The first step of combining at least one catalyst in a mixture of water and an organic solvent that is substantially immiscible with water. A suitable resorcinol moiety comprises a unit of formula V:

Wherein R is at least one of C!-] 2 alkyl or halogen, and η is Q-3. If an alkyl group is present, it is preferably a straight-chain or branched alkyl group. -11-200520948 (8) 'and most of them are often located adjacent to the oxygen atom, although other ring positions are encompassed. Suitable 2-alkyl groups include methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, tert-butyl, nonyl, decyl and aryl-substituted alkyl groups, including benzyl, Methyl is particularly preferred. Suitable halo groups are bromo 'chloro and fluoro. η 値 may be 0-3, preferably 0-2, and more preferably 0-1. The preferred resorcinol moiety is 2-methylresorcinol. The most preferred resorcinol moiety is an unsubstituted resorcinol moiety, of which n is zero. In an exemplary embodiment, at least one catalyst is combined with a reaction mixture used in the cohesive interface method. The catalyst may be present in a total amount of 0.1 to 10 mol% based on the total molar amount of acidic chlorine groups, and 0.2 to 6 mol. /. Better. Suitable catalysts include tertiary amines, quaternary salts, quaternary scale salts, hexaalkyl silver salts and mixtures thereof. Suitable tertiary amines include triethylamine, dimethylbutylamine, diisopropylethylamine, 2,2,6,6-tetramethylhexahydropyridine and mixtures thereof. Other tertiary amines include N- (C1_C6) -alkylpyrrolidine (such as ethylpyrrolidine), (ci-C6) -hexahydropyridine (such as N-ethylhexahydropyridine, .methylhexahydropyridine And N_isopropylhexahydropyridine), (C1C6) -morpholine (such as N-ethylmorpholine and N-isopropylmorpholine), N- (CI-C6) -dihydroindole , N- (C] -C6) -hydroisoindole, N- (c] -C6) -tetrahydro Dquinoline, N- (C1-C6) -tetrahydroisoDquinoline, Ν-(C 1-C 6) · benzomorpholine, azabicyclo · [3.3.0] -octane, quinine ring, N- (C1-C6) -alkylazabicyclo · [2 · 2 ·]]-octane, N. (C) _C6) _alkyl-2 · azabicyclo · [3 31] -nonane and N- (C1-C6) · alkyl · 3-azabicyclo_ [3 · 3 · 1] -nonane, N, NA ', N, tetraalkylene diamine (including ν, N, N :; Ν, -tetraethyl-12- 200520948 (9) group-1, 6-hexanediamine). Particularly preferred tertiary amines are triethylamine and N_ethylhexahydropyridine. When the catalyst is composed of at least one single tertiary amine, the catalyst may be present in a total amount of 0.1 to 10 mol% based on the total molar amount of acidic chlorine groups, ranging from 0.2 to 6 Molar% is preferred, 1 to 4 Molar% is more preferred, and 2.5 to 4 Molar% is most preferred. In a specific embodiment of the present invention, 'all at least one tertiary amine is present at the beginning of the reaction and before the resorcinol moiety is added as the diresidic acid dichloride. In another embodiment, part of any tertiary amine is present at the beginning of the reaction and part is added after or during the addition of the resorcinol moiety with dicarboxylic acid dichloride. In the latter specific embodiment, the amount of any tertiary amine present in the initial stage with the resorcinol moiety may be based on the total amines and ranges from about 0.05% by weight to about 10% by weight, ranging from About 0.001 to about 1% by weight is preferred, and more preferably from about 0.02% to about 0.3% by weight. Suitable quaternary salt, quaternary scale salt and hexadecyl silver salt include halide salts (such as tetraethylammonium bromide, tetraethylammonium chloride, tetrapropylammonium bromide, tetrapropylammonium chloride , Tetrabutylammonium bromide, tetrabutylammonium chloride, methyltributylammonium chloride, benzyltributylammonium chloride, benzyltriethylammonium chloride, benzyltrimethyl Ammonium chloride, trioctylmethylammonium chloride, cetyldimethylbenzyl ammonium chloride, octyltriethylammonium bromide, decyltrimethylammonium bromide, lauryltriethylbromide Ammonium, cetyltrimethylammonium bromide, cetyltriethylammonium bromide, N-laurylpyridine chloride, N · laurylpyridine bromide, N-heptylpyridine bromide, Trioctylmethylammonium chloride (sometimes known as ALIQUAT 3 3 6), methyldi-Cs-Ci0-nosyl chloride (sometimes known as ADOGEN 464 known from 200520948 (10)), N N5N, 5N, 5N, pentaalkyl-α5Ω-amine ammonium salt (as disclosed in US Patent No. 5 5 8 2 1, 3 2 2), tetrabutyl bromide scale, benzyltriphenyl chloride Scale, triethyloctadecylphosphonium bromide, tetraphenyl bromide scale, triphenylmethyl bromide Qian 'trioctyl ethyl bromide scale, cetyl triethyl bromide scale, silver hexaalkyl halide, silver hexaethyl silver chloride and the like and mixtures thereof. Organic solvents that are substantially immiscible with water include Those solvents which are soluble in water at less than about 5% by weight under reaction conditions, and preferably less than about 2% by weight. Suitable organic solvents include dichloromethane, trichloroethylene 'tetrachloroethane, chloroform, 1,2 -Dichloroethane, toluene, xylene, trimethylbenzene, chlorobenzene, o-dichlorobenzene and mixtures thereof. Particularly preferred solvents are dichloromethane. Suitable dicarboxylic acid dichlorides include derivatives derived from monocyclic rings Aromatic dicarboxylic acid dichloride (preferably isophthalocyanine dichloride, p-phthalocyanine dichloride or a mixture of isophthalocyanine dichloride and p-phthalocyanine dichloride), or derived from polycyclic system Aromatic dicarboxylic acid dichloride (including diphenyl dicarboxylic acid dichloride, diphenyl ether dicarboxylic acid dichloride and naphthalene dicarboxylic acid dichloride, preferably naphthalene-2,6-dicarboxylic acid dichloride) Or from a mixture of monocyclic and polycyclic aromatic dicarboxylic acid dichloride. The dicarboxylic acid dichloride is a mixture containing isophthalocyanine dichloride and / or p-phthalocyanine dichloride. Good, as is typical of Formula v j illustration.

The polymer contained in the outer layer 2 can be produced using any one or two kinds of isophthalocyanine dichloride and terephthalocyanine dichloride. In a specific embodiment, the dicarboxylic acid di-14-200520948 (11) chlorine contains about ο · 2 5-4 · 0 · · 1 isophthalofluorenyl molybdenum isophthalocyanine A mixture of dichloride and terephthalocyanine dichloride, in another specific embodiment, about 0.4-2.5: 1, and in an exemplary embodiment, about 0.67-

In a specific embodiment, the pH of the interfacial reaction mixture is maintained between about 3 to about 8.5 over the entire period in which at least one dicarboxylic acid dichloride is added to at least one resorcinol moiety, In an embodiment, it is between about 5 and about 8. Suitable reagents for maintaining pH include alkali metal hydroxides, alkaline earth metal hydroxides, and alkaline earth metal oxides. The better reagents are potassium hydroxide and sodium hydroxide. A particularly preferred reagent is sodium hydroxide. The reagents that maintain PΗ can be included in the reaction mixture in any convenient form. In a specific embodiment, the reagent is added to the reaction mixture simultaneously with at least one dicarboxylic acid dichloride as an aqueous solution.

The temperature of the interfacial reaction mixture may be any convenient temperature, providing a polymer including resorcinol arylate which has a fast reaction speed and is substantially free of anhydride bonds. Convenient temperatures include those from about -20 ° C to the boiling point of the water-organic solvent mixture under the reaction conditions. In a specific embodiment, the reaction is performed at a boiling point of an organic solvent in a water-organic solvent mixture. In an exemplary embodiment, the reaction is carried out at the boiling point of methylene chloride. The total molar amount of the acidic chlorine group added to the reaction mixture is less than the total molar amount relative to the phenolic group. It is required to use this stoichiometry 1: the hydrolysis of acidic chlorine groups is minimized, and the presence of nucleophiles (such as phenols and / or phenoxides) can be present. The damage should be under reaction conditions -15-200520948 (12) Any foreign anhydride bond formed. The total molar amount of acidic chlorine groups includes at least one dicarboxylic acid dichloride, and any monocarboxylic acid chlorine chain terminator and any tri- or tetra-carboxylic acid tri- or tetra-chloro branching agent can be used. The total moles of phenolic groups include the resorcinol moiety, and any monophenolic chain terminator and any tri- or tetra-phenolic branching agent that can be used. The stoichiometric ratio of the total phenolic group to the total acidic chlorine group is preferably about 1.5-1.0 1.0: 1, and more preferably about 1.2-1 · 02: 1. After the completion of the addition of at least one resorcinol with at least one dicarboxylic acid dichloride, the presence or absence of anhydride bonding is typically based on the actual stoichiometry of the reactants and the amount of catalyst present and other variations. set. For example, if a sufficient excess of the total phenolic group is present, it is often found that no anhydride bond is present. Often, the total amount of phenolic groups exceeding the total amount of acidic chlorine groups by at least about 1% moles is sufficient to eliminate anhydride bonding under reaction conditions, and in a specific embodiment, exceeds at least about 3%. When an anhydride bond can be present, the final pH is often required to be greater than 7, so a nucleophile (such as a phenol, phenoxide, and / or hydroxide) can be present to break any anhydride bond. Therefore, in a specific embodiment, the interfacial method of a polymer for providing at least one sublayer of the outer layer 2 may further include, after completing adding at least one resorcinol moiety with at least one dicarboxylic acid dichloride, The step of adjusting the pH of the reaction mixture to be between 7 and 2], in another embodiment, it is between 8 and 12, and in another embodiment, it is between 8.5 To] 2. The pH can be adjusted by any convenient method, preferably using an aqueous base, such as aqueous sodium hydroxide. -16-200520948 (13) The final p Η of the provided reaction mixture is greater than 7, and the interfacial method for providing the polymer contained in the outer layer 2 may further include to completely completely break any foreign anhydride bond that should be present The reaction mixture was stirred over the course of time. The necessary stirring time will depend on the reactor configuration, the shape of the stirrer, the stirring speed, temperature, total solvent volume, organic solvent volume, anhydride concentration, pH, and other factors. In some examples, the necessary stirring time must be instantaneous, for example, the pH is adjusted to be greater than 7 within a few seconds, assuming that any foreign anhydride bonds begin to exist. With respect to a typical laboratory-sized reaction device, a stirring time of at least about 3 minutes may be required, and in a specific embodiment, it is at least about 5 minutes. In this way, nucleophiles (such as phenols, phenoxides, and / or hydroxides) can be given time to completely destroy any anhydride bonds that should be present. In the interfacial method for producing a polymer containing a resorcinol arylate polyester chain member, at least one chain terminator (hereinafter sometimes referred to as a blocking agent) may also be used. The purpose of adding at least one chain terminator is to limit the molecular weight of polymers containing members of the resorcinol arylate polyester chain, thereby providing polymers with controlled molecular weight and favorable processing capabilities. Typically, at least one chain terminator is added when the polymer that does not need to include resorcinol arylate has reactive end groups for further applications. In the absence of a chain terminator, a polymer that includes resorcinol arylate can be used in or in solution or can be recovered from solution for subsequent use, such as in copolymer formation The diphenol arylate segment requires the presence of a reactive end group (typically a hydroxyl group). The chain terminator may be any one of the monophenolic compounds, monohydroxy acid chloride and / or monochloroformate. To -17- 200520948 (14) At least one type of chain terminator is typically based on the resorcinol moiety in the examples of monophenolic compounds and based on the monocarboxylic acid chloride and / or monochloroformate. The examples are present in an amount of 0.05 to 10 mole% based on acidic dichloride. Suitable monophenolic compounds include monocyclic phenols (such as phenols, phenols substituted with Cl-c22 alkyl, p-cumylphenol, p-third butylphenol, hydroxydiphenyl), monoethers of diphenols Class (such as p-methoxyfluorene). Alkyl-substituted phenols include those having a branched alkyl substituent of 8 to 9 carbon atoms. In a specific embodiment, about 47 to 89% of the hydrogen atom is a methyl moiety. In some embodiments, a monophenol-based UV screening agent is preferably used as a blocking agent. These compounds include 4-substituted 2-hydroxybenzophenone and its derivatives, aryl salicylate, monoesters of diphenols (such as resorcinol monobenzoate), 2-( 2-Hydroxyaryl) -benzotriazole and its derivatives, 2- (2-hydroxyaryl) -1,3 5 5 -Sango and its derivatives and similar compounds. In a specific embodiment, the monophenolic chain terminator is at least one of phenol, p-cumylphenol or resorcinol monobenzoate. Suitable monocarboxylic acid chlorides include monocyclic monocarboxylic acid chlorides (e.g., phenylphosphonium chloride, phenylphosphonium chloride substituted with Ci-C22 alkyl, toluenesulfonyl chloride, phenylphosphonium chloride substituted with halogen, bromophenylphosphonium chloride, Cinnamonyl chloride, 4-nadimido benzamidine chloride, and mixtures thereof), polycyclic monocarboxylic acid chlorides (such as trimellitic anhydride chloride and naphthalenesulfonyl chloride), and mixtures of monocyclic and polycyclic monocarboxylic acid chlorides . Chlorides of aliphatic monocarboxylic acids having up to 22 carbon atoms are also suitable. Functionalized chlorides of aliphatic monocarboxylic acids are also suitable, such as propylene chloride and methacrylic chloride. Suitable monochloroformates include monocyclic monochloroformates such as phenyl chloroformate, phenyl chloroformate substituted with alkyl, p-cumyl phenyl chloroformate, -18- 200520948 (15) Toluochloroformate and mixtures thereof. The chain terminator may be combined with a resorcinol moiety, may be included in a solution of dichlorodicarboxylic acid, or may be added to the reaction mixture after the preconcentrate is produced. If monocarboxylic acid chlorides and / or monochloroformates are used as chain terminators, they are preferably introduced together with dichlorodicarboxylic acid. These chain terminators can also be added to the reaction mixture when the chloride of the dicarboxylic acid has been substantially reacted or completed. If a phenolic compound is used as the chain terminator, it can be added to the reaction mixture during the reaction, or more preferably before the start of the reaction between the resorcinol moiety and the acidic chlorine moiety. In preparing preconcentrates or oligomers comprising terfinol arylates terminated with hydroxyl groups, the presence of chain terminators may be absent or may be present in small amounts to aid in controlling the molecular weight of the oligomer. In another embodiment, the interfacial method for providing a polymer containing a resorcinol arylate polyester member may include at least one branching agent such as a trifunctional or higher functional carboxylic acid chloride and / Or trifunctional or higher functional phenol. When these branching agents are included, it is preferably used in an amount of 0.5 to 1 mol% based on the dichlorodicarboxylic acid or resorcinol portion used respectively. Suitable branching agents include, for example, trifunctional or higher functional carboxylic acid chlorides (e.g., trichlorotrimelate, trichlorotricyanate, 3,3 \ 454, benzophenone tetracarboxylic acid tetrachloride , 1,4,558-naphthalenetetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride) and trifunctional or higher functional phenols (such as resorcinol, 4,6-dimethyl-254,6-tri -(4-hydroxyphenyl) -2-heptene, 4; 6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptane, 153.5-tri- (4- (Hydroxyphenyl) -benzene,] :, tris (-(4-hydroxyphenyl) -ethane, tri- (cardiohydroxyphenyl)-19-200520948 (16) phenylmethane, 2,2-bis- [4,4-bis- (4-hydroxyphenyl) -cyclohexyl], 2,4-bis- (4-hydroxyphenylisopropyl) -phenol, tetra- (4-hydroxyphenyl), 2, 6-Bis- (2-Hydroxy-5-methylbenzyl) -4-methylphenol '2 · (phenyl) -2- (2,4 -diphenylphenyl) -Cyclos'tetra_ ( 4- [4 -Phenylpropyl] -phenoxy) -methane, 1,4-bis-[(4,4 · dihydroxytrityl] -benzene). A phenolic branching agent and m The resorcinol moiety is introduced first but acidic branching agents can be introduced together with acidic dichloride. In an exemplary embodiment, resorcinol will be included The polymers of the polyester chain members are recovered from the interfacial reaction mixture by known recovery methods. The recovery methods may include, for example, acidification of the mixture (eg, phosphoric acid), liquid-liquid separation of the mixture, water and dilution. Acid (such as hydrochloric acid or phosphoric acid), washing the organic phase, common precipitation (such as by treatment with water or precipitation with, for example, methanol, ethanol and / or different anti-solvent), separation of the resulting precipitate and drying Steps such as removing a solvent. If necessary, an interfacial method which further includes a reducing agent may be used in the outer layer 2. The resorcinol arylate polymer may be used. Suitable starting agents include, for example, sodium sulfite, sodium gluconate or boron A hydride (such as sodium borate). When any reducing agent is present, it is typically used in an amount of from 0.25 to 2 mol% based on the m-phenol moire. In a specific embodiment, the The polymer of the hydroquinone arylate polymember does not substantially have a bond that links at least two polyester chain members. In a particular embodiment, the polyester contains an iso- and para-derived derivative derived from V 11 Dicarboxylic acid residues of a mixture of phthalic acids:-propane-methane 4-hydroxyisopropyl), the basic compounds are produced by the sub- / or method of the propanol residues and also the anhydride of the hydrogenated phthalate chain as shown in formula 200520948 (17)

Wherein R is at least one of C,.! 2 alkyl or halogen, η is 0-3, and m is at least about 8. In a specific embodiment, n is 0 and m is between about 10 and about 300. The molar ratio of isophthalate to terephthalate is about 0.25-4.0: 1. In one embodiment, it is about 0.4-2.5: 1, and in another embodiment, it is about 0.6. 7-1. 5: 1. Substantially no anhydride bonding means that once the polymer is heated at a temperature of about 2 80-290 ° C for 5 minutes, the polyester exhibits a molecular weight reduction of less than 30%. In a specific embodiment, a polymer containing a member of the resorcinol arylate polyester chain comprises a combination with a dicarboxylic acid or glycol alkylene chain member (also known as a "soft block" segment) A copolyester of a resorcinol arylate polyester chain member, which copolyester does not substantially have anhydride linkages in the polyester segment. Substantially no anhydride bonding means that once the copolyester is heated at a temperature of about 280-29 ° C for 5 minutes, the copolyester exhibits a molecular weight decrease of less than 10%, and preferably less than 5%. As used herein, the term soft block refers to some polymer segments derived from non-aromatic monomer units. These non-aromatic monomer units are usually aliphatic 'and are known to impart flexibility to polymers including soft blocks. Copolymers include those containing structural units of formula VII, Vln and IX:

-21-200520948 (18)

Vm

Formula IX

Wherein R and η are as previously defined, Z is a divalent aromatic group, and r2 is C3.2 ° linear alkylene, C3.] () Branched alkylene or C4.] () Ring- or bicyclic Alkylene, and R3 and R4 are independent representatives of each other

Or —ch 2 — 0 — where formula IX constitutes an ester linkage of the polyester from about 1 to about 45 mole%. In other specific embodiments, Formula IX may constitute an ester linkage of the polyester from about 5 to about 40 mole%, and particularly preferably from about 5 to about 20 mole%. Another specific embodiment provides a composition in which R2 represents C3.] 4 straight chain alkylene or c5.6 cycloalkylene. 'Wherein R2 represents c3.] G straight chain alkylene or cycloalkylene. The composition is preferred. Formula VIII represents an aromatic di-residual acid residue. The divalent aromatic group Z in Formula VIII may be derived from at least one of the suitable dicarboxylic acid residues, as defined above, and at least one of 1,3-phenylene, 1; 4-phenylene, or 2 6-naphthalene is preferred. In a more preferred embodiment, Z comprises at least about 40 mole% of 1,3 · phenylene. In an exemplary embodiment, with respect to a copolyester including a soft block chain member, n in Formula I is 0. In a specific embodiment, the outer layer 2 comprises a copolymerized vinegar, which comprises a sebacate or cyclohexanide containing from about 45 to about 45 mole%! · 4 _ diresidic acid -22-200520948 (19) A member of the resorcinol arylate chain between the ester units. In another specific embodiment, the copolyester including members of the resorcinol arylate chain contains a resorcinol isophthalate with a molar ratio between 8. 5: 1.5 and 9.5: 0.5. Copolyester of esters and resorcinol sebacate units. In an exemplary embodiment, copolyester is prepared using sebacyl chloride in combination with isophthalocyanine dichloride. In another specific embodiment, a polymer containing a resorcinol arylate polyester chain member comprises a thermally stable block copolyestercarbonate, which includes resorcinol in combination with an organic carbonate block Aryl block segment. Segments containing resorcinol arylate chain members in these copolymers do not substantially have anhydride linkages. Substantially no anhydride bonding means that once the copolyestercarbonate is heated at a temperature of about 2 0 0 to 90 ° C for 5 minutes, the copolyestercarbonate exhibits a molecular weight reduction of less than 0%, and It is preferably less than 5%. Block copolyester carbonates include those carbonates containing alternating arylate and organic carbonate blocks, typically as exemplified by Formula X, where R and η are as previously defined, and R5 is at least one of two Valence organic group:

The arylate block represented by m has a degree of polymerization (D P) of at least about 4, preferably at least about 10, more preferably at least about 20, and most preferably about 30 -1 50. The D P of the organic carbonate block represented by P is usually at least about 10, preferably at least about 2 0 ', and most preferably about 50-2 0. The distribution of the blocks may be such as to provide such distribution with any desired weight relative to the carbonate blocks of -23- 200520948 (20) compared to the arylate blocks. Generally, the content of the arylate block is about 10 to 95% by weight, and more preferably about 50 to 95% by weight. Although a mixture of iso- and terephthalate is exemplified by Formula X, the dicarboxylic acid residue in the arylate block can be derived from any suitable dicarboxylic acid residue (as defined above) or a suitable dicarboxylic acid residue. Mixtures of carboxylic acid residues, including those derived from aliphatic diacid dichlorides (also known as "soft block" segments). In a preferred embodiment, the η system 0 and the arylate block comprise a dicarboxylic acid residue derived from a mixture of iso- and terephthalate residues, wherein isophthalate versus terephthalate The mole ratio is about 0.25 to 4.0: ΐ, preferably about 0.4 to 2.5: 1, and more preferably about 0.6 7 to 1.5: 1. In the organic carbonate block, each R5 is independently a divalent organic group. The group preferably contains at least one aromatic hydrocarbon substituted with a dihydroxy group, and has at least about 60% of the total R5 group in the polymer being an aromatic organic group and the rest being aliphatic, alicyclic or aromatic. base. Suitable R5 groups include m-phenylene, p-phenylene, 4; 4, -biphenylene, 4,4, -bis (3,5-dimethyl) _phenylene, 2,2-bis (4 -Phenylene) propane, 656,-(3,353 '; 3, tetramethyl.15], helical bis [1 Η-indane]) and similar groups, such as those corresponding to U.S. Patent No. 4,2] 7 Aromatic hydrocarbons substituted with dihydroxy groups as disclosed in the name or chemical formula (general formula or special formula) described in No. 5 4 3 8 In an exemplary embodiment, each R5 is an aromatic organic group, and is more preferably based on the formula XI:-A1-Υ-Α2-wherein each of A1 and A2 is a monocyclic divalent aromatic group ' And Υ is a bridging group in which A] and A2 are separated by one or two carbon atoms. In Formula XI, the free valence bond of -24- 200520948 (21) is often tied to the position of A I and A 2 relative to Y. Wherein R5 has a compound of formula X1 which is a bisphenol, and for the sake of simplicity, the term "bisphenol" is sometimes used herein to refer to an aromatic hydrocarbon substituted with a dihydroxy group. However, it should be understood that non-bisphenol compounds of this type may be used if appropriate. In Formula XI, A1 and A2 typically represent unsaturated phenylene or a substituted derivative thereof. Exemplary substituents (one or more) are alkyl, alkenyl, and halide (particularly bromine). An unsubstituted phenylene group is preferred. Both a 1 and a 2 are preferably p-phenylene, although the two may be ortho- or m-phenylene, or one ortho- or m-phenylene, and the other p-phenylene. The bridging group Y is a group in which Ai and A2 are separated by one or two atoms. The preferred embodiment is one in which the radicals A! And A2 are separated by one atom. Exemplary radicals of this type-0-, -S-, octa- or -30-2, methylene, cyclohexylmethylene, 2- [2.2.1] -bicycloheptylmethylene, Ethylene, isopropyl fork, neopentyl fork, cyclohexyl fork, ring fifteen carbon fork, ring twelve carbon fork, Jingang Zhangwu fork and the like. It is better to use a gem (a gem_a) ky 1 ene group (often known as "丨 end fork"). However, unsaturated groups are also included. The price for applicability & with the special application of the present invention For the purpose of ability, the preferred bisphenol-based 2,2-bis (4-hydroxyphenyl) propane (bisphenol ^ or 8? Human), of which the isomeric heterodyne 'and A] and A2 are respectively P-phenylene. The RD in the carbonate block may at least partially contain a resorcinol moiety, which is based on the amount of excess resorcinol moiety present in the reaction compound. In other words, in some embodiments, the carbonate block of Formula X may include a hydroquinone moiety with at least one other dihydroxy-substituted aromatic hydrocarbon combination.-25- 200520948 (22) Polymers containing members of the resorcinol arylate chain further comprise diblock, triblock, and multiblock copolyestercarbonates. The blocks containing Chemical bonding between blocks of organic carbonate chain members may include at least one of (a) in a suitable arylate moiety Acid residue of an organic carbonic acid ester portion R -〇 _ \ portion between the parts of the ester bond 'for example, as in a typical illustration of the formula X Π, wherein R is defined in the system as previously:

And (b) the carbonate bond between the diphenol residue at the resorcinol arylate moiety and the organic carbonate moiety, as shown in the formula χ 丨] [1:

Where R and η are as previously defined. Ester linkages of type (a) present in large proportions may form undesired colors in the copolyestercarbonate. Although the present invention is not limited by theory, it is believed that, for example, when the R5 bisphenol A in Formula XII and the part of Formula XII undergo Fries reorganization during subsequent processing and / or exposure Produce color. In a specific embodiment, the copolyester is composed of a diblock copolymer having a carbonate bond between a resorcinol aryl block and an organic carbonate block. . In a more specific embodiment, the copolyestercarbonate is essentially composed of a carbonate bond between resorcinol aryl k% @ and an organic carbonate terminal block. 26- 200520948 (23 ) A block carbonate-ester-carbonate copolymer. It is typically prepared by the method of the present invention and includes an oligomer including resorcinol arylate with at least one hydroxyl terminal position (at least two are preferred). A copolyestercarbonate having at least one carbonate bond between the segment and the organic carbonate block. The oligomer typically has a weight average molecular weight of from about 105,000 to about 40,000, and more preferably from about 15,000 to about 30,000. It can be prepared by reacting an oligomer including the resorcinol arylate with phosgene, at least one chain terminator and at least one aromatic hydrocarbon substituted with dihydroxy group in the presence of a catalyst (such as a tertiary amine) Thermally stable copolyestercarbonate. In an exemplary embodiment, at least one polymer containing a member of the resorcinol arylate polyester chain comprises an isophthalic acid resorcinol (ITR) / bisphenol A copolymer. In a specific embodiment, the outer layer 2 may include one or more sub-layers, wherein at least one of the sub-layers includes a polymer containing a resorcinol arylate polyester chain member. In a specific embodiment, the outer layer 2 consists solely of a single sub-layer comprising a polymer containing a member of the resorcinol arylate polyester chain. In another embodiment, the outer layer 2 may include one or more additional sub-layers, and in an exemplary embodiment, it may include up to four additional sub-layers. For example, in a specific embodiment, the secondary layer may be a composition capable of adhering the outer layer 2 to the middle layer 4. Illustrative examples of suitable adhesive compositions include heat-sensitive adhesives, pressure-sensitive adhesives, and the like. In a particularly exemplified embodiment, the outermost layer of outer layer 2 will have -27- 200520948 (24) having at least one sub-layer comprising a polymer containing a member of the resorcinol arylate polyester chain. As used herein, the "outermost layer" refers to the secondary layer forming the outer surface 12 as exemplified in Figure 1. The outer layer 2 may contain other components, as additives recognized in the art include (but are not limited to) stabilizers , Color stabilizer, heat stabilizer, light stabilizer, auxiliary UV screening agent, auxiliary UV absorber, flame retardant, anti-dripping agent, flow aid, plasticizer, transesterification inhibitor, antistatic Agents, release agents, and colorants (such as metal flakes, glass flakes and beads, ceramic particles, other polymer particles, dyes and pigments, which can be organic, inorganic, or organic metals). In a specific embodiment, the outer layer The total thickness of 2 is about 3 to about 25 thousandths of an inch (hereinafter "mils"). In another specific embodiment, the outer layer 2 has a thickness of about 3 to about 15 mils. In one example In a specific embodiment, the thickness of the outer layer 2 is about 5 to about 15 mils. In an exemplary embodiment, the middle layer 4 of the multilayer laminate I 0 includes a thermoplastic polymer containing a carbonate polymer and is disposed on the Between outer layer 2 and connecting layer 6. In a specific embodiment, the middle layer 4 is in contact with both the outer layer 2 and the inner connection layer 6. In an exemplary embodiment, the middle layer 4 is in continuous contact with both the outer layer 2 and the inner connection layer 6. The anticipated application determines the middle layer Thickness of 4. In one embodiment, the 'middle layer 4 has a thickness of about 4 to about 200 mils, but in another specific embodiment, the middle layer 4 has a thickness of about 5 to about 50 mils. In one example In a specific embodiment, the 'middle layer 4 has a thickness of about 5 to about 30 mils. -28- 200520948 (25) In addition to the carbonate polymer, the thermoplastic polymer of the middle layer may also include other thermoplastic polymers. Other Illustrative examples of thermoplastic polymers suitable for thermoplastic blends of the middle layer include copolyestercarbonates, blends of polycarbonates and copolyestercarbonates, or with other polymers (polybutylene terephthalate ( PBT), blends of polyethylene terephthalate (PET) and the like), polyamines, acrylates (such as polymethyl methacrylate, polyethyl methacrylate), polyphthalates Carbonate (PPC), Polycarbonate (PCE), Polymers and the like containing members of the resorcinol arylate polyester chain as described above. Illustrative examples of PPC and PCE are polycarbonate, bisphenol A isophthalate, and bisphenol A terephthalate Terpolymers of acid esters: \ 〇 / a \ lb where a is an aromatic ester present in an amount of about 60 to about 80% by weight based on the total weight of the copolymer and b is about 20 to about 40% by weight BPA carbonate is present in an amount of%. In a specific embodiment, the thermoplastic polymer containing the middle layer of the carbonate polymer further comprises one or more of PPC, PC, EBT, PET, or a mixture thereof. In a particular example In a specific embodiment, the carbonate polymer-containing thermoplastic polymer further comprises one or more PPC, PCE, or a mixture thereof. These other thermoplastic materials may be present in an amount of from about 0 to about 50% by weight of other thermoplastic materials based on the total weight of the thermoplastic blend of the middle layer 4. In an exemplary embodiment, the thermoplastic -29-200520948 (26) blend contained in the middle layer 4 contains PPC and a polycarbonate homopolymer prepared from a bisphenol A and a carbochlorine precursor. In an exemplary embodiment, P P C is present in an amount of P P C that is not less than or equal to about 5 weight% based on the total weight of the thermoplastic blend of the middle layer 4. In another specific embodiment, the ppc is present in an amount of about 5 to about 40% by weight based on the total weight of the thermoplastic blend of the intermediate layer 4. However, in an exemplary embodiment, the PPC is an intermediate layer The thermoplastic blend of 4 is present in an amount of about 20 to about 30% by weight based on the total weight. In a specific embodiment, the polycarbonate or carbonate polymer comprises an aromatic polycarbonate and mixtures thereof. Aromatic polycarbonates typically have repeating structural units of formula (I):

II —0—A—O—C—— (I) where A is a divalent aromatic group of a dihydroxy compound used in a polymer reaction. Polycarbonates produced by melt polymerization often include Fries products. The Fries product is the product of the Fries reaction. The terms "Frisis reaction" and "Frisis recombination" are used interchangeably herein and refer to the amount of side chain branching measured at the branching point. Friesian Recombination is an unwanted side reaction that occurs during the production of polycarbonate using the melt process. The resulting Fries product is used as a site for branching the polycarbonate chain, which affects the flow and other properties of the polycarbonate. Although a small amount of Frisian products can be tolerated in polycarbonate, the presence of large amounts may have a negative impact on the performance characteristics of polycarbonate, such as toughness and moldability. Measure the branching point through methanol decomposition and then use high pressure liquid chromatography (HP LC) to determine the amount of Fries product 200520948 (27) The reactants used in the production of polycarbonate by polyconcentration are usually one Chemotactic compounds and divine carbonate. There are no special restrictions on the two residue formulas that can be used. For example, a bisphenol compound represented by the compound gwu (η) can be used

(Π) where R and Rb may be the same or different, wherein each _ atom or a monovalent hydrocarbon group, and p and q are each independently a subordinate number, preferably X represents one of the formula (IΠ) groups 4

Rc I -c— or

Re II-C- (III) wherein and Rd are each a halogen atom or a single bad hydrocarbon group, and Re is a divalent hydrocarbon group. Examples of compound types that can be represented by formula (π)% include bis (hydroxyaryl) alkane series 4-transphenyl) methane,]; bis (4-hydroxyphenyl) ethene 2a :, 2 · Bis (4-hydroxybenzylphenyl) propane (or bisphenol-A) 2,2-bis (4-hydroxyphenyl) octane, M • bis (4 · hydroxyphenylbis (4-transphenyl) N-butane, bis (4-hydroxyphenyl) Θfly, hydrazone, 4, fluorene, bis (4-hydroxy-i-methylphenyl) propane, M • bis (4 • triphenyl, propionyl) propane , 2: 2 > Bis ([hydroxyj bromophenyl) propane and yah_zhongbishydroxyaryl) cycloalkane series (such as): BU bis (f hydroxy-31-, 200520948 (28) '1 , 1-bis (4-transphenyl) cyclohexane and the like) and the like, and a composition comprising at least one of the above-mentioned bisphenol compounds.

Other bisphenol compounds which may be substituted by the formula (11) include those in which X is -0-, -SO-, or -SO2-. Examples of these bisphenol compounds are bis (hydroxyaryl) ethers (such as 4,4, -dihydroxydiphenyl ether and the like), diacyl-3,3 '· dimethylphenyl ether, bis (hydroxyl) Diaryl) sulfides (such as 4,45 · dihydroxydiphenylsulfide, 4,4, -dihydroxy-3,3, · dimethyldiphenylsulfide and the like), bis (hydroxydiaryl) 胩(Such as 4,4, -dihydroxydiphenylhydrazone, 4,4, -dihydroxy-3,3, -dimethyldiphenylhydrazone and the like), bis (hydroxydiaryl) fluorene (such as 4,4 , -Dihydroxydiphenylamine, 4,4, -dihydroxy-3,3'-dimethyldiphenylhydrazone and the like) and the like, and a composition comprising at least one of the above-mentioned bisphenol compounds. Other bisphenol compounds that can be used in the polyconcentration of carbonate polymers are represented by formula (IV): (Rf) n

< 〇h) 2

(IV) wherein Rf is a halogen atom of a hydrocarbon group having [to] 0 carbon atoms or a hydrocarbon group substituted with a halogen, and η is from 0 to 4. When the η system is at least 2, Bj Rf may be the same or different. Examples of bisphenol compounds that may be represented by formula (IV) are resorcinol, substituted resorcinol compounds (such as 3-methylresorcinol, 3-ethylresorcinol, 3-propyl Resorcinol, 3-butylresorcinol, 3-tert-butylresorcinol, 3-phenylresorcinol, 3-cumylresorcinol, 2: .3: 4; 6 -Tetrachlororesorcinol, 2; 3: 4; 6-tetrabromo-32- 200520948 (29) resorcinol and the like), catechol, hydroquinone, substituted chloroquinone (such as 3-methylhydroquinone, 3-ethylhydroquinone, 3-propylhydroquinone, butyl chloride, 3-tert-butylhydroquinone, 3-phenylhydroquinone, 3-cumylhydroquinone, tetramethyl Hydroquinone, 2,3,5; 6-tetrat-butylhydroquinone, 2,3,5; 6-tetrafluorohydrogen n, 2,3,556-tetrabromohydroquinone and the like) and the like, And a composition comprising at least one of the above-mentioned bisphenol compounds. It is also possible to use bisphosphonium compounds represented by the following formula (V), such as 3,353’53’-tetramethyl-151, helical bis [indane] -6 56, glycol

A preferred bisphenol compound is bisphenol A. In addition, a copolymerized polycarbonate can be produced by reacting at least two or more bisphenol compounds with a carbonic acid diester. Examples of carbonate diesters that can be used to produce polycarbonate include diphenyl carbonate, bis (2,4-dichlorophenyl) carbonate, bis (2,4,6-trichlorophenyl) carbonate, bis ( 2-cyanophenyl) carbonate, bis (o-nitrophenyl) carbonate, xylyl carbonate, m-tolyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, diethyl carbonate, carbonic acid Dimethyl, dibutyl carbonate, dicyclohexyl carbonate, and the like and a composition comprising at least one of the foregoing carbonic acid diesters. The preferred carbonic acid diester is diphenyl carbonate. The carbonic acid diester may include a dicarboxylic acid and / or a dicarboxylic acid ester. Diacetic acid carbonate is generally required to include less than or equal to about 50 mole% or dicarboxylic acid or dicarboxylic acid-33-200520948 (30) acid ester, preferably less than or equal to about 30 mole%. Examples of dicarboxylic acids or dicarboxylic acid esters that can be used are terephthalic acid, isophthalic acid, sebacic acid, decanedioic acid, diphenylsebacic acid, diphenyl terephthalic acid, diphenyl isophthalate Acid, diphenyldecanedioic acid, diphenyldodecenedioic acid and the like and a composition comprising at least one of the above carbonic acid diesters. If necessary, the diacetic acid carbonate may include at least two dicarboxylic acids and / or dicarboxylic acid esters. Additional examples of suitable dicarboxylic acids or esters are alicyclic dicarboxylic acids or esters. The terms "alicyclic system" and "cycloaliphatic group" as used herein have the same meaning and refer to a group having at least one ring system containing an atomic arrangement, but not the original trivalent group. The arrangement may include heteroatoms such as nitrogen, sulfur and oxygen or may be limited to consisting of carbon and hydrogen. Examples of the cycloaliphatic group include cyclopropyl, cyclopentyl, cyclohexyl, tetrahydrofuranyl and the like. Non-limiting examples of alicyclic dicarboxylic acids or esters include a member selected from the group consisting of: cyclopropanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 1,2-cyclo Pentanedicarboxylic acid, 1,3, cyclopentanedicarboxylic acid, hydrazone; 2. · cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 15 ·· cyclohexanedicarboxylic acid, cyclo Propane dicarboxylic acid diphenyl vinegar, 1,2-cyclobutane dicarboxylic acid diphenyl ester, 1; 3 · cyclobutane dicarboxylic acid diphenyl ester, 1,2-cyclopentane dicarboxylic acid diphenyl ester,丨 · 3 -cyclopentanedicarboxylic acid diphenyl ester, cyclohexanedicarboxylic acid diphenyl ester, ι · 3-cyclohexanedicarboxylic acid diphenyl ester, 1,4-cyclohexanedicarboxylic acid diphenyl Ester and acid or ester of a composition comprising at least two different alicyclic dicarboxylic acids or esters. Molar ratios of carbonate diesters to aromatic dihydroxy compounds are generally required to be from about 0.95 to about 1.2. Molar ratios within this range are generally required to be greater than or equal to about 1.0. It is also required to have a mole ratio in this range that is less than or equal to about -34-200520948 (31) 1.1. If necessary, a carbonate polymer or a polycarbonate can be prepared by reacting a polyfunctional compound having at least three functional groups with an aromatic dihydroxy compound and a carbonic acid diester. Suitable polyfunctional compounds include those having a phenolic hydroxyl or carboxyl group. A preferred polyfunctional compound is a phenolic compound having three functional groups. Examples of these polyfunctional compounds are 1515 (4-hydroxyphenyl) ethane, 2,2'52 ,,-(4-hydroxyphenyl) diisopropylbenzene, 0: -methyl- ( 2,61: ', 〇: 5-gins (4-transphenyl)-; 154-diethylbenzene, α, α', α- (4-hydroxyphenyl) -fluorene, 3,5 · triiso Propylbenzene, resorcinol, 4,6-dimethyl · 2,4,6-ginseno (Hydroxyphenyl) -heptane-2, [, 3,5_ ref (4-hydroxyphenyl) Benzene, 2,2-bis- [454 · (4,4, -dihydroxyphenyl) -cyclohexyl] -propane, trimellitic acid, 1 5 3,5-benzenetricarboxylic acid, pyromellitic acid and Analogues and a composition comprising at least one of the above-mentioned compounds. Preferred polyfunctional compounds are 151, Phenyl (4-hydroxyphenyl) ethane, and α 5 α, α, α, (Ref. 4_ 经Phenyl) -1,3,5 · triisopropylbenzene, or a composition comprising at least one of the above-mentioned compounds. In general, less than or equal to about 0 · 03 mole per mole of aromatic dihydroxy compound can be used. The amount of polyfunctional compounds in the ear. It is required to use an amount of greater than or equal to about 0 · 0 per mole of aromatic dihydroxy compound within this range. The amount of polyfunctional compound is 0. 1 mole. It is also required to use an amount of polyfunctional compound having less than or equal to about 0.002 mole per mole per aromatic dihydroxy compound within this range. Mole aromatic dihydroxy compounds are preferably less than or equal to about 0. 0 1 Mole. Although not wanting to be limited by a particular theory, the salt has a molecular weight of -35- 200520948 (32) from about 1,7 00 to about 22,000 carbonate polymers are suitable for injection molding, while polycarbonate compositions having a molecular weight of at least about 20,000 to about 36,000 are suitable for extrusion processing of multilayer laminates. In one example In a specific embodiment, the carbonate polymer of the thermoplastic polymer of the middle layer 4 has a weight average molecular weight in the range of about 305,000 to about 36,000. In a specific embodiment, the middle layer 4 will comprise LEX AN® polycarbonate, It is a carbonate polymer product commercially available from GE Plastics Corporation. In another embodiment, the middle layer 4 will contain at least one LEXAN® 100, ML9103, 131, or EXRL00065. In an exemplary embodiment The middle layer 4 will contain LEX AN® EXRL 0065 polycarbonate. Turning to Figure 1, it can be seen that the inner connecting layer 6 is opposite to the outer layer 2 and is in contact with the middle layer 2. In an exemplary embodiment, the contact is continuous ° The interconnect layer 6 provides the required adhesion between the multilayer laminate 10 and the substrate 8, as exemplified in Figure 6. In a specific embodiment, the interconnect layer 6 comprises a thermoplastic blend, which includes carbonate polymerization And at least one of acrylonitrile-styrene-acrylate graft copolymer (ASA) or acrylonitrile-styrene graft copolymer of acrylonitrile-butadiene-styrene graft copolymer (ABS). In a specific embodiment, the melt flow volume of the connecting layer resin is between about 2 to about 50 cubic centimeters / 10 minutes, such as in accordance with ISO 1 133 or ASTM D] 2 3 8 at 260 ° C / 5 kg Measured, but in another exemplary embodiment, the 'melt flow volume is from about 3 to about 40 cubic centimeters / 71 minutes. In another exemplary embodiment, the melt flow volume of -36- 200520948 (33) bonding layer resin is between about 3 to about 30 cubic centimeters per 10 minutes, such as 1SO 1 133 or AS TM D. 1 2 3 8 at 260. (: Measured at 5 kg. Suitable carbonate polymer compositions include those as discussed for carbonate polymers suitable for middle layer 4. In a specific embodiment, suitable carbonate polymer compositions Including those having a weight average molecular weight from about 20,000 to about 36,000, however, in another specific embodiment, the carbonate polymer suitable for the tie layer 6 will have about 21,000 to about 3], Weight-average molecular weight. In another specific embodiment, a suitable carbonate polymer composition will have a melt flow viscosity of about 3 to about 30 cm 3/10 minutes (measured at 3 00 ° C / 1.2 kg). ), However, in another specific embodiment, the carbonate polymer composition will have a melt flow viscosity of about 3 to about 26 cm / min. 0 minutes. Carbonate polymerization of the thermoplastic blend of tie layer 6 The composition may also include polyethylene terephthalate (PET), copolyester carbonate, polybutylene terephthalate (PBT), and the like, as described above for the carbonate polymer of the middle layer 4. Discuss. In a In a specific embodiment of the example, the carbonate polymer component of the thermoplastic blend of the tie layer 6 will include a polycarbonate homopolymer. The thermoplastic composition of the tie layer 6 further includes at least one of triammonil-styrene- Acrylonitrile-styrene graft copolymer or copolymer of acrylate graft copolymer (ASA) or propionitrile-butadiene__styrene-styrene graft copolymer (ABS). -37-200520948 (34) Propylene Nitrile-butadiene-styrene (ABS) graft copolymers include polymer portions of two or more different compositions that are chemically bonded. The preparation of the graft copolymers preferably involves first conjugated diene ( (E.g., butadiene or another co-niobene diene) polymerized with monomers that can be copolymerized with it (such as styrene) to provide a polymer backbone. After the polymer backbone is formed, at least one graft monomer ( And two are preferred) polymerization in the presence of the polymer backbone to obtain graft copolymers. These resins are prepared by methods well known in the art. For example, one or more emulsion or solution polymer methods, bulk / bulk polymerization can be used. Method, suspension and / or emulsion-suspension A] BS. In addition, 'for reasons of economics or product performance, or both, ABS materials can be produced by other process technologies, such as batch, semi-batch, and continuous polymerization. Polymers The main chain is preferably a conjugated diene polymer (such as polybutadiene, polyisoprene) or a copolymer (such as butadiene-styrene, butadiene-acrylonitrile) or the like. Formula (XIII) illustrates the conjugated diene monomer generally used to prepare the polymer backbone of the graft copolymer: vb Xb Xb vb \ II / c = c——c—cx / \ b (χΠΙ) where X is Halogen, c I-C5 radical, chlorine, bromine or the like. Examples of conjugated diene monomers that can be used are butadiene, polyisoprene, I; 3-heptadiene, methylheptadiene, 2; 3-dimethyl- 丨, 3-butadiene Dioxane, 2-ethyl_] heptadiene,] > and 2,4-hexadiene, with chloro and bromo groups -38-200520948 (35) Replaced with butane (such as monochlorobutane Ene, bromobutadiene, dibromobutadiene M}, mixtures and the like containing at least one of the above conjugated diene monomers and the like. The preferred conjugated diene monobutadiene system can be used in polymerization A monomer or group of monomers polymerized in the presence of a primary bond is a monoethenyl aromatic hydrocarbon. The following formula (χιν) illustrates the monovinyl aromatic monomer used:

Where X b is halogen, C!-C 5 alkyl, chlorine, bromine or the like. Examples of conjugated diene monomers that can be used are butadiene, polyisoprene, 5: 3-heptadiene, methyl-1,3-heptadiene, 2,3-dimethyl -153-butadiene, 2-ethyl-1 5 3 -heptadiene, 1 5 3-and 2 5 4 -hexadiene, butadiene substituted with chloro and bromo groups (such as dichlorobutane Diene, bromobutadiene, dibromobutadiene), mixtures and the like containing at least one of the above conjugated diene monomers. Preferred conjugated diene monosystem butadiene. The second monomer group that can be polymerized in the presence of the polymer backbone is monopropionate (such as propionate), substituted propionate and / or propionate (using acrylonitrile) As an example) and acrylic C ^ C7 alkyl vinegar (such as methyl methacrylate) and the like. The following formula (XV) illustrates acrylonitrile, substituted acrylonitrile or acrylate: -39- 200520948 (36)

Where xb is the previous definition and Y2 is cyano'c] -c] 2alkoxycarbonyl or the like. Examples of these monomers include acrylonitrile, ethacrylonitrile 'methacrylonitrile, chloroacrylonitrile, chloroacrylonitrile, bromoacrylonitrile, bromoacrylonitrile, methyl methacrylate, methyl methacrylate , Ethyl acrylate, butyl acrylate, propyl acrylate, isopropyl acrylate, a mixture containing at least one of the above monomers, and the like. Preferred monomers include acrylonitrile 'ethyl acrylate, and methyl methacrylate. In the preparation of the graft copolymer, the 'polymer main chain contains about 5 to about 60% by weight of the total graft copolymer composition. The monomers (in the case of styrene and acrylonitrile) polymerized in the presence of the polymer's main bond comprise a total graft polymer from about 40: to about 95% by weight. The second group of graft monomers of the graft polymer composition (taking acrylonitrile, ethyl acrylate, or methyl methacrylate as examples) is copolymerized with a total graft content of about 5% to about 40% by weight The composition is preferred. The monovinyl aromatic hydrocarbon, exemplified by styrene, contains from about 10 to about 70% by weight of the total graft copolymer. When preparing a graft copolymer, it is normal to combine a specific percentage of polymerized monomers grafted on the polymer main chain with each other and form a free copolymer. When styrene is used as one of the graft monomers and acrylonitrile is used as the second graft monomer, the composition at a specific site is copolymerized into a free styrene-acrylonitrile copolymer (SAN). In the case where α-methylstyrene (or other mono-40-200520948 (37) body) replaces styrene in the composition used to prepare the graft polymer, a specific percentage of the composition may be α-formaldehyde Styrene-acrylonitrile copolymer. There are also occasions when a copolymer (such as α-methylstyrene-acrylonitrile) is added to the graft polymer copolymer blend. Therefore, the graft copolymer may optionally contain up to about 80% free copolymer based on the total weight of the graft copolymer. In an exemplary embodiment, the thermoplastic polymer of the interconnect layer 6 will include an ABS graft copolymer and a SAN copolymer. The polymer main chain may be an acrylic rubber, such as n-butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, a polymerization product containing at least one of the above-mentioned mixtures and the like, if necessary. In addition, a small amount of diene can be copolymerized with the matrix polymer in the backbone of the acrylate rubber resulting in improved grafting. Particularly suitable are styrene butadiene rubber or copolymers of butadiene rubber having a glass transition temperature of less than 0 ° C. Acrylonitrile-butadiene-styrene graft copolymers' are known in the art and many copolymers are commercially available, for example, from General

Electric Company such as BLENDEX® grade 13], 336, 338,] 60 and 4 1 5 high rubber acrylonitrile-butadiene-styrene resin. ABS polymers and resins having an average particle size from about 0.1 micrometers to about 5 micrometers are particularly suitable. In one exemplary embodiment, ABS having an average particle size from about 0.1 micrometers to about 2 micrometers is used. ABS polymers and resins having a crosslink density from about 40 to about 90% are particularly suitable. In one exemplary embodiment, ABS having a crosslink density from about 45 to about 80% is used. 200520948 (38) In a specific embodiment, the thermoplastic blend of the interconnect layer 6 will comprise one or more commercially available AB polymers or resins from GE Plastics under the trademark CYCOLOY®. In an exemplary embodiment, the ABS polymer is one or more of CYCOLOY® C1000HF, C 1 2 00 'MC8800, MC8 002 > EXCY0076, and CYCLOGY® grade CI000HF, EXCY0076, and MC8002 are used in the specifically illustrated embodiment , And use EXCY0076 in a specific example. ASA polymers are typically acrylates, terpolymers of styrene and acrylonitrile, and typically include a grafted crosslinked alkyl acrylate rubber phase. Most of the ASA products consist of a two-phase system of acrylate-styrene-acrylonitrile graft elastomer terpolymer dispersed in a continuous glass matrix of styrene-acrylonitrile (SAN) copolymer. Grafting is typically composed of a polyalkyl acrylate rubber core and grafted SAN shells. Grafts of styrene and acrylonitrile on a small amount of rubber particles make the rain phase compatible. ASA is typically made by a three-step polymerization reaction. First, an elastomer component is produced in a water-based emulsion or a solution polymerization method, typically a polypropylene alkyl polyacrylate rubber or a polyalkyl acrylate rubber. In the second stage, 'copolymerization and grafting of styrene ethyl benzene and acrylonitrile with other monomers on the elastomer phase as needed' achieve the required compatibility. This stage can be carried out either in an emulsion, a bulk / bulk process or via a suspension and / or emulsion-suspension process route. In the third stage, styrene is polymerized with acrylonitrile (and other monomers as needed) or with the second, (graft) stage or separately in different operations' to form a tough matrix. Furthermore, this step may include one or more of the following processes: emulsion, bulk or suspension. In addition, for reasons of or manufacturing -42- 200520948 (39) economic or product performance reasons, or both reasons, ASA materials can be produced by other process technologies, such as batch, semi-batch, and continuous polymerization. In a specific embodiment, a suitable SA polymer is prepared from a poly (alkyl acrylate) rubber-based ASA graft phase combined with a vinyl aromatic / vinyl cyanide / vinyl carboxylate matrix. . In an exemplary embodiment, the 'ASA polymer is a two-phase system. The two-phase system includes an acrylic rubber substrate ', preferably poly (butyl acrylate) rubber, and a super substrate (or graft) copolymer of styrene-acrylonitrile (SAN) attached thereto. This phase is called a rubber graft phase, "because SAN is physically attached or grafted to rubber via a chemical reaction. In a specific example, MMASAN (methyl methacrylate and styrene acrylonitrile) is used. Terpolymer) and the "tough matrix phase" or continuous phase of PMMA (polymethyl methacrylate). The rubber graft phase (or dispersed phase) is dispersed throughout the matrix phase of PMMA / MMASAN that forms the polymer continuum The rubber interface is formed at the interface between the graft and the matrix phase. The grafted SAN is used as a compatibilizer between the rubber and the matrix phase of the interface, P MA / M MASAN, and avoid this The two are otherwise immiscible. The ASA thermoplastic resin-based vinyl carboxylate monomer, vinyl aromatic monomer, and vinyl cyanide graft copolymer are used in the present invention. As used herein ASA therefore includes polymer groups derived from vinyl carboxylic acid ester monomers, vinyl aromatic monomers, and vinyl cyanide as defined below. The vinyl carboxylic acid used in the present invention is defined herein by the following structural formula Ester mono-43- 200520948 (40) body (α-,-unsaturated carboxylic acid): H J 〇

\ I II

/ C = C-C—OA H where] is selected from hydrogen, alkyl from 1 to 8 carbon atoms, cycloalkyl, alkoxy, and hydroxyalkyl, and A is selected from 1 to 12 carbons Atomic alkyl. Examples of vinyl carboxylate monomers include butyl acrylate, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, butyl methacrylate, propyl methacrylate, propyl acrylate, Hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, decyl methacrylate, methyl ethacrylate, butyl methacrylate, cyclohexyl methacrylate, methoxyethyl acrylate Esters, hydroxyethyl methacrylate and mixtures thereof. A vinyl aromatic monomer is defined herein by the following structural formula:

Wherein each X is independently selected from hydrogen, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkoxy, aryloxy, hydroxy, and halogen, and from 5 to 5 carbon atoms, and among them R is selected from hydrogen, alkyl from 1 to 5 carbon atoms, bromine and chlorine. Examples of substituted vinyl aromatic monomers include styrene, chloromethylstyrene, vinylxylene, trimethylstyrene, 3: 5-diethylstyrene, p-tert-butylstyrene, 4.N-propylstyrene, methylstyrene, ethylstyrene, methyl-p-methylstyrene, p-hydroxystyrene, methoxystyrene, chlorostyrene, 2-methyl- 4-Chlorostyrene, bromostyrene, α-chlorostyrene, α__bromobenzene-44- 200520948 (41) vinyl, dichlorostyrene, 256-dichloromethylbenzene Ethylene, dichlorostyrene, tetrachlorostyrene and mixtures thereof. Ethyl cyanide monomer is defined herein by the following structure: \ I _ C = C—0ΞΝ / where R is selected from hydrogen, alkyl from 1 to 5 carbon atoms, bromine and chlorine. Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, ethyl acrylonitrile, α-chloroacrylonitrile, and α-bromoacrylonitrile. Various monomers other than those listed above may be further used to further improve various characteristics of suitable ASA polymers and copolymers. Suitable A S A as discussed above can be combined with copolymerizable monomers or monomers. For example, in addition to or replacing butyl acrylate, the rubber phase is composed of polybutadiene, styrene · butadiene, or butadiene-acrylonitrile copolymer, polyisoprene, EPM (ethylene / propylene rubber) , EPDM rubber (ethylene / propylene / unconjugated diene rubber) and other cross-linked acrylates and alkyl acrylate rubbers mainly composed of C 1-C 1 2 acrylates and alkyl acrylates, or alone or two Or mixtures thereof. Moreover, the rubber may contain or be a block or random copolymer. In addition to or instead of the acrylate, styrene, and acrylonitrile monomers used in the graft or matrix resin, vinyl carboxylic acids (such as acrylic acid, methacrylic acid, and itaconic acid), and acrylamide can be used. (Such as acrylamide, methacrylamide and n-butylacrylamide), ^, square-unsaturated dicarboxylic anhydrides (such as maleic anhydride and itaconic anhydride), ^ ... / 5-unsaturated dicarboxylic acids Fluorene imines (such as maleimide 'N-methyl maleimide, N-alkyl maleimide, N-aryl maleimide-45- 200520948 (42) amines and halogens -Substituted N-alkyl N-arylmaleimide), fluorinated polymethylmethacrylate (polypentaimide), unsaturated ketones (such as vinyl ketone and methyl Isopropenone), alpha-olefins (such as ethylene and propylene), vinyl esters (such as vinyl acetate and vinyl stearate), ethyl alkenyl and vinylidene halides (such as vinyl chloride and vinylidene chloride, And vinyl bromide and vinylidene bromide), vinyl aromatic substituted aromatic ring structures (such as vinyl naphthalene and vinyl anthracene) and monomers of pyridine monomers, or used alone Use or use a mixture of two or more. In a specific embodiment, the rubber is a crosslinked poly (alkyl acrylate) rubber and a poly (alkyl acrylate) rubber. In other embodiments, the rubbers are poly (butyl acrylate), poly (ethyl acrylate), and poly (2-ethylhexyl acrylate) rubber. In still other embodiments, the rubber is a poly (butyl acrylate) rubber, particularly a poly (n-butyl acrylate) rubber. In a specific embodiment, the mono-ethylenically unsaturated vinyl carboxylate mono-system used to prepare the rubber graft phase is selected from the group consisting of acrylic (C] -C] 2) alkyl vinegar and nonopropionic acid (C ]-Ci2) Ci-Cg Early vinegar and its mixture. In another specific embodiment, it is selected from alkyl acrylate monomers and mixtures thereof. The term "polyethylenically unsaturated" as used herein means that each molecule has two or more ethylenic unsaturations. Use of polyethylenically unsaturated monomers in suitable alkyl acrylate monomers, providing "crosslinked" poly (alkyl acrylate) monomer particles formed in the process and providing subsequent reaction with the graft monomers "Crosslinking" position in poly (alkyl acrylate) rubber. In -46-200520948 (43) In a specific embodiment, the polyethylene-based unsaturated cross-linking monomer includes at least two ethylenically unsaturated sites per molecule, which have the same degree of polymerization with the monoethylene under the polymerization conditions used. The unsaturated alkyl acrylate monomer has similar reactivity. In another specific embodiment, the graft linking monomers include those monomers having at least one ethylenic unsaturation site that have similar reactivity to the alkyl acrylate monomer under the emulsion or other polymerization conditions used And a monomer having at least one other ethylenically unsaturated site, which has a reactivity substantially different from that of the monoethylenically unsaturated alkyl acrylate monomer under the emulsion polymerization conditions used in the method of the present invention, Therefore, at least one unsaturated position of each molecule of the graft-linking monomer will react during the synthesis of the rubber latex and at least one unsaturated position of each molecule of the graft-linking monomer will not react after the synthesis of the rubber latex. Effective reactions were maintained under different subsequent reaction conditions. In yet another specific embodiment, the polyethyleneized unsaturated crosslinking monomer includes, for example, butene diacrylate, divinylbenzene, butene diol dimethacrylate, trimethylolpropane tri ( (Meth) acrylate, allyl methacrylate, diallyl maleate, triallyl cyanate, and mixtures thereof. In a preferred embodiment, triallyl cyanate is used as both the crosslinking monomer and the graft linking monomer. The reaction mixture may optionally include a small amount (e.g., up to about 25 pbw per 100 pbw of total monomers) of other unsaturated monomers copolymerizable with the alkyl acrylate monomer used in the present invention. Suitable copolymerizable monomers include, for example, monoethylenically unsaturated carboxylic acids, methacrylic hydroxyl (C) -C! 2) alkyl ester monomers, (meth) acrylic (C ^ C) 2) cycloalkyl Ester monomer-47-200520948 (44), acrylamide monomer, maleimide monomer and vinyl ester. The term "(C4-C 12 or C4 ·] 2) cycloalkyl" as used herein represents a ring system substituent having from 4 to 12 carbon atoms per molecule, and "propanthylamine" The terms are collectively referred to as acrylamide and methacrylamide. Vinyl aromatic monomers are also suitable, such as, for example, styrene and substituted phenethyl strips having one or more aradyl, alkoxy, hydroxy or halo substituents attached to an aromatic ring. In a specific embodiment, the ASA polymer comprises from about 10% to about 40% poly (butyl acrylate) rubber. In a second embodiment, about 15% to about 30%. In a third specific embodiment, it is about 5% to 25% rubber. In a specific embodiment, the rubber graft phase comprises 20% poly (butyl acrylate) to about 70% poly (butyl acrylate). In another specific embodiment, the rubber graft phase comprises 45% poly (butyl acrylate) and 55% San, from 65% styrene and 35% acrylonitrile to 75 ° / °. The S AN sites of the grafted phase were prepared by styrene and 25% acrylonitrile. In yet another specific embodiment, the SAN site comprises from about 70-75% styrene and about 25-30% acrylonitrile. In a specific embodiment, MMASAN includes 80% MMA, 5% styrene, and 5% acrylonitrile, and in another specific embodiment, about 60% MMA, 30% styrene, and 0% acrylonitrile. In a third embodiment, MM AS AN contains about 45% methyl methacrylate, 40% styrene, and 15% acrylonitrile. In a specific embodiment, the ratio of PMMA / MMASAN in the matrix phase copolymer ranges from about 2 0/8 0 to about 80/20, and in another specific embodiment, from 25/75 Up to about 7 5/2 5, including -48- 200520948 (45) including 5 0/5 0 〇 In a specific embodiment, the ASA contains a ratio of the graft to the matrix phase of 15/85 to 75/25, and In another embodiment, about 45 percent of the grafted phase and 55 percent of the matrix phase are present. The graft copolymer phase and the matrix phase homopolymer, copolymer, and / or terpolymer can be conjugated, blended, and colloidized with various blending methods known in the art to form an ASA polymer blend. In an exemplary embodiment, the thermoplastic blend of the interconnect layer 6 is a commercially available thermoplastic composition, which includes a carbonate polymer, an ASA graft copolymer, and a SAN copolymer. A suitable commercially available thermoplastic composition is a thermoplastic composition from the GELOYtm brand of General Electric Plastics of Washington, WV. In a specific embodiment, the interconnect layer 6 is at least one of GEL0Y ™ HRA1 50, H R A 1 7 0 'X P 7 5 5 0, and mixtures thereof. In a particularly exemplified embodiment, the tie layer 6 comprises GELOY ™ HRA150. Suitable SANs typically have a weight average molecular weight from about 60,000 to about 200,000, and in an exemplary embodiment, from about 90,000 to about 190,000. It has a weight of about 15 to 40 based on the weight of the SAN copolymer. /. SAN copolymers having an acrylonitrile (AN) content are particularly suitable. In one exemplary embodiment, ' s AN copolymers having a propionitrile nitrile content of from about 20 to about 35 weight percent are used. In a specific embodiment, the thermoplastic polymer of the tie layer 6 comprises about 25 to about 80 weight based on the total weight of the tie layer. / ° Polycarbonate, from about 0 to about 35 wt.% A S A or A B S and from about 0 to about 40% by weight of S AN. In another embodiment, the thermoplastic 200520948 (46) polymer of the tie layer 6 will comprise about 40 to about 80 weight percent polycarbonate, about 10 to about 30 weight percent based on the total weight of the tie layer. ASA or ABS and about 10 to about 30% by weight SAN. In an exemplary embodiment, the thermoplastic polymer of the tie layer 6 will comprise about 40 to about 75 weight percent polycarbonate, based on the total weight of the tie layer, and about 12 to about 30 weight. /. ASA or ABS and about 12 to about 30% by weight of SAN. The thermoplastic polymer of the inner connecting layer may include other components as required, such as additives recognized in the art, including (but not limited to) stabilizers, color stabilizers, heat stabilizers, light stabilizers, UV screening agents, UV absorption Agents, flame retardants, anti-dripping agents, flow aids, plasticizers, transesterification inhibitors, antistatic agents, release agents and coloring agents (such as metal sheets, glass sheets and beads, ceramic granules, other polymers Particles, dyes and pigments, which can be organic, inorganic or organic metals). In an exemplary embodiment, the thermoplastic polymer of the interconnect layer will comprise a stabilizer or a stabilizer system. In one particular embodiment, the ' stabilizer will comprise an alkyl thioester. In a particularly exemplified embodiment, the stabilizer will comprise a stabilizer comprising four (/ 5 · laurylthiopropionates) of isopentaerythritol. In another alternative embodiment, the stabilizer will comprise a stabilizer including four isoprene tetraols (dodecylthiopropionate). Examples of commercially available stabilizers based on or including suitable alkyl thioesters are SEENOX ™ stabilizers commercially available from Sh i p r o Kas e i Kas h i L t d ·. In a specific example, the inner linking layer 6 includes a thermoplastic polymer containing a polycarbonate polymer, an ABS graft copolymer, a SAN copolymer, and a 200520948 (47) SEENOX stabilizer. These thermoplastic polymer blends are from CYCOLOY® EXCY0076 by GE Plastics. The actual thickness of the bonding layer 6 is determined by the intended application. In a specific sinus embodiment, the linking layer 6 typically has a thickness of about 3 to about 30 mils, while in another specific embodiment, the thickness of the inner linking layer 6 is about 3 to 12 mils. In an exemplary embodiment, the bonding layer 6 has a thickness of about 3 to about 6 mils, while in another specific embodiment, the thickness is about 9 to 12 mils. Usually the total thickness of the multilayer laminate is from about 20 to about 200 mils. In an exemplary embodiment, the multilayer laminate 10 has a thickness of about 30 to about 55 mils. Multi-layer laminates can be made by any of a variety of manufacturing methods, including (but not limited to) co-injection molding, co-extrusion layering, co-extrusion blown film molding, co-extrusion, overlap Molding method, multi-shot injection molding method, sheet molding method and the like. In a specific embodiment, multiple layers can be manufactured by co-extruding layers. In another specific embodiment, the outer layer 2 can be laminated separately on a film placed on a drum from a previously extruded film. In this embodiment, the outer layer 2 may include at least one sub-layer including an adhesive or an adhesive composition. In a specific embodiment, a multi-layer laminate 10 can be prepared by co-extruding layers, wherein the layers are simultaneously extruded through a sheet or film die hole that can be a single or multi-manifold design. While still in the molten state, the layers are laminated together and then compressed together through a pair of heatable roller clamps. The laminate is then cooled. Determining multilayer laminates according to the intended application] 0 thickness -51-200520948 (48) In a specific embodiment, a multilayer laminate 10 can be formed by co-extrusion, where each molten layer 2, 4 and 6 are passed together The mold holes are injected and extruded, so multiple sheets are extruded and then cooled. In still another specific embodiment, the method for forming the multilayer laminate 10 includes a co-extrusion blown film method, in which multiple layers are extruded to form a tubular membrane embryo, and then blow-molded to form a hollow article, and then slitted. Long strips were prepared to produce flat multilayer laminates 10. In an exemplary embodiment, a multi-layer laminate can be manufactured by co-extrusion. As shown in Figure 3, the key illustration of the extrusion mechanism is designated by the number 30, and the layers 2, 4 and 6 are respectively from the bucket / extruder 3 2/3 8, 3 4/4 0 and 3 6 / 42 co-extrusion lamination can form a multilayer laminate 10. The extruder 30 includes a first bucket 32, a second bucket 34, and a third bucket 36, which respectively transfer the material to the corresponding first compression device 38 'and the second squeeze Device 40, third extruder 42. In this way, each bucket and each pressure reducer can be suitable for processing components with different pressure temperatures and viscosities. Each extruder transfers the molten material to the drum frame 44 'to compress the respective composition into a multilayer laminate. Multi-layer laminates can be further processed on a roller to hide the roller 46 or pulled into a sheet by a traction roller 48. The multilayer laminate 10 sheet is cut into smaller-sized sheets at a cutting station 50 and placed in a sheet holder 55. The layers 2, 4 and 6 are processed into multilayer laminates using an extrusion mechanism 30 with different processing temperatures]. In an exemplified embodiment, the first extruder 38 processes m-diphenol 200520948 (49) polyester outer layer 2 at a temperature of about 400 to about 550 ° C, from about 400 to about 5,000 °. F is preferred, and more preferably from about 440 to about 480 ° F. The second extruder 40 processes the thermoplastic polymer-containing polycarbonate composition of the middle layer 4 at a temperature of about 4 0 to about 5 5 0 ° F, from about 4 2 0 to about 5 3 0 ° F. Preferably, and more preferably from about 4 3 0 to about 5 3 0 ° F. The third extruder 42 processes the inner connecting layer at a temperature of about 400 to about 5 30 ° F, preferably from about 420 to about 500 ° F, and more preferably from about 440 to about 4 80 ° F. good. The layers 2, 4 and 6 are compressed as they are to a shape suitable for the multilayer laminate 10. In an exemplary embodiment, the thermoformable multilayer laminate 10 can be formed into a shaped multilayer laminate 60 having any desired configuration as exemplified in FIG. 4. It should be recognized that the cross-section of the formed multilayer laminate is the same as the multilayer laminate 10 of 1. However, the shape of the formed multilayer laminate 60 may have a configuration shadowed on the substrate 8 or the model 62 as illustrated in Fig. 4. The multilayer laminate can be formed into a multilayer laminate 60 formed by any of a variety of methods including, but not limited to, a thermoforming method, a compression molding method, a vacuum forming method, and the like. Turning now to FIG. 2, a cross-sectional view of the shaped object 20 can be observed. The shaped object 20 includes a multilayer laminate 10 adhered or bonded to the substrate 8. The inner connecting layer 6 is adhered to the substrate 8, but at the same time, the middle layer 4 of the multilayer laminate is provided with good adhesion. The substrate 8 used can be any of a variety of suitable compositions, including strong materials, raw materials, ester foams, base materials, amine materials, including plastic heat cases, and actual materials. . Hot matter △ mouth This group is limited and unexpected (chemical-53-200520948 (50) (including polyurethane foam and fiber-reinforced polyurethane), polypropylene (including Fiber-reinforced polypropylene), polycarbonate / PBT blends, and the like. Reinforced fibers include carbon fibers, glass, and the like. In a specific embodiment, the substrate 8 is at least one of the reinforced thermoplastic polyurethanes. Acid esters, shaped thermoplastic polyurethanes, and combinations thereof. In an exemplary embodiment, the substrate 8 is at least one polymer reinforced with glass fibers, polyurethane reinforced with carbon fibers, and polymer reinforced with carbon fibers. Urethanes, shaped thermoplastic polyurethanes, and combinations thereof. The internal bonding layer 6 can be bonded to the substrate 8 by molding, adhesives, chemical bonding, mechanical bonding, and similar methods and combinations thereof. In an exemplary embodiment, the substrate 8 is directly injection-molded on the inner connecting layer 6 so that the inner connecting layer 6 is adhered to the substrate 8. A forming method for manufacturing a shaped article is also disclosed, as illustrated in FIGS. 5 and 6. The reveal The method includes providing the disclosed multilayer laminates 10; placing the multilayer laminates 10 in the model 62, so a hollow body 64 is formed after or on the backside of the inner connecting layer 6 of the multilayer laminates; and placing the substrate 8 in the multilayer layers In the hollow body 64 after the assembly 10, the inner connecting layer 6 of the multilayer laminate 10 is bonded or adhered to the substrate 8 to provide a shaped object 20-in the specific embodiment shown in FIGS. 5 and 6, it is placed on the model The multilayer laminate in 62] 0 may be a shaped multilayer laminate 60. In a specific embodiment, the shaped multilayer laminate 60 may have a shape substantially conforming to the model 62. -54- 200520948 (51) 所The disclosed method further includes cooling the shaped object and / or removing the shaped object 20 from the mold 62. In one embodiment, the shaped object 20 is cooled and then removed from the mold. Placing the substrate 8 on the hollow body 64 can be performed in various ways. Including injection molding, reaction injection molding, long fiber reinforced injection molding and the like. In a specific embodiment, the substrate 8 is injected into the hollow body by reaction injection molding. 64. In a specific embodiment, the substrate 8 is injected with a liquid and then molded to form a semi-solid or solid substrate 8. The molded object 20 is particularly suitable for automobile parts, including (but not limited to) outer body surfaces. Panels, such as door panels, roofs, water tank panels, and the like. The following examples will illustrate specific sinus embodiments and manufacturing methods of the present invention. Example Example 1 Four types of compositions with different tie layers (which have ASA / SAN thermoplastic blends) multilayer laminates. Each laminate system consists of an outer layer of an isophthalic acid resorcinol / bisphenol A copolymer (commercially available from GE Plastics ITR 4 7 5 7 7), Polycarbonate homopolymer (commercially available from LEXAN ®] 3] (Example 1 & 2), LEXAN®] 00 (Example 3) prepared from bisphenol A and carbochlorine and polymer Carbonate (PC), acrylonitrile-styrene-acrylate graft copolymer (ASA), and styrene-acrylonitrile-propionitrile copolymer (SAN) are composed of internal linking layers composed of different proportions as listed in Table 1. Made of. The average thickness of the outer layer is from 5 to 15 mils. The average thickness of the middle layer is from 5 to 40 mils and the average thickness of the inner layer is -55- 200520948 (52) from 4 to 5 mils. The total thickness of the laminate is from 30 to 55 mils. Table]. Joint layer jg compound & adhesion sample p C (〇 / 〇) AS A / S AN (%) (〇: no adhesion / 2: acceptable adhesion) 1 72 28 1 2 60 40 2 3 60 40 2 4 27 7 8 0-1

Laminates were prepared via three different extrusion lines.

The samples] and 2 were extruded on extrusion line A of a single manifold mold having a width of 30 inches and a extrusion line speed of 10 · 75 feet / minute. Contact the chrome roller (240 ° F) with the outer layer and the silicone roller (130 ° F) with the inner layer. The inner layer composition was extruded using a single-stage screw extruder with a diameter of 1/4 inch. The middle composition was extruded using a 2 W2 inch diameter extruder equipped with a two-stage hindered spiral with an intermediate mixing section. The outer layer was extruded using a 2-inch diameter single-stage screw extruder. Sample 3 was extruded on extrusion line B of a single manifold mold having a width of 54 inches and a extrusion line speed from 6.2 to 8.] feet / minute. Contact the chrome roller (240 ° F) with the outer layer and the silicone roller (200 ° F) with the inner layer. The inner layer composition was extruded using a 2-inch diameter single-stage screw extruder. The middle composition was extruded using a 3 and 1/2 inch diameter extruder equipped with a two-stage hindered spiral with vacuum release. Extrude the outer layer > 56- 200520948 (53) using a single stage screw extruder with a diameter of 2 1/2 inches. Sample 4 was extruded on extrusion line C of a single manifold mold having a width of 14 inches and a extrusion line speed of about 4 to 6 feet per minute. Contact the chrome roller (240 ° F) with the outer layer and the silicone roller (130 ° F) with the inner layer. The inner layer composition was extruded using a 1-inch diameter single-stage screw extruder. The middle layer composition was extruded using a 1 1/2 inch diameter extruder. The outer layer was extruded using a 1-inch diameter single-stage screw extruder. The laminate is adhered to a long-fiber-reinforced injection molded (LFI) coated thermoplastic polyurethane foam substrate. Adhesion was measured using a visually determined tensile strength meter. A report of the observed results is presented in Table 1 above. As shown above, the tie layer of the present invention usually exhibits acceptable adhesion between the tie layer and the substrate. Peel tests were also performed on samples 2 and 3 using a 90 ° peel test. The average results (pounds per inch, pounds per inch) are as follows: average peel strength (lbs / inch) of 6.5, standard deviation of 2.5. Digitally prove the adhesion strength and adhesion of the disclosed linking layer. Example 2 produced multilayer laminates similar to those produced in Example 1, but replacing ASA with ABS. Each laminate system consists of the outer layer of an isophthalic acid resorcinol / bisphenol A copolymer (commercially available from GE P] astics ITR- # 7577), a polycarbonate prepared from bisphenol A and carbochlorine The middle layer of an ester homopolymer (commercially available from LEXAN® EXRL00 65) and a polycarbonate (pC), acrylonitrile · butadiene-styrene graft copolymer (ABS), and styrene-propylene 200520948 ( 54) Sulfonitrile copolymer (S AN) is made of inner connecting layer composed of different proportions as listed in Table 2. The average thickness of the outer layer is from 5 to 15 mils, the average thickness of the middle layer is from 15 to 4 G mils and the average thickness of the inner layer is from 4 to 15 mils. The total thickness of the laminate is from 30 to 55 mils. Table 2. Adhesive layer blends & adhesion samples PC (%) ABS / S AN (%) peel test (mean / standard deviation) 1 5 1 19/3 0 21.1 / 5 2 73 14/13 14.5 / 4.3 3 82 8/10 4.5 / 0.4 4 65 19/16 13.4 / 1 .2

Sample 4 was formed on the extrusion line C of a single manifold mold having a width of 4 inches and a extrusion line speed of about 4 to 6 feet per minute. The chrome roller (240 ° F) is in contact with the outer layer and the chrome roller (130 ° F) is in contact with the inner layer. The inner layer composition was extruded using a 1-inch diameter single-stage screw extruder. The middle layer composition was extruded using a 1 1/2 inch diameter extruder. The outer layer was extruded using a 1-inch diameter single-stage screw extruder. The peel test was carried out in accordance with Example 1, and the results are reported in Table 2 above. The laminate of Sample 4 was adhered to a long-fiber-reinforced injection-molded (LF1) coated thermoplastic polyurethane foam substrate. The adhesion of the linking layer to the LF1-PU foam was measured according to Example 1. The results are about -58- 200520948 (55)

Example 3 A multilayer laminate was made according to sample 4 of Example 2, except that about 0.3% by weight of SEENOX stabilizer was added to the inner tie layer composition. The peel strength was evaluated according to Examples 1 and 2. The initial peel strength of the interconnect layer to the middle layer is about 32, but the expanded peel strength is about 13 pounds / inch to about 14 pounds / inch. After the LFI-PU foam was coated in accordance with Examples 1 and 2, the peel strength of the interconnecting layer to the foam was evaluated. The initial peel strength is about 24 pounds per inch, but the expanded peel strength is about 16 pounds per inch. Multi-layer laminates allow the production of shaped articles with the necessary surface qualities and appearance of automotive exterior parts, while providing improved adhesion to substrates. The final multilayer laminate has the advantage that it can be made by coextrusion. Although the present invention has been described with reference to preferred embodiments, those skilled in the art understand that various changes can be made without departing from the scope of the present invention and equivalents can be substituted for its elements. In addition, the modification can be made without departing from its basic scope to suit the particular situation or material guided by the present invention. Therefore, it is hoped that the present invention is not limited to the specific specific embodiments disclosed in the best mode covered for carrying out the present invention, but the present invention will include all the specific embodiments within the scope of the attached patent application. All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. [Brief description of the drawings] -59- 200520948 (56) Figure I is a cross-sectional view of a specific embodiment of the multilayer laminate disclosed in the figure. Fig. 2 is a cross-sectional view of a specific embodiment of a molded article containing a multilayer laminated body including a drawing bonded to a substrate]. Fig. 3 is a schematic illustration of a specific embodiment of a co-extrusion mechanism for forming a multilayer laminate of the present invention. FIG. 4 is a cross-sectional view of a specific embodiment of a method of manufacturing an object. FIG. 5 is a cross-sectional view of a specific embodiment of a method of manufacturing an object. FIG. 6 is a cross-sectional view of a specific embodiment of a method of manufacturing an object. Sectional view 〇 [Description of main component symbols] 2: Outer layer 4: Middle layer 6: Connecting layer 8: Substrate 10: Multi-layer laminate 2 0: Auto parts 3 0: Co-extrusion mechanism 3 2: First bucket 34 : The second bucket 3 6: The third bucket-60- (57) 200520948 3 8: The first squeezer 4 0: The second squeezer 4 2: The third squeezer 4 4: Roller stand 4 6: Hidden roll 48: Pulling roll 50 0: Shearer 5 2: Sheet stand 60: Formed multilayer laminate 62: Model 64: Hollow body

Claims (1)

200520948 Π) Pickup, patent application scope] · A formable thermoplastic multilayer laminate (10), which includes an outer layer (2) 'which contains a polymer containing members of a resorcinol arylate polyester chain, a middle layer ( 4), which includes a thermoplastic polymer, and an inner connecting layer (6), which includes a thermoplastic polymer including a carbonate polymer and acrylonitrile-styrene-acrylate graft copolymer (ASA) or propylene The acrylonitrile-styrene graft copolymer of at least one of the nitrile-butadiene-styrene graft copolymer (ABS), the middle layer (4) is between the outer layer (2) and the inner connecting layer (6), It is in contact with both the outer layer (2) and the inner connecting layer (6). 2. Multi-layer laminate (1) according to item 1 of the scope of patent application, wherein the styrene copolymer is a styrene acrylonitrile copolymer (S AN). 3. The multilayer laminate (10) according to item 1 of the scope of the patent application, wherein the acrylonitrile-styrene graft copolymer comprises an acrylonitrile-butadiene-styrene graft copolymer (A B S). 4. The multilayer laminate according to item [Scope of the patent application] ()), wherein the thermoplastic polymer contained in the inner connecting layer (6) contains from about 25 to about 80% by weight of polycarbonate, and from about]. To about 35% by weight of the acrylonitrile-styrene graft copolymer and from about 10 to about 40% by weight of the styrene copolymer. The weight% is based on the total weight of the tie layer (6). 5. The multilayer laminate (1) according to item 1 of the scope of the patent application, wherein the inner linking layer (6) further comprises a stabilizer containing an alkyl thioester. 6. Multi-layer laminate according to item [Scope of the patent application] () 0), which is -62- 200520948 (2) the middle and outer layer (2) has a secondary layer composed of at least one member containing a resorcinol arylate polyester chain The outermost surface of the composition. 7. The multilayer laminate () 0) according to item 1 of the scope of the patent application, wherein the at least one secondary layer comprises an isophthalic acid resorcinol / bisphenol A copolymer. 8-The multilayer laminate (] 0) according to item 1 of the patent application, wherein the middle layer comprises polycarbonate. 9. A formed multilayer laminate (10), comprising the multilayer laminate (10) in the scope of patent application No. 1 and formed by at least one of a thermoforming method and a compression molding method. 10. An article comprising a formable thermoplastic multilayer laminate (10), the laminate comprising an outer layer (2) 'which comprises a polymer containing a member of the resorcinol arylate polyester chain, a middle layer (4 ), Which comprises a thermoplastic polymer, and an inner linking layer (6), which comprises a thermoplastic polymer, which comprises a carbonate polymer and an acrylonitrile-styrene-acrylate graft copolymer (ASA) or acrylonitrile -Butadiene-styrene graft copolymer (ABS), at least one of which is an acrylonitrile-styrene graft copolymer, wherein the middle layer (4) is listed between the outer layer (2) and the inner connecting layer (6), and Continuous contact with both the outer layer (2) and the inner junction layer (6); and the substrate bonded to the inner junction (6). Π. A shaped article according to the scope of the patent application] 0, wherein the substrate is at least one of the following: thermosetting materials, thermoplastic materials, foaming materials, reinforced thermoplastic materials, and combinations thereof. ^ 63- (3) 200520948] 2. A method of manufacturing an article, comprising providing a polyfluorene laminate (10), the laminate comprising an outer layer (2), which comprises a polyester chain containing resorcinol arylate Members of the polymer, the middle layer (4), which contains a thermoplastic polymer, the inner linking layer (6), which contains a thermoplastic polymer, the thermoplastic polymer comprising a carbonate polymer and containing an acrylonitrile-styrene-acrylate graft Copolymer (ASA) or acrylonitrile-butadiene-styrene graft copolymer (ABS), at least one of which is an acrylonitrile-styrene graft copolymer. The middle layer (4) is interposed between the outer layer (2) and the inner layer. Between the layers (6) and in contact with both the outer layer (2) and the inner connecting layer (6); placing the multilayer laminate (10) in a model so that a hollow body is formed after the multilayer laminate (10); And placing the substrate in the hollow body after the multilayer laminate (10), wherein the inner connecting layer (6) of the multilayer laminate (] 0) is adhered to the substrate to obtain an object. -64 ^