KR20060114000A - Weatherable multilayer articles and method for their preparation - Google Patents

Abstract

Disclosed are weatherable multilayer articles comprising (i) a coating layer comprising a block copolyestercarbonate comprising structural units derived from at least one 1,3-dihydroxybenzene and at least one aromatic dicarboxylic acid, (ii) a second layer comprising a polymer comprising carbonate structural units, (iii) a substrate layer comprising a polypropylene, and (iv) at least one adhesive layer comprising the reaction product of an amine-functionalized polypropylene and a polyurethane, wherein the coating layer is in contiguous contact with the second layer, and the adhesive layer is in contiguous contact with the second layer and the substrate layer. Also disclosed is a method for making the multilayer article.

Description

Weatherable multilayer products and methods of making the same {WEATHERABLE MULTILAYER ARTICLES AND METHOD FOR THEIR PREPARATION}

The present invention relates to weatherable multilayer dendritic products and methods of making the same. More specifically, the present invention provides a protective block copolyestercarbonate coating, a second layer comprising a polymer comprising a carbonate structural unit, a substrate, and at least one adhesive layer between the second layer and the substrate. It relates to a multilayer product comprising.

Various dendritic products suffer from long term color instability. This causes yellowing of the polymer resin in some embodiments, which degrades its transparency and attractiveness. Gloss loss can also be an undesirable long term development.

Sulfurization of polymers is often caused by the action of ultraviolet radiation, which is why this sulfation is often referred to as "photoyellowing". Numerous means of suppressing photosulfurization have been used and proposed. Many of these means include incorporation of ultraviolet absorbing compounds (UVAs) into polymers. In most cases, UVA is a low molecular weight compound and should be used at relatively low levels, typically up to 1% by weight, to avoid degradation of polymer properties such as high temperature properties, as reflected by impact strength and thermal warping temperature. This level may be inadequate to provide sufficient protection.

One method of protecting dendritic products from photosulfurization and gloss loss is to coat with a weather resistant second polymer. As used herein, the term "weather resistant" refers to resistance to the phenomenon. Weather resistant polymers suitable for this purpose include lesosinol isophthalate / terephthalate copolyarylate. This is described by Cohen et al., J. Poly. Sci., Part A-1, 9, 3263-3299 (1971) and certain related patents, including US Pat. Nos. 3,444,129, 3,460,961, 3,492,261 and 3,503,779 to Monsanto Company. It is a topic. General proprietary US Pat. No. 6,572,956 relates to weather resistant multilayer articles having a coating layer comprising structural units derived from 1,3-dihydroxybenzene organodicarboxylate. General proprietary US Pat. No. 6,306,507 discloses at least one coating comprising a thermally stable polymer comprising a resorcinol arylate polyester chain that is substantially free of anhydrous linking groups connected to two or more dimers of the polymer chain, prepared by interfacial methods. A weather resistant multilayer article having a coating layer comprising a layer thereon. In some embodiments, the polymer comprising a resorcinol arylate polyester chain source is copolyestercarbonate.

Weathering copolyestercarbonates are often used as coatings on a second layer which is a polymer resin comprising carbonate units. When the assembly of weatherable polymer and the second layer is applied to a base resin having a second layer adjacent the substrate, special problems may arise. When the substrate is very nonpolar, such as a polypropylene substrate, there is practically no adhesion between the substrate and the second layer comprising polar carbonate units. Therefore, the problem to be solved is to manufacture a weather resistant multilayer product comprising a polypropylene-containing substrate which can be used for various purposes as body parts for outdoor vehicles and devices such as automobiles and exhibits proper adhesion between the various layers. To develop a method.

Summary of the Invention

We have found a multilayer article with a coating layer that provides protection of the underlying layers from weathering and exhibits good adhesion between the various layers. In one aspect, the invention provides a coating layer comprising (i) a block copolyestercarbonate comprising structural units derived from at least one 1,3-dihydroxybenzene and at least one aromatic dicarboxylic acid, (ii) carbon At least one adhesive comprising a second layer comprising a polymer comprising an acid structural unit, (iii) a substrate layer comprising polypropylene, and (iv) a reaction product of an amine-functionalized polypropylene and polyurethane A layer, wherein the coating layer is in close contact with the second layer and the adhesive layer is in contact with the second layer and the substrate layer. In another aspect, the present invention includes a method of making the multilayer article.

Various other features, aspects, and advantages of the invention will become more apparent by reference to the following detailed description of the invention and the appended claims.

In the following specification and claims, reference is made to a number of terms that are defined as having the following meanings. The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. “Optional” or “optionally” means that an event or situation described below may or may not occur, and the description includes cases where the event occurred and when it did not occur. The term "layer" is used herein interchangeably with the terms "film" and "sheet". The terms "adhesive layer" and "binding layer" are used interchangeably.

In the multilayer article of the invention the copolyestercarbonate film comprises one or more block copolyestercarbonates comprising alternating carbonate and arylate blocks. The block copolyestercarbonate comprises a polymer comprising a 1,3-dihydroxybenzene structural unit and an aromatic dicarboxylic acid structural unit of formula (I):

Where

Each R ¹ is independently halogen or C ₁ -C ₁₂ alkyl;

p is 0 to 3;

Each R ² is independently a divalent organic radical;

m is at least 1;

n is about 4 or greater.

In some embodiments n is at least about 10, in other embodiments at least about 20, and in still other embodiments from about 30 to 150. In some embodiments m is at least about 3, in other embodiments at least about 10, and in still other embodiments from about 20 to 200. In another embodiment m is about 20-50. “Alternative carbonate and arylate blocks” herein means that the copolyester carbonate includes at least one carbonate block and at least one arylate block. In certain embodiments the block copolyestercarbonates include one or more arylate blocks and two or more carbonate blocks. In another particular embodiment the block copolyestercarbonates comprise an A-B-A structure having at least one arylate block ("B") and at least two carbonate blocks ("A").

The arylate block contains structural units comprising 1,3-dihydroxybenzene moieties which may be unsubstituted or substituted. Alkyl substituents, when present, are often straight or branched alkyl groups and are quite often located in the ortho position for both oxygen atoms, although other ring positions are also contemplated. Suitable C ₁ -C ₁₂ alkyl groups include, but are not limited to, aryl-substituted alkyls including methyl, ethyl, n-propyl, isopropyl, butyl, iso-butyl, t-butyl, nonyl, decyl and benzyl. In some embodiments any alkyl substituent is methyl. Suitable halogen substituents include bromo, chloro and fluoro. Also suitable are 1,3-dihydroxybenzene moieties containing a mixture of alkyl and halogen substituents. The value of p may be 0 to 3 in one embodiment, 0 to 2 in another embodiment, and 0 to 1 in another embodiment. In one embodiment the 1,3-dihydroxybenzene moiety is 2-methyl resorcinol. In many embodiments the 1,3-dihydroxybenzene moiety is unsubstituted resorcinol with p of zero. Also contemplated are polymers containing mixtures of 1,3-dihydroxybenzene moieties, such as unsubstituted resorcinol and mixtures of 2-methyl resorcinol.

The 1,3-dihydroxybenzene moiety in the arylate structural unit may be an aromatic dicarboxylic acid moiety which may be a monocyclic moiety such as isophthalate or terephthalate or a halogen-substituted derivative thereof; Or polycyclic moieties such as biphenyl dicarboxylate, diphenylether dicarboxylate, diphenylsulfone dicarboxylate, diphenylketone dicarboxylate, diphenylsulfide dicarboxylate or naphthalenedicarboxylate. To a dicarboxylic acid residue. In some embodiments the polycyclic moiety is naphthalene-2,6-dicarboxylate; Or mixtures of monocyclic and / or polycyclic aromatic dicarboxylates. In many embodiments the aromatic dicarboxylic acid residues are isophthalates and / or terephthalates. One or both of these residues may be present. In one embodiment both are present in a molar ratio of isophthalate to a terephthalate of about 0.20 to 5.0: 1, and in another embodiment both are present in a molar ratio of isophthalate to a terephthalate of about 0.25 to 4.0: 1. If the ratio of isophthalate to terephthalate is greater than about 4.0: 1, an acceptable level of cyclic oligomers may be formed in some embodiments. If the ratio of isophthalate to terephthalate is less than about 0.25: 1, an acceptable level of insoluble polymer may be formed in some other embodiments. In some embodiments the molar ratio of isophthalate to terephthalate is about 0.40 to 2.5: 1 and in other embodiments about 0.67 to 1.5: 1.

In various embodiments, the arylate block fragment in the copolyestercarbonate is substantially free of anhydrous linking groups linked to two or more dimers of the polymer chain. Substantially free of anhydrous linkages herein means that the copolyestercarbonate exhibits a molecular weight reduction of less than 10% in some embodiments and 5% in other embodiments upon heating the copolyestercarbonate at about 280-290 ° C. for 5 minutes. It indicates a molecular weight decrease of less than%.

In the carbonate blocks of the copolyestercarbonates, each of R ² in the formula (I) is independently an organic radical derived from a dihydroxy compound. In most cases, at least about 60% of the total number of R ² groups in the polymer are aromatic organic radicals and the remainder are aliphatic, cycloaliphatic or aromatic radicals. Suitable R ² radicals include, but are not limited to, m-phenylene, p-phenylene, 4,4'-biphenylene, 4,4'-bi (3,5-dimethyl) phenylene, 2,2-bis ( 4-phenylene) propane and similar radicals such as those corresponding to dihydroxy-substituted aromatic hydrocarbons disclosed by the name or formula (general or specific) in US Pat. No. 4,217,438. In some embodiments of the invention the dihydroxy compound is 6-hydroxy-1- (4'-hydroxyphenyl) -1,3,3-trimethylein, 4,4 '-(3,3,5- Trimethylcyclohexylidene) diphenol; 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane; 2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol-A); 4,4-bis (4-hydroxyphenyl) heptane; 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane; 2,2-bis (4-hydroxy-3-methylphenyl) propane; 2,2-bis (4-hydroxy-3-ethylphenyl) propane; 2,2-bis (4-hydroxy-3-isopropylphenyl) propane; 2,4'-dihydroxydiphenylmethane; Bis (2-hydroxyphenyl) methane; Bis (4-hydroxyphenyl) methane; Bis (4-hydroxy-5-nitrophenyl) methane; Bis (4-hydroxy-2,6-dimethyl-3-methoxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane; 1,1-bis (4-hydroxy-2-chlorophenyl) ethane; 2,2-bis (3-phenyl-4-hydroxyphenyl) propane; Bis (4-hydroxyphenyl) cyclohexylmethane; 2,2-bis (4-hydroxyphenyl) -1-phenylpropane; (3,5,3 ', 5'-tetrachloro-4,4'-dihydroxyphenyl) propane; 2,4'-dihydroxyphenyl sulfone; 2,6-dihydroxynaphthalene; Hydroquinone, resorcinol; C ₁ -C ₃ alkyl-substituted resorcinol. In certain embodiments the dihydroxy compound comprises bisphenol A.

In addition, suitable dihydroxy compounds are the compounds represented by the following formula (II) which is 3- (4-hydroxyphenyl) -1,1,3-trimethylindan-5-ol and 1- (4-hydroxyphenyl) -1 Compounds containing an indene structural unit, such as a compound represented by the following formula (III), which is a 3,3-trimethylindan-5-ol:

Among the suitable dihydroxy-substituted aromatic hydrocarbons include 2,2,2 ', 2'-tetrahydro-1,1'-spirobi [1H-indene] diol of formula IV:

Where

Each R ³ is independently selected from a monovalent hydrocarbon radical and a halogen radical;

R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently C ₁ -C ₆ alkyl;

R ⁸ and R ⁹ are each independently H or C ₁ -C ₆ alkyl;

n is each independently selected from a positive integer having a value of 0-3.

In certain embodiments the 2,2,2 ', 2'-tetrahydro-1,1'-spirobi [1H-indene] diol is 2,2,2', 2'-tetrahydro-3,3,3 ', 3'-tetramethyl-1,1'-spirobi [1H-indene] -6,6'-diol (often known as "SBI").

The term "alkyl" as used in various embodiments of the present invention refers to linear alkyl, powder containing carbon and hydrogen atoms and optionally containing atoms other than carbon and hydrogen, such as atoms selected from Groups 15, 16 and 17 of the Periodic Table of the Elements. It is intended to represent topographic alkyl, aralkyl, cycloalkyl, bicycloalkyl, tricycloalkyl and polycycloalkyl radicals. Alkyl groups may be substituted or unsubstituted and may include, for example, vinyl and allyl. The term "alkyl" also encompasses the alkyl portion of the alkoxide group. In various embodiments the normal and branched alkyl radicals contain from 1 to about 32 carbon atoms and are optionally selected as one or more groups selected from C ₁ -C ₃₂ alkyl, C ₃ -C ₁₅ cycloalkyl or aryl as non-limiting examples C ₁ -C ₃₂ alkyl substituted with; And C ₃ -C ₁₅ cycloalkyl optionally substituted with one or more groups selected from C ₁ -C ₃₂ alkyl. Some specific illustrative examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodec Contains thread. Some illustrative non-limiting examples of cycloalkyl and bicycloalkyl radicals include cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, bicycloheptyl, and adamantyl. In various embodiments the aralkyl radical contains 7 to about 14 carbon atoms and includes, but is not limited to, benzyl, phenylbutyl, phenylpropyl and phenylethyl. In various embodiments The aryl radicals used in the various embodiments of the present invention are substituted or unsubstituted aryl or heteroaryl radicals containing 6 to 18 ring carbon atoms. Illustrative non-limiting examples of such aryl radicals include C ₆ -C ₁₅ aryl optionally substituted with one or more groups selected from C ₁ -C ₃₂ alkyl, C ₃ -C ₁₅ cycloalkyl or aryl. Some specific illustrative examples of aryl radicals include substituted or unsubstituted phenyl, biphenyl, toluyl and naphthyl. Heteroaryl groups contain about 3 to about 10 ring carbon atoms and include, but are not limited to, triazinyl, pyrimidinyl, pyridinyl, furanyl, thiazolinyl and quinolinyl.

In some embodiments each R ² is an aromatic organic radical and in certain embodiments is a radical of the formula V:

Where

A ¹ and A ² are each a monocyclic divalent aryl radical;

Y is a bridging radical in which one or two carbon atoms separate A ¹ and A ² .

Free valence bonds in formula (V) are typically in the meta or para position of A ¹ and A ² with respect to Y. Compounds in which R ² has the formula (V) are bisphenols and for the sake of simplicity the term "bisphenol" is often used herein to refer to dihydroxy-substituted aromatic hydrocarbons, but non-bisphenol compounds of this type may also be suitably used. Should understand.

In formula (V), A ¹ and A ² typically represent unsubstituted phenylene or substituted derivatives thereof, and exemplary substituents (one or more) are alkyl, alkenyl and halogen (particularly bromine). In many embodiments A ¹ and A ² represent unsubstituted phenylene radicals. A ¹ and A ² may both be p-phenylene, but both may be o- or m-phenylene or one may be o- or m-phenylene and the other may be p-phenylene.

The bridging radicals Y are those in which one or two atoms separate A ¹ from A ² . In certain embodiments one atom separates A ¹ from A ² . Exemplary radicals of this type are -C = O, -O-, -S-, -SO- or -SO _2- , methylene, cyclohexylmethylene, 2- [2.2.1] -bicycloheptylmethylene, ethylene, Isopropylidene, neopentylidene, cyclohexylidene, cyclopentadedecylidene, cyclododecylidene and adamantylidene. In some embodiments the radical is a gem-alkylene radical. However, unsaturated radicals are also included. For the purposes of this invention and for the reasons of availability and particular suitability a particular bisphenol is 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A or BPA), wherein Y is isopropylidene and A ¹ and A ² are each p-phenylene.

Depending on whether any unreacted 1,3-dihydroxybenzene moieties are present in the reaction mixture as described below, R ² in the carbonate block consists of radicals derived from 1,3-dihydroxybenzene moieties or At least in part thereof. Thus, in one aspect of the invention the copolyestercarbonate comprises a carbonate block having an R ² radical derived from the same dihydroxy compound as one or more 1,3-dihydroxybenzene moieties in the polyarylate block. . In another embodiment the copolyestercarbonate comprises a carbonate block having R ² radicals derived from a dihydroxy compound different from any 1,3-dihydroxybenzene moiety in the polyarylate block. In another embodiment the copolyestercarbonate is derived from a dihydroxy compound, at least one of which is the same as any 1,3-dihydroxybenzene moiety in the polyarylate block and the other at least is different from the moiety. Carbonate blocks containing a mixture of R ² radicals. When a mixture of R ² radicals derived from a dihydroxy compound is present, the molar ratio of the same dihydroxy compound as present in the polyarylate block to a different dihydroxy compound than that present in the polyarylate block is typically About 1: 999 to 999: 1. In some specific embodiments the copolyestercarbonate comprises a carbonate block containing a mixture of unsubstituted resorcinol, substituted resorcinol and R ² radicals derived from two or more of bisphenol A.

Diblock, triblock and multiblock copolyestercarbonates are included in the present invention. The chemical linkage between the block containing the arylate chain source and the block containing the organic carbonate chain source is typically between the diphenol residue of the arylate residue and the-(C = O)-O-- residue of the organic carbonate residue. Carbonate linkages, but other types of linkages, such as esters and / or anhydrides, are also possible. Typical carbonate linkages between the blocks are shown in Formula VI:

Where

R ¹ and p are as defined above.

In one embodiment the copolyestercarbonate is substantially composed of a diblock copolymer having a carbonate linkage between the arylate block and the organic carbonate block. In another embodiment the copolyestercarbonate is substantially comprised of a triblock carbonate-ester-carbonate copolymer having a carbonate linkage between the arylate block and the organic carbonate end-block. Copolyestercarbonates having at least one carbonate linkage between the arylate block and the organic carbonate block are typically 1,3-dihydroxybenzene arylate- containing one or more and often two hydroxy-termination sites. It is prepared from containing oligomers (often referred to as hydroxy-terminated polyester intermediates below).

In another embodiment, the copolyestercarbonate comprises arylate blocks linked by carbonate bonds as shown in Formula VII:

Where

R ¹ , p and n are as defined above and the arylate structural unit is as described in formula (I).

Copolyestercarbonates comprising Formula VII may arise from the reaction of the hydroxy-terminated polyester intermediate with a carbonate precursor in the substantial absence of any dihydroxy compound that is different from the hydroxy-terminated polyester intermediate. have. In other embodiments, the copolyestercarbonates may comprise a mixture of copolyestercarbonates having different structural units and different structures, as described herein, for example.

For copolyestercarbonates suitable for use in the present invention, the blocks may be distributed such that a copolymer having arylate blocks in any desired weight ratio relative to the carbonate blocks is provided. The copolyestercarbonate, in one embodiment, from about 5% to about 99% by weight of the arylate block, in another embodiment from about 20% to about 98% by weight of the arylate block, in another embodiment about 40% by weight To about 98 weight percent arylate blocks, in another embodiment from about 60 weight percent to about 98 weight percent arylate blocks, in another embodiment from about 80 weight percent to about 96 weight percent arylate blocks, in another embodiment Contains about 85% to about 95% by weight arylate blocks.

Copolyester carbonate films include, but are not limited to, stabilizers, color stabilizers, heat stabilizers, light stabilizers, auxiliary sunscreens, auxiliary ultraviolet absorbers, flame retardants, antidropping agents, flow aids, plasticizers, ester exchange inhibitors, antistatic agents And other ingredients such as release agents and colorants such as additives known in the art, including metal flakes, glass flakes and beads, ceramic particles, other polymer particles, dyes and pigments, which may be organic, inorganic or organometallic. Can be. In certain embodiments, the copolyestercarbonate-containing layer is substantially transparent.

The thickness of the coating layer is provided sufficient to protect the underlying layer from the effects of weathering, in particular ultraviolet irradiation, as measured by retention of properties such as gloss and color stability in any colorant-containing layer. . In one embodiment, the thickness of the coating layer is in the range of about 2 to 2,500 μm, in another embodiment about 10 to 250 μm, and in other embodiments about 50 to 175 μm.

If desired, an overlayer may be included on the coating layer to provide, for example, wear or scratch resistance. In certain embodiments, a silicon overlayer is provided on the copolyestercarbonate-containing coating layer.

The multilayer article of the present invention comprises a second layer comprising a polymer comprising carbonate units. In one embodiment, the polymer of the second layer comprises one or more homopolycarbonates. Any polycarbonate that can be processed into a film or sheet is suitable. In various embodiments, suitable polycarbonates include those having structural units derived from monomers selected from the group consisting of all of the above used in the carbonate blocks of the block copolyestercarbonates. In certain embodiments, the polycarbonate film comprises bisphenol A homo- or copolycarbonate. In another particular embodiment, the polycarbonate film comprises bisphenol A homopolycarbonate. In other embodiments, the polycarbonate film may comprise one or more first polycarbonates and one or more other polymeric resins, such as, but not limited to, different agents than the first polycarbonate in terms of structural units or molecular weight or both. 2 polycarbonates or blends with polyesters or additive polymers such as acrylonitrile-butadiene-styrene copolymers or acrylonitrile-styrene-acrylate copolymers.

The second layer includes, but is not limited to, stabilizers, color stabilizers, heat stabilizers, light stabilizers, sunscreens, ultraviolet absorbers, flame retardants, antidropping agents, flow aids, plasticizers, ester exchange inhibitors, antistatic agents, mold release agents, fillers and Other ingredients such as additives known in the art, including colorants such as metal flakes, glass flakes and beads, ceramic particles, other polymer particles, dyes and pigments, which may be organic, inorganic or organometallic. Can be. In certain embodiments, the second layer further comprises one or more colorants. In another particular embodiment, the second layer comprises both bisphenol A polycarbonate and one or more colorants selected from the group consisting of dyes, pigments, glass flakes and metal flakes. In certain embodiments, the metal flakes comprise aluminum flakes. In another particular embodiment, the metal flakes comprise aluminum flakes having dimensions of about 20-70 μm. Additional examples of colorants include, but are not limited to, Solvent Yellow 93, Solvent Yellow 163, Solvent Yellow 114 / Disperse Yellow 54, Solvent Violet 36, Solvent Violet 13, Solvent Red 195, Solvent Red 179 , Solvent Red 135, Solvent Orange 60, Solvent Green 3, Solvent Blue 97, Solvent Blue 104, Solvent Blue 101, Macrolex Yellow E2R, Dispers Yellow 201, Dispers Red 60, Diamond Red K ( Diaresin Red K), Colorplast Red LB, Pigment Yellow 183, Pigment Yellow 138, Pigment Yellow 110, Pigment Violet 29, Pigment Red 209, Pigment Red 202, Pigment Red 178, Pigment Red 149, Pigment Red 122, Pigment Orange 68, Pigment Green 7, Pigment Green 36, Pigment Blue 60, Pigment Blue 15: 4, Pigment Blue 15: 3, Pigment Yellow 53, Pigment Yellow 184, Pigment Yellow 119, Pigment White 6, Pigment Red 101, Pigment Green 50, Pigment Green 17, Pigment Brown 24, Pigment Blue 29, pigment blue 28, pigment black 7, lead molybdate, lead chromate, cerium sulfide, cadmium sulfoselenide, and cadmium sulfide. Exemplary extender and reinforcing fillers include, but are not limited to silica, silicate, zeolite, titanium dioxide, stone powder, glass fiber or glass spheres, carbon fiber, carbon black, graphite, calcium carbonate, talc, mica, lithopone, zinc oxide , Zirconium silicate, iron oxide, diatomaceous earth, calcium carbonate, magnesium oxide, chromium oxide, zirconium oxide, aluminum oxide, crushed quartz, calcined clay, talc, kaolin, asbestos, cellulose, wood flour, cork, cotton and synthetic Reinforcing fillers such as textile fibers, in particular glass fibers, carbon fibers and metal fibers.

The thickness of the second layer is in the range of about 2 to 2,500 μm in one embodiment, about 10 to 1,000 μm in another embodiment and about 50 to 600 μm in another embodiment. An adhesive layer may optionally be present between the copolyestercarbonate-containing coating layer and the second layer comprising the carbonate structural unit. In various embodiments, the optional adhesive layer includes those known in the art to provide adhesion to a surface or layer comprising a polymer comprising carbonate units. In some embodiments, the optional adhesive layer is transparent and in other embodiments the optional adhesive layer has the same color as the second layer.

Suitable substrates for the multilayer articles of the present invention include one or more polymers comprising polypropylene structural units. The term "polypropylene" as used herein denotes a polymer comprising structural units derived from propylene, and includes homopolypropylenes and copolymers comprising structural units derived from propylene. In some embodiments, the polypropylene may be a copolymer having at least about 70%, or at least about 80%, or at least about 90% by weight structural units derived from the polymerization of propylene.

The polypropylene-containing substrate may comprise functionalized or nonfunctionalized polypropylene, or a mixture of functionalized polypropylene and nonfunctionalized polypropylene. Illustrative examples of suitable polypropylene-containing substrates are random, conjugated and block copolymers of propylene further comprising up to about 30% by weight of units derived from C ₂ -C ₁₀ alpha-olefins comprising aromatic alpha-olefins. It may include. In one particular embodiment, the suitable alpha-olefin is ethylene. In other embodiments, suitable substrates include polypropylene homopolymers or polypropylene-containing copolymers, vinyl carboxylic acids or anhydrides, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, malic acid and Acid- or anhydride-functionalized polypropylene homopolymers or copolymers formed by the reaction of at least one polar functionalizing agent selected from the group consisting of monoesters of maleic acid and fumaric acid with monohydroxy alcohols. In some embodiments, it will be understood that both the acid and anhydride functional groups may be present simultaneously on the polypropylene-containing substrate. In another embodiment, suitable substrates include, for example, acid-functionalized polypropylenes and especially anhydride-functionalized polypropylenes, and illustrative examples include alpha, omega alkylenediamines; Ethylene diamine, propylene diamine, butylene diamine, hexamethylene diamine; Polyoxyalkylene diamines; N-alkyl alpha, omega alkylenediamine; N-alkyl alpha, omega ethylenediamine; N-hexylethylene diamine; Bis (alpha-aminoalkyl) aromatic compounds; amine-functionalized polypropylenes formed by the reaction of a functionalizing agent comprising one or more primary or secondary amine groups, including p-xylene diamine and m-xylene diamine. In some embodiments, the preferred polypropylene may have a flexural modulus of at least about 100,000 pounds / inch ² (689 MPa) at 23 ° C., measured according to ASTM D790. In another embodiment, the polypropylene, when measured according to ASTM DI 238 at 2.16 kg and 200 ° C., may have a melt flow rate of about 0.1 to about 50 g / 10 minutes, preferably about 1 to about 30 g / 10 minutes. The polypropylene-containing substrate further comprises a combination of the above homopolymers and copolymers. In another embodiment, the polypropylene-containing substrate comprises a blend of the homopolymer and copolymer with one or more thermoplastics. Illustrative examples of suitable thermoplastics include, but are not limited to, polyphenylene ether, polyamide, polyester, polyetherimide, polyethylene and polystyrene. In certain embodiments, the polypropylene-containing substrate comprises a mixture of polypropylene homopolymer or copolymer and poly (2,6-dimethyl-1,4-phenylene ether). In another exemplary embodiment, a suitable polypropylene-containing substrate is a thermoplastic polyolefin, also known as "TPO".

In embodiments wherein the polypropylene-containing substrate is homopolypropylene, the homopolypropylene typically has a crystalline content of at least about 20%, preferably at least about 30%. In other embodiments, the homopolypropylene substrate has a crystalline content of less than about 90% or less than about 80%.

There is no particular limitation on the thickness of the polypropylene-containing substrate layer as long as the multilayer article comprising the substrate can proceed to the final wood form. The thickness of the polypropylene-containing substrate layer is in one embodiment about 2 to 12,500 μm, in another embodiment about 5 to 10,000 μm, in another embodiment about 10 to 6,000 μm, in another embodiment about 10 to 2,500 μm, in another embodiment about 10 To 1000 μm, in another embodiment from about 10 to 600 μm, in other embodiments from about 10 to 375 μm, in other embodiments from about 20 to 300 μm, in other embodiments from about 20 to 250 μm, in other embodiments from about 25 to 175 μm.

Polypropylene-containing substrate layers include, but are not limited to, colorants, pigments, dyes, impact modifiers, stabilizers, color stabilizers, heat stabilizers, light stabilizers, sunscreens, ultraviolet absorbers, flame retardants, antidropping agents, fillers, flow aids It may further contain additives known in the art, including plasticizers, ester exchange inhibitors, antistatic agents and release agents. In one aspect of the invention, the polypropylene-containing substrate also incorporates one or more fillers and / or colorants. Exemplary extender and reinforcing fillers and coloring agents include silica, silicates, zeolites, titanium dioxide, stone powders, glass fibers or glass spheres, carbon fibers, carbon black, graphite, calcium carbonate, talc, mica, lithopone, zinc oxide, Zirconium silicate, iron oxide, diatomaceous earth, calcium carbonate, magnesium oxide, chromium oxide, zirconium oxide, aluminum oxide, crushed quartz, calcined clay, talc, kaolin, asbestos, cellulose, wood flour, cork, cotton and synthetic textile fibers, especially glass Reinforcing fillers such as fibers, carbon fibers and metal fibers, as well as colorants such as metal flakes, glass flakes and beads, ceramic particles, other polymer particles, dyes and pigments, which may be organic, inorganic or organometallic.

The multilayer article of the present invention comprises at least one adhesive layer comprising the reaction product of amine-functionalized polypropylene and polyurethane. In some embodiments of the invention, the adhesive layer can optionally include a second polypropylene that is not amine-functionalized. In one particular embodiment, the second polypropylene includes any polypropylene suitable for use as the substrate layer. In another embodiment, the second polypropylene comprises the same polypropylene present in the substrate layer.

As used herein, amine-functionalized polypropylene refers to amine-functionalized polypropylene homopolymers or copolymers, or mixtures thereof. The amine-functionalized polypropylene can be derived from any polypropylene suitable for use as, but not limited to, the substrate layer. Amine-functionalized polypropylenes can be prepared by any known manufacturing method, and can be prepared by primary amine-functionalized polypropylene, secondary amine-functionalized polypropylene, or primary and secondary amine-functionalized Both polypropylene can be included. In one embodiment, suitable amine-functionalized polypropylenes may be both (i) polypropylene with one or more amine-reactive groups (sometimes referred to herein as amine-functional polypropylenes) and (ii) both primary, It may be prepared via a reaction between one or more amine compounds having two or more amine groups, which may be multi-secondary, or one may be primary and one secondary. Although the present invention is not limited by any theory of operation, a statistically high proportion of only one amine group on the amine compound reacts with a polypropylene having an amine-reactive group to produce a functionalized polypropylene having free amine groups. It is believed to produce. Exemplary polypropylenes having amine-reactive groups include those having one or more functional groups selected from the group consisting of acids, esters and anhydrides. In certain embodiments, exemplary polypropylenes having amine-reactive groups include polypropylene and vinyl carboxylic acids or anhydrides, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid in a melt or solid state process. It can be derived from the reaction of monoesters of maleic acid and fumaric acid with maleic or monohydric alcohols. In some embodiments, it will be understood that both the acid and anhydride functional groups may be present simultaneously on the polypropylene having amine-reactive groups. Exemplary methods for preparing amine-functionalized polypropylenes are described in Q. -W. Lu et al., Macromolecular Symposia, volume 198, pp. 221-232 (2003).

In various embodiments, polyurethanes suitable for use include thermoplastic polyurethanes known in the art that provide adhesion to a surface or layer comprising a polymer comprising carbonate units. Thermoplastic polyurethanes typically comprise structural units derived from polyol chains joined together by hard segments derived from one or more organic diisocyanates and one or more optional chain extenders. Polyol chains are typically represented as soft segments that impart low temperature flexibility and room temperature elasticity. In general, the higher the soft segment concentration, the higher the elongation will be, while the lower the modulus, tensile strength and hardness of the polyurethane.

In some embodiments, polyols for thermoplastic polyurethanes include, but are not limited to, one or more polyols selected from the group consisting of polyether polyols, polyester polyols, and mixtures thereof. In some specific embodiments, the thermoplastic polyurethanes comprise structural units derived from chain extenders selected from the group consisting of substantially linear polyether polyols or polyester polyols, and C ₂ -C ₁₀ glycols. Illustrative examples of C ₂ -C ₁₀ glycol chain extenders include, but are not limited to, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6 -Hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol; Hydroquinone bis- (hydroxyethyl) ether; Cyclohexylene diol (1,4-, 1,3-, and 1,2-isomers), isopropylidene bis (cyclohexanol); Diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol; Ethanolamine, N-methyl diethanolamine and the like; And mixtures of any of the above compounds. In another particular embodiment, the thermoplastic polyurethanes may comprise one or more polyoxyethylene glycols, polyoxypropylene glycols, polyoxytetramethylene glycols, copolymers of ethylene oxide and propylene oxide, polytetramethylene glycol And structural units derived from copolymers of tetrahydrofuran and ethylene oxide and / or propylene oxide. Suitable polyether polyols typically have a number average molecular weight of at least 400, preferably at least 1,250, more preferably at least 2,000, and less than 20,000, preferably less than 10,000, more preferably less than 8,000.

In another specific embodiment, the thermoplastic polyurethane is selected from polyester polyols derived from the reaction of adipic acid with at least one diol selected from the group consisting of C ₂ -C ₁₀ glycols, the illustrative examples of which are cited above. And derived structural units. Thermoplastic polyurethanes also include eta-caprolactone using initiators such as ethylene glycol, ethanolamine, and the like and ethylene glycol with polycarboxylic acids such as phthalic acid, terephthalic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, and the like. Structural units derived from polyester polyols derived from the polymerization of those prepared by esterification of polycarboxylic acid alcohols such as cole, butanediol, cyclohexanedimethanol and the like.

Typical diisocyanates used to prepare thermoplastic polyurethanes include MDI (methylene diphenyl diisocyanate) including, but not limited to, 4,4'-isomers, 2,4'-isomers and mixtures thereof. ); Hexamethylene diisocyanate, isophorone diisocyanate, methylene bis (cyclohexyl isocyanate) and 4,4'-isomer, 2,4'-isomer and mixtures thereof, and trans / trans, All geometrical isomers thereof, including the cis / trans, cis / cis and mixtures thereof, cyclohexylene diisocyanate and its 1,2-isomers, 1,3-isomers and 1,4-isomers, 1-methyl-2,5-cyclohexylene diisocyanate, 1-methyl-2,4-cyclohexylene diisocyanate, 1-methyl-2,6-cyclohexylene diisocyanate And 4,4'-isopropylidene bis (cyclohexyl isocyanate), m- and p-phenylene diisocyanate, chlorophenylene diisocyanate, alpha, alpha'-xylene dia Isocyanate, 2,4- and 2,6-toluene die Isocyanate and mixtures of these latter two isomers, tolidine diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanatodicyclohexyl, and all geometrics thereof Isomers, mixtures and the like. Also included are modified forms of MDI. In some embodiments, suitable thermoplastic polyurethanes include those having a hardness of about 60 ° Shore A to about 75 ° Shore D as measured by ASTM D2240 or ISO 868. In another embodiment, a suitable thermoplastic polyurethane has a melt flow rate of about 4 to 100 g / 10 minutes, more preferably 10 to 90 g / 10 minutes, as measured by ASTM D-1238. The thermoplastic polyurethanes optionally comprise one or more fillers such as crystalline silica or quartz or carbon black.

An adhesive layer comprising the reaction product of amine-functionalized polypropylene and polyurethane can be prepared by combining a mixture comprising amine-functionalized polypropylene and polyurethane under the conditions of direct mixing. . In certain embodiments, mixtures comprising amine-functionalized polypropylene and polyurethane may be combined in the melt using, but not limited to, extruders, kneading apparatuses, roll mills, high viscosity mixing apparatuses, and the like. In one particular embodiment, the mixture comprising the amine-functionalized polypropylene and polyurethane is supplied to the feed inlet of the extruder by feeding the amine-reactive polypropylene and amine compound to the amine-functionalized polypropylene in front of the extruder. Can be combined in a one-stage extrusion process by preparing and then optionally devolatilizing and then feeding the polyurethane to the downstream feed port. In some embodiments of the invention, an optional amine quencher may be added following the combination of the amine-functionalized polypropylene and polyurethane, for example following the optional devolatilization step. Suitable amine quenchers are well known in the art, and illustrative examples include, but are not limited to, epoxy, anhydride, acid, oxazoline and isocyanate.

Although the present invention is not limited by any theory of operation, the free amine groups on the amine-functionalized polypropylenes are urethane linkages or isocyanate end groups (eg resulting from degradation of the polyurethane) It is believed that it can react with to form polypropylene-polyurethane copolymers that act as a compatibilizer for polypropylene and polyurethane. Thus, in another embodiment of the present invention, the adhesive layer comprises a polypropylene-polyurethane copolymer. Thus, the polypropylene portion of the copolymer is compatible with the polypropylene-containing substrate and thus provides suitable adhesion between the multilayer product components. Exemplary methods of preparing blends of amine-functionalized polypropylenes and polyurethanes are described in Q. -W. Lu et al., Macromolecular Symposia, volume 198, pp. 221-232 (2003).

The adhesive layer may also optionally comprise unreacted amine-functionalized polypropylene or polyurethane or both. In another aspect of the invention, the adhesive layer comprises a fused polypropylene-polyurethane blend, wherein the fusion is provided by the reaction product of amine-functionalized polypropylene and polyurethane. Optionally, a second polypropylene that is not amine-functionalized may also be present in the adhesive layer. The second polypropylene may be combined by direct mixing with the amine-functionalized polypropylene and polyurethane during or before or after the direct mixing of the amine-functionalized polypropylene and polyurethane. . In one embodiment, the second, non-amine-functionalized polypropylene is with the amine-reactive polypropylene at the feed inlet or with the polyurethane at the downstream feed port, or with the feed inlet and downstream feed port. Can be supplied in both.

The weight / weight ratio of polyurethane to amine-functionalized polypropylene is in one embodiment from about 5:95 to about 98: 2. Within this range, the proportion of polyurethane in the adhesive layer is often greater than about 20 weight percent, preferably greater than about 30 weight percent, more preferably greater than about 40 weight percent based on the weight of the adhesive layer. . Also preferred within this range is an amount of polyurethane of up to about 90% by weight, preferably up to about 85% by weight, more preferably up to about 80% by weight, based on the weight of the adhesive layer.

When there is an optional second polypropylene that is not amine-functionalized, various polymer resins in the adhesive layer may be present in any desired weight ratio, provided that proper adhesion between the second layer and the substrate layer is obtained. The optional second polypropylene may be from about 5% to about 80% in some embodiments, from about 5% to about 45% in other embodiments, from about 10% to about 50% by weight based on the weight of the adhesive layer. It is present in the range of 30% by weight.

For use in multilayer articles, the adhesive layer comprising the reaction product of amine-functionalized polypropylene and polyurethane may be in the form of a film or sheet. In various embodiments, the thickness of the adhesive layer is from about 8 to about 2500 μm, in another embodiment from about 25 to about 2000 μm, in other embodiments from about 50 to about 1500 μm, in other embodiments from about 100 to about 1300 μm, in another embodiment. From about 500 to about 1300 μm. In some other embodiments the thickness of the adhesive layer may be about 10 to about 650 μm, in other embodiments about 25 to about 400 μm, and in still other embodiments about 50 to about 260 μm.

In some embodiments of the invention, the multilayer article comprises (i) a first adhesive layer comprising a reaction product of an amine-functionalized polypropylene and a polyurethane and (ii) optionally a thermoplastic polyurethane It may comprise a second adhesive layer. The optional second adhesive layer is in close contact with the second layer and the first adhesive layer. The thermoplastic polyurethane of the optional second adhesive layer can be any thermoplastic polyurethane known in the art that provides adhesion to a surface or layer comprising a polymer comprising a carbonate structure unit. . In certain embodiments, the thermoplastic polyurethane of the optional second adhesive layer is the same as the thermoplastic polyurethane used in the first adhesive layer.

In another aspect, the present invention provides a method of making a multilayer article comprising the layer components described herein. In some embodiments, a copolyestercarbonate / carbonate-containing polymer assembly comprising a coating layer comprising a block copolyestercarbonate and a second layer comprising a polymer comprising a carbonate structural unit comprise at least two layers. Is formed. The assembly can be prepared by known methods such as coextrusion of a film or sheet of two materials. In other embodiments, the assembly can be prepared by lamination or by solvent or melt coating. In certain embodiments, application of the coating layer to the second layer is performed in a melting process. Suitable application methods include a method of making a sheet of separate coating layer and then applying it to a second layer, and a method of making two layers simultaneously. Thus, in secondary molding, compression molding, thermoforming, co-injection molding, coextrusion, overmolding, multi-shot injection molding, sheet molding, and typically in injection molding apparatus, An exemplary method such as placing a film of coating layer material on the surface of the layer and then adhering the two layers, such as in-mold decoration, may be used. Such manipulations can be performed under conditions known in the art.

An assembly comprising a coating layer and a second layer may comprise the combined thickness of the layers. The assembly has a thickness of about 10 to about 2500 μm in some embodiments, about 10 to about 1000 μm in other embodiments, about 10 to about 500 μm in other embodiments, and about 10 to about 250 μm in another embodiment.

Multilayer articles can be formed by combining various layers, including coating layers, second layers, adhesive layers, and substrates, by methods known in the art. In one aspect, the copolyestercarbonate / carbonate-containing polymer assembly and the separate adhesive layer can be combined with the substrate layer by known methods to form a multilayer article. Known methods include, but are not limited to, lamination and compression molding. Optionally, the adhesive layer can be formed adjacent to the assembly during or after the process (eg, coextrusion) for producing a copolyestercarbonate / carbonate-containing polymer assembly, using known methods, It becomes an integral part of the film assembly which can subsequently be formed directly adjacent to the substrate layer by the use of methods such as heat and pressure, for example. Optionally, the copolyestercarbonates are used, for example, using known methods, including but not limited to direct coextrusion of the layers together to form the second layer adjacent to the adhesive film, and then, without limitation, lamination and compression molding. An assembly with a coating layer can be formed. The assembly can then be formed directly adjacent to the substrate layer using known methods. The copolyestercarbonate / carbonate-containing polymer assembly may optionally be thermoformed into a product having a suitable shape prior to molding. In various aspects, the step of forming one layer adjacent to the other layer can be performed by known methods including, but not limited to lamination and compression molding.

Applying a structure comprising a coating layer, a second layer and an adhesive layer to the substrate layer is also achieved by filling the injection mold with a structure comprising the coating layer, the second layer and the adhesive layer and then injecting the substrate thereafter. Can be. In this way, in-mold decoration and the like are possible. In one embodiment, both sides of the substrate layer may accommodate other layers, while in other embodiments they apply only to one side of the substrate layer.

Multilayer articles comprising the various layer components of the present invention typically exhibit improved initial gloss, improved initial color, improved resistance to UV radiation and retention of gloss, improved impact strength, and their final application, in addition to weather resistance. It is characterized by the conventional advantageous properties of the substrate layer, which can be demonstrated by properties such as resistance to organic solvents. Depending on factors such as the coating layer / substrate combination, the multilayer article may have a regenerating ability to make the regrind material available as a substrate for further manufacture of the inventive article. Multilayer articles often appear to have little low internal thermal stress, sometimes derived from CTE mismatches between layers. Multilayer articles may also have good environmental stability, for example thermal stability and hydrolysis stability. In an embodiment of the present invention, the multilayer article exhibits a 90 ° peel force that is higher than that observed in similar multilayer articles made of the bonding layer, or without a bonding layer composed of thermoplastic polyurethane alone. In another embodiment, the multilayer article exhibits a 90 ° peel force of at least 700 N / m. In another embodiment, the multilayer article exhibits a 90 ° peel force of at least 1750 N / m.

In some specific embodiments, the multilayer article comprises (a) preparing an assembly of a coating layer and a second layer and (b) combining the assembly with a separate adhesive layer and a substrate layer; (a) preparing an assembly of a coating layer and a second layer, (b) forming an adhesive layer adjacent to the substrate layer, and (c) combining the assembly with an adhesive layer / substrate layer combination A method comprising (ii); And (b) forming an assembly of the coating layer, the second layer, and the adhesive layer, and (b) forming the assembly adjacent to the substrate layer. do.

Multilayer articles that can be prepared, comprising the various layer components of the present invention, include products for OVAD applications; Aircraft, automobiles, trucks, military vehicles (e.g. military vehicles, aircraft and water vehicles), scooter and motorcycle panels, quarter panels, rocker panels, vertical panels, horizontal panels, Trim, pillar, center column, fender, door, deck lid, trunk lid, hood, bonnet, roof, bumper, dashboard, grille, mirror housing, pillar applique, cladding, body side molding, wheel cover External or internal components including wheelcaps, door handles, spoilers, window frames, headlamp bezels, headlights, taillights, taillight housings, taillight bezels, license plate enclosures, roof shelves and scaffoldings; Enclosures, housings, panels and components for outdoor vehicles and devices; Wind turbine blades and housings; Enclosures for electrical and telecommunication equipment; Outdoor furniture; Aircraft components; Boats and offshore equipment, including trims, enclosures, and housings; Outboard motor housings; Echo sounder housing, personal vessels; Jet-ski; pool; Spa; Hot tub; stairs; Staircase cover; Building and building supplies such as glazing, roofs, windows, floors, decorative window furnishings and processing materials; Treated glass cover for photos, pictures, posters or display items; Optical lenses; Ophthalmic lens; Corrective ophthalmic lenses; Implantable ophthalmic lenses; Wall panels and doors; Counter tops; Protected graphics; Outdoor and indoor signs; Enclosures, housings, panels, and parts for automatic teller machines (ATMs); Enclosures, housings, panels and parts for tools, including lawn and garden tractors, lawn mowers, and lawn and garden tools; Window and door trim; Sports equipment and toys; Snowmobile enclosures, housings, panels and parts; Recreational vehicle panels and components; Playground equipment; Shoelaces; Products made of plastic-wood combinations; Golf course markers; A utility pit cover; Computer housings; Desktop computer housings; Portable computer housings; Laptop computer housings; Palmtop computer housing; Monitor housings; A printer housing; keyboard; A fax machine housing; Copier housing; Telephone housing; Telephone bezels, mobile phone housings; Radio transmitter housings; Radio receiver housings; Fixed lighting; Lighting fixtures; reflector; A network interface device housing; Transformer housing; Air conditioner housings; Cladding or seating for public transport; Cladding or seating for trains, subways or buses; Instrument housing; An antenna housing; Cladding for satellite dish antennas; Coated helmets and personal protective equipment; Coated synthetic or natural fabrics; Coated photographic film and photographic prints; Coated paint products; Coated dyeing products; Coated fluorescent products; Articles such as coated foam products. The present invention further contemplates additional manufacturing operations on such products, such as but not limited to molding, in-mold decorating, roasting in paint ovens, lamination and / or thermoforming.

Without further effort, it is believed that one skilled in the art can, using the teachings herein, utilize the present invention to its fullest extent. The following examples are intended to provide those skilled in the art with additional guidance to practice the claimed invention. The examples provided are merely representative of the work contributing to the teachings herein. Accordingly, these examples are in no way intended to limit the invention as defined in the appended claims.

The sample was cut into 2.54 cm wide stripes and peeled off of the adhesive bond of the bond layer using a 90 ° peel test at a crosshead separation rate of 2.54 cm per minute using an Instron test apparatus (Model 4505). Sex was tested. Such adhesion test methods are well known to those skilled in the art and are generally described in references such as US Pat. No. 3,965,057. The test apparatus for this test procedure consisted of a series of movable rollers or supports that allowed the specimen to be peeled at a constant 90 ° angle along its entire uncut length. This device consisted of two side supports and a series of five 1.3 cm rollers geometrically fixed to the substrate. The two lower rollers were adjustable so that the device could accommodate specimens of varying thickness. Suitable top clamps were used to secure the plastic layer. The specimen was 15.2 cm in length and 2.54 cm in width. Some of the specimens were left unbound. Three or more specimens were tested for each adhesive sample. In the course of the actual test, the fixture was fixed to the moving head of the tester in a position to form a 90 ° angle to the specimen during testing of the peeled plastic layer. The specimen was placed in the fixture and the free skin was clamped stably. The clamp was then pinned to the upper head of the tester. After the specimen had no load, the weighing apparatus was equilibrated to zero. The peel load for the movement of the head with respect to the peel distance of 10.2 cm or more was prepared to be automatically recorded. Ignoring the first peel of 2.54 cm, the load needed to peel the plastic layer from the automatically recorded curve was taken. Then, the peel strength P was calculated according to the following equation:

In the examples below, the copolyestercarbonate-polycarbonate film assembly comprised a layer of copolyestercarbonate film and a layer of polycarbonate. Copolyestercarbonate films comprised copolyestercarbonates having arylate structural units derived from unsubstituted resorcinol, isophthalic acid and terephthalic acid and carbonate structural units derived from bisphenol A. The polycarbonate film included bisphenol A polycarbonate. Copolyestercarbonate-polycarbonate film assemblies were prepared by coextrusion of a 0.254 mm thick clear copolyestercarbonate film with a 0.5 mm thick colored polycarbonate layer. Maleate treated polypropylene (Fusabond MZ-109D; hereinafter referred to as PP-MA) derived from the reaction of polypropylene and maleic anhydride and comprising about 0.55% by weight anhydride structural units from Dupont Obtained. Both thermoplastic polyurethane (Avalon 70AE; hereinafter referred to as TPU) and polypropylene random copolymer (grade 13M11; hereinafter referred to as PP) comprising about 90% polypropylene structural units, Huntsman Obtained from. Diamines (primary-secondary diamines) comprising N-hexylethylenediamine were obtained from Aldrich. The base material was an ESCORENE PP8224 resin containing polypropylene structural units and was obtained from ExxonMobil.

Example 1

Functionalized polypropylene containing grafted amine groups was prepared. A mixture of PP-MA and N-hexylethylenediamine was prepared such that the molar ratio of MA to diamine was 1: 1. The mixture was extruded in a 16 mm co-rotating intermeshing twin-screw extruder with L / D = 25 at 180 ° C. and 40 rpm. The melt was extruded through a 2 mm-diameter circular die, cooled in a room temperature water bath and pelletized. Functionalized polypropylene was obtained, hereinafter referred to as PP-F1.

Example 2

A harmonized TPU / PP blend was prepared. The blend of TPU, PP and functionalized polypropylene (PP-F1) of Example 1, with a weight ratio of 70/25/5, was extruded in a twin screw extruder at 200 ° C. 70 rpm. The screw arrangement included two dough portions. The melt was extruded through a 2 mm-diameter annular die, cooled in a room temperature water bath and pelletized. A harmonized TPU / PP blend was obtained.

Example 3

Multilayer articles based on (i) copolyestercarbonate-polycarbonate film assemblies, (ii) the blended TPU / PP blend of Example 2, and (iii) the escorene polypropylene-containing substrate were prepared by compression molding. Five grams of the sample of the blended TPU / PP blend of Example 2 was compressed into a 0.18 mm thick film and cut into samples having dimensions of 6.4 cm x 12.7 cm. The escorene polypropylene-containing substrate was injection molded into a 3.2 mm thick plaque. The escorene plaque substrate was placed in a 3.2 mm thick TEFLON frame (6.4 cm x 12. cm opening) inside the compression molding press, and a TPU / PP blend film was placed on the substrate and copolyestercarbonate The polycarbonate film assembly was placed on the TPU / PP blend with the polycarbonate side adjacent to the TPU / PP blend film. The assembly was preheated at 170 ° C. for 5 minutes between heated press plates and then subjected to a pressure of 2.76 MPa for an additional 3 minutes. The press was then opened and the molded part was removed. The adhesion of the copolyestercarbonate-polycarbonate film assembly to the substrate has been found to be excellent. The 90 ° peel force was 3748 N / m. The delamination failure form was a combination of interfacial bond layer / copolyestercarbonate-polycarbonate film assembly, interfacial bond layer / substrate and adhesive substrate failure.

Comparative Example 1

For the purposes of comparison, an unmelted TPU / PP blend having a weight ratio of 70/30 was prepared by extrusion without using polypropylene functionalized under the same processing conditions as in Example 2. Multilayer articles based on (i) copolyestercarbonate-polycarbonate film assemblies, (ii) unmelted TPU / PP blends, and (iii) escorene polypropylene-containing substrates were prepared by compression molding. Five grams of sample of TPU / PP were compressed into a 0.18 mm thick film and cut into samples with dimensions of 6.4 cm x 12.7 cm. Multilayer articles of layer components were prepared using the same method described in Example 3. It has been found that the adhesion of copolyestercarbonate-polycarbonate film assemblies to an escorene substrate is very lacking. It was found that the 90 ° peel force was less than 525 N / m.

Comparative Example 2

For purposes of comparison, an unmelted TPU / PP / PP-MA blend having a weight ratio of 70/25/5 was prepared by extrusion under the same processing conditions as in Example 2. Multilayer articles based on (i) copolyestercarbonate-polycarbonate film assemblies, (ii) TPU / PP / PP-MA formulations, and (iii) escorene polypropylene-containing substrates were prepared by compression molding. Five grams of sample of TPU / PP / PP-MA were compressed into a 0.18 mm thick film and cut into plaques measuring 6.4 cm x 12.7 cm. Multilayer articles of layered components were prepared using the same method described in Example 3. It has been found that the adhesion of copolyestercarbonate-polycarbonate film assemblies to an escorene substrate is very lacking. It was found that the 90 ° peel force was less than 525 N / m.

Comparative Example 3

For the purposes of comparison, (i) copolyestercarbonate-polycarbonate film assemblies, (ii) TPU and (iii) escorene polypropylene-containing substrates were prepared by compression molding. Five grams of sample of TPU were compressed into a 0.18 mm thick film and cut into plaques measuring 6.4 cm x 12.7 cm. Multilayer articles of layered components were prepared using the same method described in Example 3. It has been found that the adhesion between the TPU and the substrate is very lacking. The product peels with a 90 ° peel force of less than 350 N / m at the interface between the TPU and the substrate.

Although the present invention has been illustrated and described in typical embodiments, it is not intended to be limited to the details given, as various modifications and substitutions are possible without departing from the spirit of the invention in any way. As such, further modifications and equivalent forms of the inventions disclosed herein may occur to those skilled in the art using only routine experimentation, and all such modifications and equivalent forms are intended to be defined by the following claims. It is believed to belong. All patents, patent applications, and publications cited herein are hereby incorporated by reference.

Claims (63)

(i) a coating layer comprising a block copolyestercarbonate comprising structural units derived from at least one 1,3-dihydroxybenzene and at least one aromatic dicarboxylic acid, and (ii) a polymer comprising a carbonate structural unit A second layer comprising (iii) a base layer comprising polypropylene and (iv) at least one adhesive layer comprising a reaction product of amine-functionalized polypropylene and polyurethane; Wherein the coating layer is in contact with the second layer and the adhesive layer is in contact with the second layer and the substrate layer. The method of claim 1, Wherein the coating layer comprises at least one 1,3-dihydroxybenzene selected from the group consisting of unsubstituted resorcinol, 2-methyl resorcinol and mixtures thereof. The method of claim 2, Multilayer article wherein 1,3-dihydroxybenzene is unsubstituted resorcinol. The method of claim 1, A multilayer article wherein the aromatic dicarboxylic acid is selected from the group consisting of isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid and mixtures thereof. The method of claim 4, wherein Multilayer article wherein the aromatic dicarboxylic acid is a mixture of isophthalic acid and terephthalic acid. The method of claim 5, Wherein the ratio of isophthalic acid-derived structural units to terephthalic acid-derived structural units is from about 0.25 to 4.0: 1. The method of claim 5, Wherein the ratio of isophthalic acid-derived structural units to terephthalic acid-derived structural units is from about 0.40 to 2.5: 1. The method of claim 1, A multilayer article of copolyestercarbonate comprising from about 10% to about 99% by weight arylate blocks. The method of claim 1, A multilayer article of copolyestercarbonate comprising from about 60% to about 98% by weight arylate blocks. The method of claim 1, A multilayer article, wherein the carbonate portion of the copolyester carbonate comprises structural units derived from bisphenol A. The method of claim 1, A multilayer article, wherein the second layer comprises bisphenol A polycarbonate. The method of claim 1, Wherein the second layer further comprises at least one colorant selected from the group consisting of dyes, pigments, metal flakes and glass flakes. The method of claim 1, A multilayer article wherein the substrate layer comprises one or more homopolypropylenes or copolymers comprising structural units derived from propylene, or combinations thereof. The method of claim 13, A multilayer article of manufacture, wherein the substrate layer comprises a copolymer comprising at least about 70% by weight of structural units derived from propylene. The method of claim 13, A multilayer article of manufacture, wherein the substrate layer comprises a copolymer comprising at least about 90% by weight of the structural units derived from propylene. The method of claim 1, A multilayer article wherein the amine-functionalized polypropylene is derived from the reaction of a polypropylene having at least one amine-reactive group and an amine compound having at least two amine groups. The method of claim 16, Multilayer article wherein the amine-reactive group comprises anhydride. The method of claim 16, A multilayer article having two amine groups, wherein both the amine compounds are primary, or one primary and one secondary. The method of claim 1, Wherein the polyurethane is a thermoplastic polyurethane comprising structural units derived from at least one polyol, at least one organic diisocyanate and at least one optional chain extender. The method of claim 19, The multilayer article of polyurethane has a hardness of about 60 ° Shore A to about 75 ° Shore D. The method of claim 19, The multilayer article of polyurethane having a melt flow rate of about 4 to 100 g / 10 minutes as measured by ASTM D-1238. The method of claim 1, Wherein the ratio of polyurethane to amine-functionalized polypropylene is from about 5:95 to about 98: 2. The method of claim 1, A multilayer article wherein the adhesive layer further comprises at least one second polypropylene that is not amine-functionalized. The method of claim 23, wherein The multilayer article of the same polypropylene in which the second polypropylene is used in the substrate layer. The method of claim 23, wherein And wherein the second polypropylene is present from about 5% to about 80% by weight based on the weight of the adhesive layer. The method of claim 1, Multi-layer products with 90 ° peel force of 700 N / m or more. The method of claim 26, Multi-layer product with 90 ° peel force of 1750 N / m or more. The method of claim 1, The multilayer article has a thickness of about 2 to 2,500 mu m for the coating layer, about 2 to 2,500 mu m for the second layer, and about 8 to 2,500 mu m for the adhesive layer. The method of claim 1, OVAD device; Aircraft, automobiles, trucks, military vehicles (military cars, military aircraft or military water vehicles), scooter or motorcycle panels, quarter panels, rocker panels, vertical panels, horizontal panels, trims, fillers, center columns, fenders, Door, Deck, Trunk Reed, Hood, Bonnet, Roof, Bumper, Fascia, Grill, Mirror Housing, Filler Applique, Cladding, Body Side Molding, Wheel Cover, Wheel Cap, Door Handle, Spoiler, Window Frame, Headlight Bezel exterior or interior components including bezels, headlights, taillights, taillight housings, taillights bezels, license plate enclosures, roof shelves or scaffoldings; Enclosures, housings, panels or parts for outdoor vehicles and devices; Wind turbine blades or housings; Enclosures for electrical or telecommunication devices; Outdoor furniture; Aircraft components; External or internal components for boat or marine equipment items including trims, enclosures or housings; Outboard motor housings; Echo sounder housing, personal vessels; Jet-ski; pool; Spa; Hot tub; stairs; Staircase cover; Building or building articles including glazing, roofs, windows, floors, decorative window furniture or processing materials; Treated glass cover for photos, pictures, posters or display items; Optical lenses; Ophthalmic lens; Corrective ophthalmic lenses; Implantable ophthalmic lenses; Wall panels or doors; Counter tops; Protected graphics; Outdoor or indoor signs; Enclosures, housings, panels or parts for automatic deposit withdrawal-preventing devices (ATMs); Enclosures, housings, panels or parts for tools, including lawn or garden tractors, lawn mowers, or lawn or garden tools; Window or door trim; Sporting equipment items or toys; Snowmobile enclosures, housings, panels or parts; Recreational vehicle panels or components; Playground equipment items; Shoelaces; Products made of plastic-wood combinations; Golf course markers; Utility pit cover; Computer housings; Desktop computer housings; Portable computer housings; Laptop computer housings; Palmtop computer housing; Monitor housings; A printer housing; keyboard; A fax machine housing; Copier housing; Telephone housing; Telephone bezel; Cell phone housings; Radio transmitter housings; Radio receiver housings; Fixed lighting; Lighting fixtures; reflector; A network interface device housing; Transformer housing; Air conditioner housings; Cladding or seating for public transport; Cladding or seating for trains, subways or buses; Instrument housing; An antenna housing; Cladding for satellite dish antennas; Coated helmets or personal protective equipment items; Coated synthetic or natural fabrics; Coated photographic film or photographic prints; Coated paint products; Coated dyeing products; Coated fluorescent products; Or a multilayer product which is a coated foam product. (i) a coating layer comprising block copolyestercarbonate comprising an unsubstituted resorcinol, a mixture of isophthalic acid and terephthalic acid, and structural units derived from bisphenol A, and (ii) optionally containing at least one colorant A second layer comprising bisphenol A polycarbonate, (iii) a base layer selected from the group consisting of homopolypropylene and copolymer comprising at least about 70% by weight of structural units derived from propylene, and (iv) amine-function An adhesive layer comprising the reaction product of cyclized polypropylene and polyurethane, Wherein the coating layer is in close contact with the second layer, the adhesive layer is in contact with the second layer and the substrate layer, and exhibits a 90 ° peel force of at least 700 N / m. (i) a coating layer comprising a block copolyestercarbonate comprising structural units derived from at least one 1,3-dihydroxybenzene and at least one aromatic dicarboxylic acid, and (ii) a polymer comprising a carbonate structural unit A film assembly comprising a second layer comprising a (iii) and an adhesive layer comprising a reaction product of an amine-functionalized polypropylene and polyurethane. The method of claim 31, wherein Block copolyestercarbonates in which the coating layer comprises an unsubstituted mixture of resorcinol, isophthalic acid and terephthalic acid and structural units derived from bisphenol A; And a second layer comprising bisphenol A polycarbonate, optionally containing one or more colorants. (i) a coating layer comprising a block copolyestercarbonate comprising structural units derived from at least one 1,3-dihydroxybenzene and at least one aromatic dicarboxylic acid, and (ii) a polymer comprising a carbonate structural unit A second layer comprising (iii) a base layer comprising polypropylene and (iv) at least one adhesive layer comprising a reaction product of amine-functionalized polypropylene and polyurethane; Wherein the coating layer is in contact with the second layer and the adhesive layer is in contact with the second layer and the substrate layer. (i) preparing a pre-assembly of the coating layer and the second layer, and (b) combining the pre-assembly with a separate adhesive layer and a substrate layer; (a) preparing a pre-assembly of the coating layer and the second layer, (b) forming an adhesive layer adjacent to the substrate layer, and (c) combining the pre-assembly with an adhesive layer / substrate layer combination (Ii) comprising the step of; And (a) preparing a pre-assembly of the coating layer, the second layer and the adhesive layer, and (b) forming a pre-assembly adjacent to the substrate layer. . The method of claim 33, wherein The assembly of the coating layer and the second layer is formed by coextrusion. The method of claim 33, wherein The formation of the assembly adjacent to the adhesive layer is carried out by lamination or compression molding. The method of claim 33, wherein And wherein the coating layer comprises at least one 1,3-dihydroxybenzene selected from the group consisting of unsubstituted resorcinol, 2-methyl resorcinol and mixtures thereof. The method of claim 33, wherein 1,3-dihydroxybenzene is unsubstituted resorcinol. The method of claim 33, wherein The aromatic dicarboxylic acid is selected from the group consisting of isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid and mixtures thereof. The method of claim 38, The aromatic dicarboxylic acid is a mixture of isophthalic acid and terephthalic acid. The method of claim 39, Wherein the ratio of isophthalic acid-derived structural units to terephthalic acid-derived structural units is about 0.25 to 4.0: 1. The method of claim 39, Wherein the ratio of isophthalic acid-derived structural units to terephthalic acid-derived structural units is about 0.40 to 2.5: 1. The method of claim 33, wherein Wherein the copolyestercarbonate comprises from about 10 wt% to about 99 wt% arylate blocks. The method of claim 33, wherein Wherein the copolyestercarbonate comprises from about 60% to about 98% by weight arylate blocks. The method of claim 33, wherein And wherein the carbonate portion of the copolyester carbonate comprises structural units derived from bisphenol A. The method of claim 33, wherein And the second layer comprises bisphenol A polycarbonate. The method of claim 33, wherein And the second layer further comprises at least one colorant selected from the group consisting of dyes, pigments, metal flakes and glass flakes. The method of claim 33, wherein Wherein the substrate layer comprises one or more homopolypropylenes or copolymers comprising structural units derived from propylene, or combinations thereof. The method of claim 47, Wherein the substrate layer comprises a copolymer comprising at least about 70% by weight of the structural units derived from propylene. The method of claim 47, Wherein the substrate layer comprises a copolymer comprising at least about 90% by weight of the structural units derived from propylene. The method of claim 33, wherein Wherein the amine-functionalized polypropylene is derived from the reaction of a polypropylene having at least one amine-reactive group and an amine compound having at least two amine groups. 51. The method of claim 50, And the amine-reactive group comprises an anhydride. 51. The method of claim 50, Wherein the amine compounds are both primary or one having two amine groups, one primary and one secondary. The method of claim 33, wherein Wherein the polyurethane is a thermoplastic polyurethane comprising structural units derived from at least one polyol, at least one organic diisocyanate, and at least one optional chain extender. The method of claim 53 wherein Wherein the polyurethane has a hardness in the range of about 60 ° Shore A to about 75 ° Shore D. The method of claim 53 wherein Wherein the polyurethane has a melt flow rate of about 4 to 100 g / 10 minutes as measured by ASTM D-1238. The method of claim 33, wherein Wherein the ratio of polyurethane to amine-functionalized polypropylene is from about 5:95 to about 98: 2. The method of claim 33, wherein And the adhesive layer further comprises at least one second polypropylene that is not amine-functionalized. The method of claim 57, The same method as the polypropylene in which the second polypropylene is used in the substrate layer. The method of claim 57, Wherein the second polypropylene is present from about 5% to about 80% by weight based on the weight of the adhesive layer. The method of claim 33, wherein Multi-layer products exhibit a 90 ° peel force of 700 N / m or more. The method of claim 60, Wherein the multilayer article exhibits a 90 ° peel force of at least 1750 N / m. The method of claim 33, wherein Wherein the thickness of the layer is about 2 to 2,500 μm, the second layer is about 2 to 2,500 μm, and the adhesive layer is about 8 to 2,500 μm. (i) a coating layer comprising a block copolyestercarbonate comprising a mixture of unsubstituted resorcinol, isophthalic acid and terephthalic acid and structural units derived from bisphenol A, (ii) optionally containing one or more colorants A second layer comprising bisphenol A polycarbonate, (iii) a base layer selected from the group consisting of homopolypropylene and copolymer comprising at least about 70% by weight of structural units derived from propylene, and (iv) amine-function An adhesive layer comprising the reaction product of cyclized polypropylene and polyurethane, Wherein the coating layer is in close contact with the second layer, the adhesive layer is in contact with the second layer and the substrate layer, and has a 90 ° peel force of 700 N / m or more. (i) preparing an assembly of a coating layer and a second layer, and (b) combining the assembly with a separate adhesive layer and a substrate layer; (a) preparing an assembly of the coating layer and the second layer, (b) forming an adhesive layer adjacent to the substrate layer, and (c) combining the assembly with an adhesive layer / substrate layer combination. Method (ii); And (a) preparing an assembly of the coating layer, the second layer and the adhesive layer, and (b) forming the assembly adjacent to the substrate layer.