Multilayer composite articles including a cap layer and a pc / abs layer and methods thereof

Abstract

Multilayer articles and methods for making the same, the multilayer articles comprising a base layer and a polyurethane and / or polyurea cover layer, the cover layer being directly bonded to the base layer. The base layer has a polymeric composition comprising two or more polymers, the two or more polymers comprising a polycarbonate component and a toughening component, wherein the toughening component comprises a styrene-acrylonitrile copolymer and an impact modifier. The base comprises 70-100 weight percent of the two or more polymers, 3-23 weight percent of the impact modifier based on the total weight of the two or more polymers, and a weight ratio of polycarbonate to toughening component of 10:90 to 55:45. The base forms a durable bond with the cover layer that remains adhered even after aging (e.g., heat, thermal cycling, UV light, visible light, humidity, weathering, or any combination thereof).

Description

[0001] This application is a divisional application of application number 201780054851.6.

[0002] priority

[0003] This application claims priority to European Patent Application No. EP 16188106.5, filed September 9, 2016, entitled “Multi-layer composite article including polyurethane layer and PC / ABS layer”, and U.S. Provisional Patent Application No. 62 / 409,636, filed October 18, 2016, each of which is incorporated herein by reference in its entirety. Technical Field

[0004] The teachings herein relate to multilayer articles comprising a cover layer (e.g., a polyurethane layer, a polyurea layer, or both) in direct contact with a base layer (e.g., a polycarbonate-containing layer). The base layer preferably comprises a blend containing polycarbonate and a toughening component. The toughening component may comprise a styrene-acrylonitrile copolymer and an impact modifier (preferably an elastomer, such as polybutadiene). The weight ratio of the polycarbonate to the toughening component is preferably less than 55:45. The multilayer articles can be used in automotive interior and / or interior and / or exterior trim components and preferably have strong adhesion between the cover layer and the base layer before and / or after aging. The cover layer is preferably molded on the surface of the base layer in a method comprising injecting a polymerizable composition into a mold to fill gaps on the surface of the base layer and polymerizing the polymerizable composition at least partially to form a polyurethane and / or a polyurea. Background Technology

[0005] Composite materials comprising a poly(methyl methacrylate) (PMMA) matrix and an overmolded polyurethane layer have been used in automotive parts. However, PMMA typically has a high density (approximately 1.18 g / cm³ for pure resin). 3 Furthermore, the PMMA base layer typically needs to be thicker to meet structural requirements (and for filled resins, the thickness is higher), and to improve the weight reduction of composite parts, efforts have recently been made to replace PMMA with polycarbonate-containing compositions.

[0006] Various polymer compositions, including polycarbonate (i.e., PC) and acrylonitrile-butadiene-styrene thermoplastic (i.e., ABS), have been used in automotive interior and / or exterior components. These PC / ABS-containing compositions can be formulated to possess the performance properties required for these applications, such as high ductility and / or impact resistance, good heat resistance, and dimensional stability. In some applications, such as those requiring durable surface properties (e.g., scratch and abrasion resistance) and / or specific aesthetic properties, PC / ABS-containing compositions are coated with a polyurethane layer. However, after aging of automotive interior and exterior components (e.g., weathering requirements), the adhesion between the substrate (e.g., PC / ABS-containing compositions) and the polyurethane layer may easily deteriorate.

[0007] Various articles comprising polyurethane layers and / or base layers (including polycarbonate and / or ABS) are described in U.S. Patent Application Publication 2011 / 0135934A1 (Published June 9, 2011 by Seidel et al.), 2005 / 0218547A1 (Published October 6, 2005 by Roche et al.), 2013 / 0196130A1 (Published August 1, 2013 by Hufen et al.), 2011 / 0027575A1 (Published February 3, 2011 by Drube et al.), U.S. Patent 6,461,732 B1 (Published October 8, 2002 by Wittmann et al.), and European Patent Application Publication EP 1736293 A1 (Published December 27, 2006), the contents of which are each incorporated herein by reference in their entirety.

[0008] U.S. Patent Application Publication 2011 / 0135934 (Seidel et al., June 9, 2011) describes a composite structure comprising a base layer containing typically high concentrations of polycarbonate, aromatic polyester carbonate, and aromatic polyester, and an overmolded polyurethane or polyurea layer. This patent application teaches the need for high concentrations of polycarbonate in the base layer and provides little or no guidance on the requirement for durable adhesion after aging.

[0009] U.S. Patent Application Publication 2013 / 0196130 A1 describes the adhesion of polyurethane to polycarbonate / ABS blend compositions, thus requiring polybutylene terephthalate or polyethylene terephthalate to achieve acceptable adhesion.

[0010] European patent application publication EP 1736293A1 describes the difficulties in adhering PC / ABS compositions to polyurethane (see, for example, paragraph 003), and the use of polyamide blends (e.g., with ABS) to improve adhesion.

[0011] U.S. Patent 6,461,732 B1 describes a composition using AlO(OH) particles (believed to be typically spherical particles with a median particle size of about 40 μm) for adhesion to thick polyurethane foam.

[0012] U.S. Patent Application Publication US2011 / 0027575 A1 describes an article comprising a polyurethane layer and a base layer, wherein a nitrogen-based foaming agent is used to mold the base layer to improve adhesion. The base layer comprises a high concentration of polycarbonate and is free of fillers (see, for example, PCS-2 in Table 1) or is substantially composed of polycarbonate, SAN copolymer, and glass fiber (see, for example, PCS-1 in Table 1).

[0013] US Patent Application Publication US 2005 / 0218547 A1 describes various composite components including a polyurethane layer, but does not mention the need for adhesion after aging (e.g., at elevated temperatures and / or humidity) and having a low linear coefficient of thermal expansion.

[0014] There remains a demand for polymer compositions (e.g., blends of PC and ABS) for use as substrates in automotive parts. In particular, such compositions are needed to also exhibit good adhesion durability. Additionally, composite articles with uniform in-mold color in the substrate layer and / or cover layer are required. Furthermore, lighter-weight components are needed by reducing thickness and / or using compositions with lower density. Improved methods for producing composite parts are also required. Additionally, composite articles comprising a substrate layer formed from a polymer composition (e.g., a PC / ABS blend) and permanently attached to an overmolded cover layer comprising polyurethane, polyurea, or both are needed. For example, articles in which strong adhesion between the layers is required even after aging (e.g., exposure to elevated temperatures, light, humidity, thermal cycling, or any combination thereof). Preferred compositions for the substrate layer are substantially or completely free of polyesters (e.g., substantially or completely free of polybutylene terephthalate and polyethylene terephthalate) and / or substantially or completely free of polyamides. Preferred compositions for use in the substrate layer are substantially or completely free of non-reinforcing fillers. Summary of the Invention

[0015] In one aspect, the teachings herein relate to polymer compositions and / or articles exhibiting good adhesion to polyurethane, said articles comprising a substrate comprising such polymer compositions as a cover layer adhered to polyurethane, polyurea, or both. The polymer composition preferably has a low density and adheres to the cover layer even after aging under high temperature, humidity, and / or light exposure, and most preferably adheres to the cover layer after a climate aging test. Preferred polymer compositions comprise a polycarbonate component and a toughening component. The toughening component comprises a styrene-acrylonitrile copolymer and an impact modifier. The toughening component may comprise, substantially comprise (e.g., about 75% by weight or more, or about 90% by weight or more, or about 95% by weight or more) or consist entirely of: one or more styrene-acrylonitrile copolymers, one or more acrylonitrile-styrene-butadiene thermoplastics (e.g., bulk ABS, emulsion ABS, grafted ABS concentrates, or combinations thereof), or any combination thereof. The weight ratio of the polycarbonate component to the toughening component is preferably about 55:45 or less, more preferably about 50:50 or less. The toughening component preferably comprises 3% to 23% by weight of an impact modifier (e.g., polybutadiene, as found in ABS). Existing PC / ABS formulations often suffer from adhesion loss of the polyurethane topcoat and / or require additional polymers that may affect various performance properties. It has now been found that a substrate formed from a combination of ABS with a specified maximum amount of polycarbonate and a specified amount of impact modifier produces improved adhesion properties (initial adhesion and adhesion after aging) when molded with a polyurethane and / or polyurea layer overcoating.

[0016] One aspect of the teachings relates to a multilayer article comprising: a base layer comprising a polymer composition; and a polyurethane and / or polyurea overlay bonded directly to the base layer. The polymer composition is preferably a blend comprising: a polycarbonate polymer and a toughening component comprising one or more styrene-containing copolymers. Optionally, the polymer composition comprises one or more reinforcing fillers (preferably fibers, such as glass fiber or wollastonite). The amount of polyester in the polymer composition is preferably less than about 5% by weight, and more preferably about 0%.

[0017] Another aspect of the teachings relates to a multilayer article comprising: i) a base layer comprising a polymer composition, wherein the polymer composition is a blend comprising two or more polymers, the polymers comprising a polycarbonate component and a toughening component, wherein the toughening component comprises a styrene-acrylonitrile copolymer and an impact modifier; and ii) a cover layer comprising polyurethane and / or polyurea, the cover layer being directly bonded to the base layer; wherein the concentration of the two or more polymers is based on the total weight of the polymer composition, about 70% by weight or higher (preferably about 83% by weight or higher, and more preferably about 88% by weight or higher) and about 100% by weight or lower (preferably about 99% by weight or lower). The total weight of the polycarbonate component and the toughening component is preferably based on about 75% by weight to about 100% by weight of the total weight of the two or more polymers in the polymer composition. The weight ratio of the polycarbonate component to the toughening component is preferably about 10:90 or higher (preferably about 20:80 or higher, and more preferably about 25:75 or higher) and about 55:45 or lower (preferably about 50:50 or lower, and more preferably about 45:55 or lower). The concentration of the impact modifier can be based on the total weight of the two or more polymers, about 3% by weight or higher (preferably about 5% by weight or higher, and more preferably about 7% by weight or higher) and about 23% by weight or lower (preferably about 18% by weight or lower, more preferably about 15% by weight or lower, and most preferably about 13% by weight or lower).

[0018] Another aspect of the invention relates to a method for producing composite articles, such as those taught herein. Preferably, the method may include the steps of: i) creating a gap in a mold cavity on the surface of a substrate layer having a surface, wherein the substrate layer comprises a polycarbonate having a glass transition temperature; ii) injecting a polymerizable composition into the mold cavity to form a polyurethane and / or a polyurea; iii) contacting the surface with the polymerizable composition, wherein the surface has a temperature below the glass transition temperature; and iv) polymerizing the polyurethane and / or polyurea at least partially when the mold cavity is closed. Preferably, the base layer comprises a polymer composition, which is a blend comprising two or more polymers, the polymers comprising polycarbonate and a toughening component, wherein the toughening component comprises a styrene-acrylonitrile copolymer and an impact modifier; wherein the concentration of the two or more polymers is based on the total weight of the polymer composition, about 70% by weight or higher (preferably about 83% by weight or higher, and more preferably about 88% by weight or higher) and about 100% by weight or lower (preferably about 99% by weight or lower), and the total weight of the polycarbonate and the toughening component is based on the weight of the two or more polymers in the polymer composition. The total weight is approximately 75% to approximately 100% by weight, and the weight ratio of the polycarbonate to the toughening component is approximately 10:90 or higher (preferably approximately 20:80 or higher, and more preferably approximately 25:75 or higher) and approximately 55:45 or lower (preferably approximately 50:50 or lower, and more preferably approximately 45:55 or lower), and the concentration of the impact modifier is based on the total weight of the two or more polymers, approximately 3% by weight or higher (preferably approximately 5% by weight or higher, and more preferably approximately 7% by weight or higher) and approximately 23% by weight or lower (preferably approximately 18% by weight or lower, more preferably approximately 15% by weight or lower, and most preferably approximately 13% by weight or lower). The method preferably includes the step of forming a base layer (e.g., molding a base layer). The method preferably includes the step of forming a cover layer on the base layer (e.g., molding a cover layer). The method preferably includes the step of polymerizing and / or crosslinking the cover layer on the base layer.

[0019] The features of the various aspects taught herein may further be found in one or any combination of the following features: the amount of polyester in the polymer composition is about 0 or less than about 5% by weight; the impact modifier is present in an amount of 25 to 85% by weight (preferably 45 to 75% by weight and more preferably 55 to 75% by weight) based on the total weight of the toughening component; the impact modifier is polybutadiene rubber; the toughening component comprises bulk ABS; the toughening component comprises a grafted ABS impact modifier; the ABS impact modifier contains (about 45% by weight or more, more preferably about 55% by weight or more) polybutadiene; the ABS impact modifier contains about 85% by weight or less (preferably about 75% by weight or less) polybutadiene based on the total weight of the grafted ABS impact modifier; the polymer composition The polymer composition comprises, based on the total weight of the polymer composition, about 20% by weight or more (preferably about 25% by weight or more, more preferably about 30% by weight or more; and most preferably about 35% by weight or more) of a polycarbonate component; the polymer composition comprises about 70% by weight or less (preferably about 55% by weight or less, more preferably about 50% by weight or less, and even more preferably about 45% by weight or less) of a polycarbonate composition; the polymer composition comprises ABS thermoplastic (i.e., acrylonitrile-butadiene-styrene thermoplastic). The ABS thermoplastic comprises a polybutadiene-containing phase dispersed in a styrene-containing phase (comprising a styrene-acrylonitrile copolymer); the styrene-acrylonitrile copolymer comprises about 60% by weight or more styrene (and preferably about 82% by weight or less styrene) and about 15% by weight or more acrylonitrile (and preferably about 33% by weight or less acrylonitrile) based on the total weight of the acrylonitrile-styrene copolymer; the styrene-acrylonitrile copolymer is a random copolymer, which is substantially composed of (e.g., about 90% by weight or more, about 95% by weight or more, about 97% by weight or more, or about 99% by weight or more, and preferably entirely composed of) acrylonitrile and styrene; the impact modifier is grafted onto the styrene-acrylonitrile copolymer; the polymer composition comprises about 3% by weight to about 30% by weight (preferably about 5% by weight to about 23% by weight, and most preferably about 7% by weight to about 15% by weight) of reinforcing filler based on the total weight of the polymer composition; the reinforcing filler comprises glass fiber, wollastonite, or both; the base layer has about 0.3 The thickness is from about 1 mm to about 10 mm (preferably from about 0.5 mm to about 5 mm); the covering layer has a thickness of about 0.2 mm to about 1.5 mm (preferably from about 0.3 mm to about 1.0 mm and more preferably from about 0.3 mm to about 0.5 mm).The polymer composition has a thickness of 8 mm; the amount of any talc in the polymer composition is about 2% by weight or less (preferably about 1% by weight or less, and more preferably the polymer composition is talc-free); the cover layer is a dense layer having a porosity of about 20% by volume or less (preferably about 10% by volume or less, more preferably about 5% by volume or less, and most preferably about 2% by volume or less); the base layer includes an in-mold colorant; the cover layer includes an in-mold colorant; the polymer composition contains about 0.2 to about 9% by weight (preferably about 1 to about 7% by weight, even more preferably about 1.5 to about 5% by weight, and most preferably about 2 to about 4% by weight) of one or more ethylene copolymers; the ethylene copolymers contain functionalized monomers; the base layer is colored by pigments or other colorants; the cover layer is substantially clear and / or substantially transparent; the total amount of the filler (preferably wollastonite), toughening components (preferably bulk ABS and any other styrene-acrylonitrile copolymers) and polycarbonate in the base layer is based on the total weight of the base layer. The substrate comprises approximately 95% by weight or more; the weight ratio of the polycarbonate component to the toughening component is approximately 55:45 or less (preferably approximately 50:50 or less, and most preferably approximately 45:55 or less); the substrate is a dense substrate (e.g., with a porosity of approximately 10% by volume or less, preferably 5% by volume or less); the amount of toughening components other than bulk ABS is preferably less than 60% by weight (more preferably less than 40% by weight, even more preferably less than 25% by weight, based on the total weight of the toughening components); the substrate is formed without a foaming agent; the amount of any styrene copolymer (containing maleic anhydride, maleic acid, or other monomers that provide carboxyl groups to the copolymer) in the substrate is approximately 0.9% by weight or less (based on the total weight of the polymer composition, or based on the total weight of the substrate); the substrate comprises one or more additives selected from: antioxidants, processing aids, light stabilizers, heat stabilizers, release agents, and flow modifiers; the wollastonite is coated wollastonite; or the wollastonite comprises an organic sizing agent. . Attached Figure Description

[0020] Figure 1A This is an illustrative cross-sectional view of a composite material article 10 including a base layer 20 and a cover layer 30. The interface between the base layer and the cover layer may be generally planar, such as... Figure 1A As shown in the image.

[0021] Figure 1B This is an illustrative cross-sectional view of a composite article 10' including a base layer 20' and a cover layer 30'. The interface between the base layer and the cover layer may be curved, such as... Figure 1B As shown in the image.

[0022] Figure 2These are illustrative optical micrographs of needle-like fillers as taught in this article. Detailed Implementation

[0023] The explanations and descriptions presented herein are intended to familiarize others skilled in the art with the invention, its principles, and its practical applications. Those skilled in the art may adapt and apply the invention in various forms, which may be best suited to the requirements of a particular application. Therefore, the specific embodiments of the invention set forth are not intended to be exhaustive or limiting of the teachings. The scope of the teachings should therefore not be determined by reference to the foregoing description, but rather by reference to the appended claims together with their equivalents. All publications and references (including patent applications and publications) are incorporated herein by reference for all purposes. Other combinations that may be obtained from the following claims are also hereby incorporated by reference in this written description.

[0024] Polymer compositions comprising polycarbonate and toughening components including rubber-modified monovinyl aromatic thermoplastics achieve the need for a base layer that exhibits good adhesion (including durable adhesion) to the cover layer and possesses one or more of the properties described herein. Such compositions preferably provide high stiffness, a low coefficient of linear thermal expansion (i.e., CLTE), and maintain good adhesion to polyurethane or polyurea after aging (e.g., after climate aging). The polymer compositions can be used in composite materials comprising a base layer that is in direct contact with and bonded to the cover layer, the cover layer comprising polyurethane, polyurea, or both. The polymer composition of the base layer preferably comprises a specified amount of polycarbonate and a specified amount of impact modifier.

[0025] Preferably, the initial adhesion between the base layer and the cover layer is about 2.5 MPa or higher, more preferably about 3.0 MPa or higher, even more preferably about 3.5 MPa or higher, even more preferably about 4.0 MPa or higher, and most preferably about 4.2 MPa or higher (e.g., as measured using a PosiTest® AT-A automated adhesion tester as described herein). Preferably, the adhesion between the base layer and the cover layer is durable even after exposure to accelerated aging, such as short thermal cycling (Volkswagen PV1200 aging test, 8 cycles unless otherwise specified), thermo-photo-aging test (VDA 75202, 4 cycles of exposure using type 3 conditions unless otherwise specified), thermo-oxidative aging (240 hours at 120°C unless otherwise specified), solar simulation test (DIN 75220 indoor 1T, 240 hours at about 42°C and less than about 30% relative humidity unless otherwise specified), hydrolysis test (based on DBL 7384-8.1.18, about 72 hours at about 90°C and at least 87% relative humidity unless otherwise specified) or any combination thereof. Upon exposure to this accelerated aging, the adhesion between the base layer and the capping layer is preferably about 2.3 MPa or higher, more preferably about 2.7 MPa or higher, even more preferably about 3.1 MPa or higher, even more preferably about 3.5 MPa or higher, and most preferably about 3.7 MPa or higher. For example, the adhesion between the capping layer and the base layer may initially be about 4 MPa or higher, and may be about 3.5 MPa or higher after a short thermal cycle, after a thermo-photo-aging test, after a thermo-oxidative aging test, after a solar simulation test, after a hydrolysis test, or any combination thereof.

[0026] basal layer

[0027] The base layer comprises, is substantially composed of, or is entirely composed of the polymer composition as taught herein. Preferably, some or all of the surface of the base layer in contact with the cover layer is formed of the polymer composition.

[0028] polymer composition

[0029] The base layer is formed of and / or comprises a polymer composition containing a variety of polymers. Optionally, the polymer composition contains one or more fillers. The combination of materials is selected such that the base layer provides the article with the necessary overall properties (such as strength, impact resistance, low linear coefficient of thermal expansion, or any combination thereof) while maintaining adhesion to the cover layer even after aging.

[0030] polycarbonate

[0031] The polycarbonate is preferably an aromatic polycarbonate. Such aromatic polycarbonates may include or consist substantially of the aromatic polycarbonates described in the following: U.S. Patent Application Publication 2013 / 0196130 A1 (Hufen et al., published August 1, 2013, see, for example, paragraphs 0025 to 0053) and 2011 / 0129631 A1 (Van Nuffel, published June 2, 2011, see, for example, paragraphs 0035 to 0058); and International Patent Application Publication WO2011 / 107273 (Van Nuffel et al., see, for example, page 5, lines 21 to 9, line 23), each of which is incorporated herein by reference in its entirety.

[0032] Suitable aromatic polycarbonates according to the teachings herein may be known from the literature or may be produced by methods known from the literature (e.g., for the production of aromatic polycarbonates, see Schnell, “Chemistry and Physics of Polycarbonates”, Interscience Publishers, 1964, and U.S. Patent Nos. 3,028,365; 4,529,791; and 4,677,162; which are hereby incorporated herein by reference in their entirety).

[0033] Aromatic polycarbonates are produced, for example, by reacting bisphenol with a carbonate halide (preferably phosgene) and / or with an aromatic dicarboxylic acid dihalide (preferably a benzene dicarboxylic acid dihalide), by a phase boundary process, optionally using a chain terminator (e.g., monophenol) and optionally using a trifunctional branching agent or a branching agent with a functionality greater than 3 (e.g., triphenol or tetraphenol).

[0034] The bisphenols used to produce aromatic polycarbonates and / or aromatic polyester carbonates are preferably those of formula I:

[0035] Formula I

[0036] Where A represents a single bond, C1-C5 alkylene, C2-C5 subalkyl, C5-C6 cycloalkyl, —O—, —SO—, —CO—, —S—, —SO2—, or C6-C 12 arylene, which may be condensed with other aromatic rings optionally containing heteroatoms; or groups of formula II or III.

[0037] Formula II

[0038] Formula III

[0039] B is independently hydrogen, C1-C in each case. 12 Alkyl (preferably methyl) or halogen (preferably chlorine and / or bromine);

[0040] x is 0, 1, or 2 independently in each case;

[0041] p is 0 or 1;

[0042] R c and R d They are independent of each other, and for each X 1 It can be selected individually and is either hydrogen or C1-C6 alkyl, preferably hydrogen, methyl or ethyl;

[0043] X 1 It represents carbon; and

[0044] m represents an integer from 4 to 7, preferably 4 or 5, provided that R c and R d Simultaneously represents at least one X 1 Alkyl group on an atom.

[0045] Preferred bisphenols include hydroquinone, resorcinol, dihydroxybiphenyl, bis(hydroxyphenyl)-C1-C5 alkanes, bis(hydroxyphenyl)-C5-C6 cycloalkanes, bis(hydroxyphenyl) ethers, bis(hydroxyphenyl) sulfoxides, bis(hydroxyphenyl) ketones, bis(hydroxyphenyl) sulfones, and α,α'-bis(hydroxyphenyl)diisopropylbenzene, as well as their derivatives having brominated and / or chlorinated nuclei.

[0046] Particularly preferred bisphenols are 4,4'-dihydroxybiphenyl, bisphenol A, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,1-bis(4-hydroxyphenyl)-cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4-dihydroxydiphenyl sulfone, and 4,4-dihydroxydiphenyl sulfone, as well as their dibrominated, tetrabrominated, or chlorinated derivatives, such as 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)propane, or 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane. 2,2-bis-(4-hydroxyphenyl)propane (bisphenol A) is particularly preferred. Bisphenols can be used alone or as any mixture. Bisphenols are known from the literature or can be obtained by methods known from the literature.

[0047] Examples of suitable chain terminators for producing aromatic polycarbonates include phenol, p-chlorophenol, p-tert-butylphenol, or 2,4,6-tribromophenol, as well as long-chain alkylphenols such as 4-(1,3-dimethyl-butyl)phenol or monoalkylphenols or dialkylphenols (containing a total of 8 to 20 C atoms in their alkyl substituents), such as 3,5-di-tert-butylphenol, p-iso-octylphenol, p-tert-octylphenol, p-dodecylphenol, 2-(3,5-dimethylheptyl)phenol, and 4-(3,5-dimethylheptyl)phenol. The amount of chain terminator used relative to the total molar amount of the bisphenols used in each case is typically between 0.1 mol% and 10 mol%.

[0048] Aromatic polycarbonates preferably have a weight-average molecular weight of about 10,000 or higher, more preferably about 15,000 or higher, even more preferably about 20,000 or higher, and most preferably about 22,000 or higher. Aromatic polycarbonates preferably have a weight-average molecular weight of about 200,000 or lower, more preferably about 100,000 or lower, and most preferably about 50,000 or lower. For example, the weight-average molecular weight can be about 10,000 to about 200,000 or about 20,000 to about 80,000. Unless otherwise stated, references to “molecular weight” in this document for aromatic polycarbonates and / or aromatic polyester carbonates refer to the weight-average molecular weight (Mw) determined by gel permeation chromatography (GPC) using laser scattering with bisphenol A polycarbonate standards, and are given in grams per mole (g / mol).

[0049] Aromatic polycarbonates can be linear or branched. Branched polycarbonates can be branched in known ways, for example by incorporating 0.05 to 2.0 mol% of a trifunctional compound or a compound with a functionality greater than 3 (e.g., those containing three or more phenolic groups) relative to the total amount of bisphenols used. Branched polycarbonates suitable for use in this invention can be prepared by known techniques, such as several suitable methods disclosed in U.S. Patent Nos. 3,028,365; 4,529,791; and 4,677,162, which are hereby incorporated herein by reference in their entirety.

[0050] Suitable branching agents that can be used are, for example, trifunctional or polyfunctional carboxylic acid chlorides in amounts of 0.01 to 1.0 mol% (relative to the dicarboxylic acid dichloride used), such as pyromellitic acid trichloride, cyanuric acid trichloride, 3,3′-,4,4′-benzophenone tetracarboxylic acid tetrachloride, 1,4,5,8-naphthalene-tetracarboxylic acid tetrachloride, or pyromellitic acid tetrachloride; or trifunctional or polyfunctional phenols in amounts of 0.01 to 1.0 mol% relative to the diphenol used, such as phloroglucinol, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)-2-heptene, 4,4-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3 5-Tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, tris(4-hydroxyphenyl)-phenyl-methane, 2,2-bis[4,4-bis(4-hydroxyphenyl)cyclohexyl]-propane, 2,4-bis[1-(4-hydroxyphenyl)-1-methylethyl]phenol, tetra(4-hydroxyphenyl)-methane, 2,6-bis(2-hydroxy-5-methyl-benzyl)-4-methyl-phenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)propane, or tetra(4-[1-(4-hydroxyphenyl)-1-methylethyl]-phenoxy)-methane. Phenolic branching agents can be placed in the reaction vessel together with bisphenols. Acyl chloride branching agents can be introduced together with acyl chlorides.

[0051] Both homopolymers and copolymers are suitable. For the production of the copolymer according to component (i) of the invention, 1 to 25 parts by weight, preferably 2.5 to 25 parts by weight (relative to the total amount of bisphenol to be used), of a polydiorganosiloxane containing hydroxyl-aryloxy terminal groups can also be used. These are known (see, for example, U.S. Patent No. 3,419,634) or can be produced by methods known from the literature.

[0052] In addition to bisphenol A homopolymer polycarbonate, the preferred polycarbonate is a copolymer polycarbonate of bisphenol A and other bisphenols with a molar total of up to 15 mol% relative to the bisphenols, wherein the bisphenols are listed as preferred or particularly preferred, especially 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane.

[0053] The relative solution viscosity (η) of aromatic polycarbonates rel Preferably, it is in the range of 1.18 to 1.4, more preferably 1.22 to 1.3 (as measured at 25°C in a solution of 0.5 g polycarbonate and polyester carbonate in 100 mL of dichloromethane).

[0054] toughening components

[0055] The toughening component includes a monovinyl aromatic copolymer (e.g., a styrene-containing copolymer) and an impact modifier. For example, the toughening component may include a rubber-modified monovinyl aromatic thermoplastic (e.g., ABS plastic).

[0056] The polymer composition used as the substrate typically comprises one or more monovinyl aromatic copolymers. The monovinyl aromatic copolymer can be any such copolymer described herein, and preferably comprises a first monomer of styrene and a second monomer of acrylonitrile. Preferably, some or all of the monovinyl aromatic copolymers are included in one or more rubber-modified monovinyl aromatic thermoplastics. The substrate composition comprises one or more rubber-modified monovinyl aromatic thermoplastics.

[0057] Examples of rubber-modified monovinylamine aromatic thermoplastics include those described in U.S. Patent Application Publication 2011 / 0040035 A1 (Shields et al., published February 17, 2011, see, for example, paragraphs 0048-0087), US 2007 / 106028 A1 (Maes et al., published May 10, 2007, see, for example, paragraphs 0010-0064), and International Patent Application Publication WO 2011 / 107273 (see, for example, page 10, lines 5-14, line 30, Van Nuffel et al., published September 9, 2011, claiming priority to US 61 / 309,634), each of which is incorporated herein by reference in its entirety.

[0058] Rubber-modified monovinyl aromatic thermoplastics used in polymer compositions typically comprise a monovinyl aromatic and olefinically unsaturated nitrile copolymer in a matrix or continuous phase, and rubber particles dispersed in said matrix. The matrix or continuous phase of the present invention is a copolymer comprising a monovinyl aromatic monomer and an olefinically unsaturated nitrile monomer polymerized therein, or a copolymer comprising a monovinyl aromatic monomer, an olefinically unsaturated nitrile monomer, and one or more vinyl monomers copolymerizable therewith. As used herein, a copolymer is defined as a polymer having two or more monomers polymerized with each other. These compositions are often referred to as SAN-type or SAN because poly(styrene-acrylonitrile) is the most common example.

[0059] Various techniques suitable for producing rubber-modified monovinylene aromatic thermoplastics are well known in the art. Examples of these known polymerization methods include bulk polymerization, bulk-solution polymerization, or bulk-suspension polymerization, commonly referred to as bulk polymerization. For a detailed discussion of how to prepare rubber-modified monovinylene aromatic thermoplastics, see “Modern Styrenic Polymers” of Series In Polymer Science (Wiley), edited by John Scheirs and Duane Priddy, ISBN 0 471 497525. Furthermore, U.S. Patent Nos. 3,660,535; 3,243,481; and 4,239,863, for example, are incorporated herein by reference.

[0060] Continuous bulk polymerization techniques are generally advantageously used to prepare the rubber-modified monovinylene aromatic thermoplastics of the present invention. Preferably, polymerization is carried out in one or more substantially linear stratified flow or so-called “plug flow” reactors (as described in U.S. Patent No. 2,727,884, sometimes referred to as multi-zone plug flow bulk methods, which may or may not include recycling of a portion of the polymerized product), or alternatively in stirred tank reactors in which the contents of the reactor are substantially completely homogeneous, typically used in combination with one or more plug flow reactors. Alternatively, parallel reactor configurations, as taught in EP 412801, may also be suitable for preparing the rubber-modified monovinylene aromatic thermoplastics of the present invention.

[0061] Multi-zone plug flow bulk polymerization involves a series of polymerization vessels (or towers) continuously connected to each other, providing multiple reaction zones. A rubber, such as butadiene rubber (stereospecific), is dissolved in a mixture of monovinyl aromatic comonomers, such as styrene (ST) and acrylonitrile (AN), and then the rubber solution is added to the reaction system. Polymerization can be thermally or chemically initiated, and the viscosity of the reaction mixture will gradually increase. During the reaction, the rubber will graft with the ST / AN polymer (grafted SAN), and bulk SAN (also called free SAN, matrix SAN, or ungrafted SAN) will also form in the rubber solution. When the free SAN (i.e., ungrafted SAN) can no longer "remain" as a single continuous "phase" in the rubber solution, it begins to form domains of the SAN phase. The polymerization mixture is now a two-phase system. As polymerization proceeds, more and more free SAN is formed, and the rubber phase itself begins to disperse as particles (rubber domains) within the matrix of the continuously growing free SAN. Eventually, the free SAN becomes the continuous phase. This is essentially the formation of an oil-in-oil emulsion system. Some matrix SAN is also enclosed within the rubber particles. This stage is typically referred to as phase transformation. Before phase transformation, rubber is a continuous phase and no rubber particles have formed; after phase transformation, essentially all rubber phases have been transformed into rubber particles and a continuous SAN phase exists. Following phase transformation, more matrix SAN (free SAN) is formed, and possibly, the rubber particles acquire more grafted SAN.

[0062] Monovinylene aromatic monomers include, but are not limited to, those described in U.S. Patent Nos. 4,666,987; 4,572,819 and 4,585,825, which are incorporated herein by reference. Preferably, the monomer has the following formula:

[0063]

[0064] Wherein R' is hydrogen or methyl, and Ar is an aromatic ring structure having 1 to 3 aromatic rings with or without alkyl, halogen, or haloalkyl substitution, wherein any alkyl group contains 1 to 6 carbon atoms and haloalkyl refers to a halosubstituted alkyl group. Preferably, Ar is phenyl or alkylphenyl, wherein alkylphenyl refers to an alkyl-substituted phenyl group, most preferably phenyl. Preferred monovinylene aromatic monomers include: all isomers of styrene, α-methylstyrene, vinyltoluene, especially p-vinyltoluene, ethylstyrene, propylstyrene, vinylbiphenyl, vinylnaphthalene, vinylanthracene, etc., and mixtures thereof.

[0065] Typically, this monovinylene aromatic monomer will be present in an amount equal to or greater than about 50% by weight, preferably equal to or greater than about 60% by weight, more preferably equal to or greater than about 65% by weight, and most preferably equal to or greater than about 70% by weight, based on the total weight of the matrix copolymer. Typically, this monovinylene aromatic monomer will be present in an amount less than or equal to about 95% by weight, preferably less than or equal to about 85% by weight, more preferably less than or equal to about 80% by weight, and most preferably less than or equal to about 75% by weight, based on the total weight of the matrix copolymer.

[0066] Unsaturated nitrile materials include, but are not limited to, acrylonitrile, methacrylonitrile, ethyl acrylonitrile, fumaronitrile, and mixtures thereof. Unsaturated nitrile materials are typically used in matrix copolymers in an amount equal to or greater than about 5% by weight, preferably equal to or greater than about 10% by weight, more preferably equal to or greater than about 15% by weight, and most preferably equal to or greater than about 20% by weight, based on the total weight of the matrix copolymer. Unsaturated nitrile materials are typically used in matrix copolymers in an amount less than or equal to about 50% by weight, preferably equal to or less than about 45% by weight, more preferably less than or equal to about 35% by weight, and most preferably less than or equal to about 30% by weight, based on the total weight of the matrix copolymer.

[0067] Other vinyl monomers may also be included in the matrix copolymer in polymeric form, including conjugated 1,3-dienes (e.g., butadiene, isoprene, etc.); α- or β-unsaturated monocarboxylic acids and their derivatives (e.g., acrylic acid, methacrylic acid, etc., and their corresponding esters, such as methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, methyl methacrylate, etc.); vinyl halides, such as vinyl chloride, vinyl bromide, etc.; vinylidene chloride, vinylidene chloride, etc.; vinyl esters, such as vinyl acetate, vinyl propionate, etc.; olefinic unsaturated dicarboxylic acids and their anhydrides and derivatives, such as maleic acid, fumaric acid, maleic anhydride, dialkyl maleate or fumarate, such as dimethyl maleate, diethyl maleate, dibutyl maleate, the corresponding fumarate, N-phenylmaleimide (NPMI), etc.; and the like. These additional comonomers can be incorporated into the composition in several ways, including by interpolymerizing with monovinyl aromatic and olefinically unsaturated nitrile matrix copolymers and / or polymerizing into polymeric components, which can be combined, for example, blended into the matrix. If present, the amount of such comonomers will generally be equal to or less than about 20% by weight, more preferably equal to or less than about 10% by weight, and most preferably less than or equal to about 5% by weight, based on the total weight of the matrix copolymer. The matrix copolymer is preferably substantially free of or even completely free of maleic anhydride and carboxylic acid groups (e.g., the amount of maleic anhydride, maleic acid, or other monomers that generate carboxylic acid groups is preferably about 4% by weight or less, more preferably about 0.9% by weight or less, even more preferably about 0.25% by weight or less, and most preferably about 0% by weight, based on the total weight of the styrene copolymer).

[0068] The matrix copolymer is present in an amount equal to or greater than about 60% by weight of the rubber-modified monovinylamine aromatic thermoplastic, preferably equal to or greater than about 70% by weight, more preferably equal to or greater than about 75% by weight, even more preferably equal to or greater than about 80% by weight, and most preferably equal to or greater than about 82% by weight. The matrix copolymer is present in an amount equal to or less than about 90.5% by weight of the rubber-modified monovinylamine aromatic thermoplastic, preferably equal to or less than about 90% by weight, more preferably equal to or less than about 89% by weight, and most preferably equal to or less than about 88% by weight.

[0069] Various types of rubber are suitable for use in this invention. Rubbers include diene rubber, ethylene propylene rubber, ethylene propylene diene (EPDM) rubber, ethylene copolymer rubber, acrylate rubber, polyisoprene rubber, halogenated rubber, and mixtures thereof. Interpolymers of rubber forming monomers with other copolymerizable monomers are also suitable.

[0070] Preferred rubbers are diene rubbers, such as polybutadiene, polyisoprene, polypentadiene, polychloroprene, etc., or mixtures of diene rubbers, i.e., any rubbery polymer of one or more conjugated 1,3-dienes, particularly preferably 1,3-butadiene. Such rubbers include homopolymers and copolymers of 1,3-butadiene with one or more copolymerizable monomers, such as the monovinylene aromatic monomers described above, preferably styrene. Preferred 1,3-butadiene copolymers are based on the weight of the 1,3-butadiene copolymer, comprising at least about 30% by weight of 1,3-butadiene rubber, more preferably about 50% by weight, even more preferably about 70% by weight, and most preferably about 90% by weight of 1,3-butadiene rubber, and at most about 70% by weight of monovinylene aromatic monomers, more preferably at most about 50% by weight, even more preferably at most about 30% by weight, and most preferably at most about 10% by weight of monovinylene aromatic monomers in a block or cone block rubber configuration.

[0071] filler

[0072] The polymer composition may be substantially free of fillers or completely free of fillers, so as to generally maintain the low density of the selected polymer. For example, the filler concentration may be about 20% by weight or less, about 15% by weight or less, about 10% by weight or less, or about 3% by weight or less.

[0073] If used, the filler preferably comprises or is substantially composed of reinforcing filler, such as fibers with a length-to-diameter ratio of about 4 or greater. The amount of other fillers (e.g., non-reinforcing fillers, such as talc, clay, etc.) is preferably based on the total weight of the polymer composition, about 6% by weight or less, about 4% by weight or less, about 2% by weight or less, or about 1% by weight or less.

[0074] Reinforcing fillers can be used to improve the strength of the polymer composition and / or reduce the linear coefficient of thermal expansion of the composition.

[0075] The reinforcing filler may include glass fiber, carbon fiber, metal fiber, or any combination thereof. Other reinforcing fillers include mineral fillers with a needle-like shape, such as wollastonite.

[0076] The reinforcing filler may include one or more needle-like fillers. Preferred fillers are elongated particles with an aspect ratio (e.g., length-to-diameter ratio) of about 2 or higher, more preferably about 3 or higher, even more preferably about 4 or higher, and most preferably about 6 or higher. The aspect ratio of the filler may be about 1000 or lower, about 40 or lower, about 30 or lower, about 20 or lower, or about 15 or lower. Particularly preferred needle-like fillers are needle-like wollastonite. Wollastonite is calcium metasilicate (i.e., CaSiO3). Preferred wollastonite is essentially composed of CaSiO3. The amount of any impurities (e.g., the total amount of oxides other than calcium and silicon) is preferably about 10% by weight or less, more preferably about 7% by weight or less, even more preferably about 5% by weight or less, and most preferably about 3% by weight or less.

[0077] Based on the total weight of the filler, the amount of any Mg in the filler is preferably about 1% by weight or less, more preferably about 0.5% by weight or less, and most preferably about 0.2% by weight or less.

[0078] The filler may be treated or untreated. For example, the filler may include a sizing agent for improving the adhesion of the filler to one or more polymers of the thermoplastic composition. Preferred wollastonite includes a sizing agent.

[0079] The needle-like filler preferably has a hardness of about 3 Mohs or higher, more preferably about 3.5 Mohs or higher, and most preferably about 4 Mohs or higher. The filler preferably has a hardness of about 8 Mohs or lower, more preferably about 6 Mohs or lower, and most preferably about 5 Mohs or lower. The needle-like filler (e.g., wollastonite) may have one or any combination of the following characteristics: a specific gravity of about 2.5 to about 3.5 (preferably about 2.7 to about 3.1, more preferably about 2.90 g / cm³). 3The wollastonite comprises, for example, a median length of about 25 µm to about 150 µm (e.g., about 40 µm to about 75 µm, preferably about 50 µm or about 63 µm); a median diameter of about 1 to about 20 µm, preferably about 2 to about 10 µm and more preferably about 4 µm to about 8 µm); a percentage of particles with a diameter of about 2.0 µm to about 20 µm of about 50% or more (e.g., about 70% or more, or about 80% to about 100%); a specific surface area of ​​about 0.5 m² / g to about 10 m² / g (e.g., about 2.9 m² / g, as measured by BET); a pH of about 7 to about 13 in a 10% slurry (e.g., about 9.9); or any combination thereof. Preferred wollastonite comprises (e.g., about 80% or more, or about 90% or more, or about 95% or more) calcium metasilicate (i.e., CaSiO3).

[0080] Examples of usable fillers include NYGLOS® 4W and NYGLOS® 4W10992 wollastonite, commercially available from NYCO MINERALS. NYGLOS® 4W has a specific gravity of approximately 2.90 g / cm³. 3 The median length is approximately 63 µm; the median diameter is approximately 4 μm to approximately 8 μm; the percentage of particles with a diameter of approximately 2.0 μm to approximately 20 μm is approximately 80% to approximately 100%; the specific surface area is approximately 2.9 m² / g, as measured by BET; the pH in a 10% slurry is approximately 9.9; and the hardness (Mohs) is approximately 4.5. This wollastonite contains approximately 95% or more calcium metasilicate (i.e., CaSiO3). The aspect ratio of NYGLOS® 4W is approximately 11:1. Based on the total weight of the wollastonite, the amount of Mg is approximately 0.2% by weight or less.

[0081] The polymer composition comprises a variety of polymers. As described above, the various polymers include polycarbonate and a toughening component, which preferably includes, or is, an acrylonitrile-butadiene-styrene thermoplastic (preferably, bulk ABS) and optionally an acrylonitrile-styrene copolymer. Although the polymer composition may contain additional polymers, these are typically present as minor components in the polymer composition. Preferably, the total amount of polycarbonate, acrylonitrile-butadiene-styrene thermoplastic (e.g., bulk ABS), and any acrylonitrile-styrene copolymer is based on the total weight of the various polymers in the polymer composition, about 70% by weight or more, more preferably about 80% by weight or more, even more preferably about 90% by weight or more, and most preferably about 95% by weight or more, and is about 100% by weight or less.

[0082] The total weight of the polymer in the polymer composition is preferably about 75% by weight or more, more preferably about 83% by weight or more, and most preferably about 88% by weight or more. The total weight of the polymer in the polymer composition may be about 100% by weight or less, about 99% by weight or less, or about 98% by weight or less, based on the total weight of the polymer composition.

[0083] Polycarbonate (e.g., aromatic polycarbonate) is preferably present in an amount of about 10% by weight or more, more preferably about 20% by weight or more, even more preferably about 25% by weight or more, even more preferably about 28% by weight or more, and most preferably about 30% by weight or more, based on the total weight of the polymer composition and / or the total weight of the polymers in the polymer composition. Polycarbonate is preferably present in an amount of about 55% by weight or less, more preferably about 54% by weight or less, even more preferably about 53% by weight or less, even more preferably about 50% by weight or less, even more preferably about 48% by weight or less, even more preferably about 45% by weight or less, even more preferably about 42% by weight or less, and most preferably about 40% by weight or less, based on the total weight of the polymer composition. For example, the amount of polycarbonate may be about 20% by weight to about 55% by weight, about 30% to about 50% by weight, about 28% by weight to about 48% by weight, about 25% to about 50% by weight, or about 30% to about 55% by weight, based on the total weight of the polymer composition.

[0084] The amount of toughening components in the polymer composition (including rubber-modified monovinyl aromatic thermoplastics (e.g., the amount of ABS thermoplastics) and any additional impact modifiers and / or styrene-acrylonitrile copolymers) is preferably about 90% by weight or less, more preferably about 80% by weight or less, even more preferably about 75% by weight or less, and most preferably about 70% by weight or less, based on the total weight of the polymer composition and / or the total weight of the polymers in the polymer composition. The toughening components are preferably present in an amount of about 40% by weight or more, more preferably about 45% by weight or more, even more preferably about 50% by weight or more, and most preferably 55% by weight or more, based on the total weight of the polymer composition and / or the total weight of the polymers in the polymer composition.

[0085] The weight ratio of the polycarbonate component (i.e., polycarbonate) to the toughening component is preferably about 10:90 or higher, more preferably about 20:80 or higher, and most preferably about 25:75 or higher. The weight ratio of the polycarbonate component (i.e., polycarbonate) to the toughening component is preferably about 55:45 or lower, more preferably about 50:50 or lower, and most preferably about 45:55 or lower.

[0086] The concentration of the impact modifier (e.g., polybutadiene) is preferably about 3% by weight or higher, more preferably about 5% by weight or higher, and most preferably about 7% by weight or higher, based on the total weight of the polymer composition. The concentration of the impact modifier (e.g., polybutadiene) is preferably about 23% by weight or lower, more preferably about 18% by weight or lower, even more preferably about 15% by weight or lower, and most preferably about 13% by weight or lower, based on the total weight of the polymer composition.

[0087] If used, any additional styrene-acrylonitrile copolymer (i.e., copolymers other than those in rubber-modified monovinylamine aromatic thermoplastics) is preferably about 25% by weight or less, more preferably about 20% by weight or less, even more preferably about 15% by weight or less, and most preferably about 10% by weight or less, based on the total weight of the thermoplastic composition. Such additional styrene-acrylonitrile copolymer may be present in an amount of about 0% by weight or more. The ratio of the weight of such additional styrene-acrylonitrile copolymer to the weight of the rubber-modified monovinylamine aromatic thermoplastic is preferably about 1.0 or less, more preferably about 0.8 or less, even more preferably about 0.6 or less, and most preferably about 0.45 or less.

[0088] In one aspect of the invention, some or all of the rubber-modified monovinyl aromatic thermoplastics may be replaced by a combination of i) a styrene-acrylonitrile copolymer (as described herein) and ii) a rubber modifier. Preferably, the amount of rubber modifier is based on the total weight of the styrene-acrylonitrile copolymer and the rubber modifier, about 2% to about 30% by weight, more preferably about 3% to about 20% by weight, and most preferably about 3% to about 15% by weight. The rubber modifier may comprise any polymer with a glass transition temperature of about 0°C or lower. The rubber modifier preferably imparts ductility to the styrene-acrylonitrile copolymer. Particularly preferred rubber modifiers include butadiene monomers, styrene monomers, or both. Another particularly preferred rubber is an acrylic rubber, such as a rubber comprising butyl acrylate or ethylhexyl acrylate or substantially composed thereof. The rubber modifier may contain sufficient styrene to improve the compatibility of the rubber modifier with the styrene-acrylonitrile copolymer. The rubber modifier is preferably a copolymer comprising butadiene and styrene. The rubber modifier may be a core-shell polymer. The core preferably comprises an elastomeric polymer, and the shell preferably comprises a polymer with a melt temperature and / or glass transition temperature greater than about 100°C. For example, a rubber modifier may include a core comprising or substantially composed of a polymer, including butadiene and styrene. As another example, the core may comprise one or more acrylic rubbers, such as rubbers comprising butyl acrylate or ethylhexyl acrylate. A rubber modifier may have a shell comprising acrylate monomers. A rubber modifier may have a shell comprising polymethyl methacrylate. A rubber modifier may be a core-shell MBS modifier comprising a poly(butadiene / styrene) core and a polymethyl methacrylate shell. Examples of core-shell impact modifiers that can be used as rubber modifiers include PARALOID™ impact modifiers, commercially available from THE DOWCHEMICAL COMPANY. Rubber modifiers may be provided as emulsion ABS and / or grafted rubber concentrates. The amount of elastomer in the grafted rubber concentrate is preferably about 20% by weight or more, more preferably about 30% by weight or more, even more preferably about 45% by weight or more, and most preferably about 55% by weight or more, based on the total weight of the grafted rubber concentrate. The grafted rubber concentrate may be grafted onto a SAN copolymer (e.g., produced by an emulsion method). The grafted rubber concentrate may consist substantially (i.e., about 95% by weight or more) or entirely of one or more elastomers (e.g., butadiene) and one or more styrene-containing polymers (e.g., SAN). The grafted rubber concentrate may be added separately to the polymer composition, for example, along with additional SAN. Prior to addition to the polymer composition, the grafted rubber concentrate may be mixed with the additional styrene-containing polymer (e.g., SAN).The amount of toughening components other than bulk ABS (e.g., GRC or core-shell copolymer) is preferably less than 60% by weight, more preferably less than 40% by weight, and even more preferably less than 25% by weight, based on the total weight of the toughening components.

[0089] The amount of reinforcing filler (e.g., the amount of wollastonite and / or glass fiber) is preferably based on the total weight of the polymer composition, about 3% by weight or more, more preferably about 4% by weight or more, even more preferably about 5% by weight or more, and most preferably about 6% by weight or more. The amount of reinforcing filler (e.g., the amount of wollastonite and / or glass fiber) is preferably based on the total weight of the polymer composition, about 25% by weight or less, more preferably about 20% by weight or less, even more preferably about 17% by weight or less, even more preferably about 14% by weight or less, and most preferably about 11% by weight or less. For example, the reinforcing filler may be present in amounts from about 3% to about 25% by weight, from about 5% to about 14% by weight, from about 4% to about 11% by weight, or from about 3% to about 14% by weight, based on the total weight of the polymer composition.

[0090] The total amount of the rubber-modified monovinyl aromatic thermoplastic, polycarbonate, and any other styrene-acrylonitrile copolymer in the polymer composition is preferably about 70% by weight or more, more preferably about 80% by weight or more, even more preferably about 90% by weight or more, and most preferably about 95% by weight or more, based on the total weight of the polymer in the polymer composition. The total amount of the rubber-modified monovinyl aromatic thermoplastic, polycarbonate, and any other styrene-acrylonitrile copolymer in the polymer composition may be about 100% by weight or less, based on the total weight of the polymer in the polymer composition. Preferably, the total amount of the rubber-modified monovinyl aromatic thermoplastic, polycarbonate, and any other styrene-acrylonitrile copolymer in the polymer composition is about 50% by weight or more, more preferably about 65% by weight or more, more preferably about 77% by weight or more, and most preferably about 82% by weight or more, based on the total weight of the polymer composition. Preferably, the total amount of the rubber-modified monovinyl aromatic thermoplastic, polycarbonate and any other styrene-acrylonitrile copolymer in the polymer composition is based on the total weight of the polymer composition, about 97% by weight or less, more preferably about 95% by weight or less, even more preferably about 92% by weight or less and most preferably about 89% by weight or less.

[0091] The total amount of reinforcing filler, rubber-modified monovinyl aromatic thermoplastic, polycarbonate, and any other styrene-acrylonitrile copolymer in the polymer composition is preferably about 80% by weight or more, more preferably about 90% by weight or more, even more preferably about 95% by weight or more, and most preferably about 97% by weight or more, based on the total weight of the polymer composition. The total amount of reinforcing filler, rubber-modified monovinyl aromatic thermoplastic, polycarbonate, and any other styrene-acrylonitrile copolymer in the polymer composition may be about 100% by weight or less based on the total weight of the polymer composition.

[0092] The polymer composition may optionally contain one or more other polymers, as described herein. Examples of other polymers include olefin copolymers (e.g., containing 50% by weight or more ethylene and / or propylene), polyesters, and polyamides.

[0093] olefin copolymers

[0094] Usable olefin copolymers include polyolefin copolymers having one or more functional groups comprising oxygen and / or nitrogen atoms. Preferred olefin copolymers comprise about 50% by weight or more, more preferably about 60% by weight or more, and most preferably about 65% by weight or more of one or more α-olefins. The olefin copolymer preferably comprises one or more comonomers having at least one oxygen atom. As used herein, the olefin copolymer is substantially free of maleic anhydride and carboxylic acid groups (e.g., the amount of maleic anhydride, maleic acid, or other monomers that generate carboxylic acid groups is preferably about 4% by weight or less, more preferably about 0.9% by weight or less, and most preferably about 0.25% by weight or less, based on the total weight of the olefin copolymer). Preferred comonomers include acrylates and acetates; for example, the olefin copolymer may be an ethylene-acrylate copolymer. A particularly preferred olefin copolymer is Amplify AE ethylene-acrylate copolymer. If used, the amount of the olefin copolymer is preferably about 25% by weight or less, more preferably about 20% by weight or less, even more preferably about 12% by weight or less, and most preferably about 8% by weight or less, based on the total weight of the polymer composition. The amount of olefin copolymer can be about 0% by weight or more.

[0095] Polyester

[0096] The polymer composition (e.g., the polymer composition of the base layer) may comprise one or more polyesters. Examples of usable polyesters include aromatic polyesters, such as polyalkylene terephthalate. Examples of usable polyesters include those described in U.S. Patent Application Publication 2013 / 0196130 A1 (Hufen et al., published August 1, 2013, see, for example, paragraphs 0123 to 0132), which is incorporated herein by reference. The polymer composition is preferably substantially or completely free of polyester. If present, the total amount of polyester is preferably about 10% by weight or less, more preferably about 5% by weight or less, even more preferably about 2% by weight or less, even more preferably about 1.9% by weight or less, even more preferably about 1.0% by weight or less, and most preferably about 0.4% by weight or less, based on the total weight of the polymer composition. For example, the total amount of polyester may be about 0% by weight to about 10% by weight, about 0% by weight to about 1.9% by weight, or about 0% by weight to about 0.4% by weight, based on the total weight of the polymer composition.

[0097] polyamide

[0098] The polymer composition (e.g., the polymer composition of the base layer) may optionally contain one or more polyamides. The polyamide can be of any type. Suitable polyamides include reaction products of diamines and diacids, as well as monobasic polyamides. Polyamides formed from diamines and diacids may include polyamides containing reaction products of adipic acid or terephthalic acid with diamines (e.g., nylon). Examples of monobasic polyamides include nylon 6 and poly(terephthalamide). Nylons that can be used in this invention include nylon 3, nylon 4, nylon 5, nylon 6, nylon 6T, nylon 66, nylon 6 / 66, nylon 6 / 66 / 610, nylon 610, nylon 612, nylon 69, nylon 7, nylon 77, nylon 8, nylon 9, nylon 10, nylon 11, nylon 12, and nylon 91. Copolymers containing any of the above-described polyamides may also be used. Polyamide copolymers may include polyethers. Polyamide copolymers may be random copolymers, block copolymers, or combinations thereof. The polymer composition is preferably substantially or completely free of polyamide. If present, the total amount of polyamide is preferably about 3% by weight or less, more preferably about 2% by weight or less, even more preferably about 1.9% by weight or less, even more preferably about 1.0% by weight or less, and most preferably about 0.4% by weight or less, based on the total weight of the polymer composition. For example, the total amount of polyamide may be about 0% by weight to about 3% by weight, about 0% by weight to about 1.9% by weight, or about 0% by weight to about 0.4% by weight, based on the total weight of the polymer composition.

[0099] additive

[0100] The polymer composition may contain one or more additives. For example, the polymer composition may contain one or more stabilizers (e.g., heat stabilizers, light stabilizers, antioxidants, or UV stabilizers), one or more colorants, one or more processing aids, one or more flame retardants, one or more release agents, one or more antistatic agents, one or more conductive additives, one or more additives for improving scratch resistance, or one or more anti-dripping agents. Examples of additives that may be used include those described in, for example, paragraphs 0144 to 0147 of U.S. Patent Application Publication 2013 / 0196130 A1 (Hufen et al., published August 1, 2013, see paragraphs 0144 to 0147), which is incorporated herein by reference.

[0101] Preferred additives include those commonly used in polycarbonate compositions and / or those commonly used in polystyrene and / or ABS compositions.

[0102] Preferred antioxidants include sterically hindered phenolic antioxidants. Particularly preferred antioxidants are octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate, such as IRGANOX® 1076 (CAS #2082-79-3), which is commercially available from BASF.

[0103] Preferred release agents include polyol ester type release agents. A particularly preferred release agent is LOXIOL® P 861 / 3.5, which is commercially available from SAFICALCANNECARBO BV. Another particularly preferred release agent is LOXIOL® VPG 861, which is commercially available from EMERYOLEOCHEMICALS LLC (CINCINNATI, OH).

[0104] If present, the total amount of one or more additives is preferably based on the total weight of the polymer composition, about 10% by weight or less, more preferably about 5% by weight or less, and most preferably about 2.5% by weight or less. The total amount of one or more additives may be about 0% by weight or more, about 0.1% by weight or more, or about 0.3% by weight or more.

[0105] The polymer composition is preferably substantially free of or even completely free of polymers containing maleic anhydride and carboxylic acid groups (e.g., maleic anhydride, maleic acid, or other monomers that generate carboxylic acid groups). Without being bound by theory, it is believed that in the presence of such monomers, poorer durability (e.g., after humidity and / or weathering) is associated with oxidation and / or degradation of the material. Preferably, the amount of any polymer containing such monomers is about 1.2% by weight or less, more preferably about 0.9% by weight or less, even more preferably about 0.25% by weight or less, and most preferably about 0% by weight, based on the total weight of the styrene copolymer, the total weight of the polymer composition, or the total weight of the base layer.

[0106] The polymer composition can be formed as a base layer by any means. For example, the base layer can be formed by molding (e.g., injection molding, compression molding, overmolding, or co-injection molding), extrusion (e.g., profile extrusion, sheet extrusion, or blown film extrusion), calendering, 3D printing methods, or any other method known in polymer material processing. The base layer can have any thickness. The thickness of the base layer typically depends on the requirements of a particular application. Preferably, the base layer has a thickness of about 0.2 mm or greater, more preferably about 0.5 mm or greater, even more preferably about 1.0 mm or greater, and most preferably about 2.0 mm or greater. The thickness of the base layer is preferably about 30 mm or less, more preferably about 20 mm or less, even more preferably about 20 mm or less, even more preferably about 10 mm or less, and most preferably about 8 mm or less. It should be understood that the thickness of the base layer can be uniform or variable. If the thickness of the base layer varies, the above thickness values ​​refer to the average thickness of the base layer in the area to be adhered to the cover layer.

[0107] The substrate layer is preferably a dense material (e.g., a porosity of 10 vol% or less, preferably about 3 vol% or less, and most preferably about 0.8 vol% or less). The amount of porosity in the dense substrate layer can be 0 vol% or more, or about 0.3 vol% or more. It has been found that by using a dense substrate, the thickness and / or total weight of the substrate layer can be reduced. Using a dense substrate presents additional challenges in terms of adhesion and durability. Without being bound by theory, it is believed that the porosity of the foamed substrate layer can provide a means for mechanical attachment layers and / or provide a means for absorbing energy during durability testing. Preferably, the substrate layer is formed without the use of a foaming agent (e.g., a physical or chemical foaming agent). Thus, the resulting substrate layer is preferably free of residual foaming agent or its byproducts. Although a dense material for the substrate is preferred, it should be understood that the teachings herein can also be applied when the substrate layer is a foamed material (e.g., a porosity greater than 10 vol%, preferably about 20 vol% or more, and most preferably about 40 vol% or more). The foamed substrate may have a porosity of about 75% by volume or less, about 60% by volume or less, or about 50% by volume or less.

[0108] The base layer can be colored, clear, or transparent. For example, the base layer may include one or more colorants to provide a predetermined color to the substrate. Using a colored base layer in articles having a clear or transparent overlay may be particularly advantageous.

[0109] nature

[0110] The polymer composition taught herein preferably has a density of about 75 x 10⁻⁶. -6 cm / cm / ℃ or less, more preferably 65 x 10 -6 cm / cm / ℃ or less, or even more preferably about 60 x 10 -6 cm / cm / ℃ or smaller, or even more preferably about 50 x 10 -6 cm / cm / ℃ or less, with the most preferred being about 40 x 10 -6 The linear coefficient of thermal expansion is cm / cm / ℃ or less, as measured from -30℃ to 30℃. The polymer composition may have a linear coefficient of thermal expansion of approximately 5 x 10⁻⁶ cm / ℃. -6 cm / cm / ℃ or higher or approximately 20 x 10 -6 A linear thermal expansion coefficient of cm / cm / ℃ or higher.

[0111] The polymer composition preferably has one or more of the following characteristics: a notched treble impact strength of about 8 to about 40 kJ / m2 as measured according to ISO 179-1eA; a tensile modulus of about 2000 to about 6000 MPa as measured according to ISO 527 (polymer compositions containing fillers such as wollastonite and / or glass fibers have a modulus of about 3000 MPa or higher); or an elongation at break of about 5% to about 80% as measured according to ISO 527 (polymer compositions containing fillers preferably have an elongation at break of less than 40%).

[0112] Cover layer

[0113] Articles of manufacture according to the teachings herein include a cover layer on a base layer. The cover layer covers some or all of the surface of the base layer. Preferably, the cover layer is in direct contact with the base layer and is bonded to the base layer in the contact area.

[0114] The cover layer may have any thickness, but preferably a thickness less than that of the base layer. Thus, the base layer can provide one or more advantageous properties to the “body” of the article, while the cover layer can provide one or more properties to the surface of the article. Preferably, the cover layer has a thickness of about 0.15 mm or greater, more preferably about 0.30 mm or greater, even more preferably about 0.5 mm or greater, and most preferably about 0.6 mm or greater. The cover layer preferably has a thickness of about 3 mm or less, more preferably about 1.5 mm or less, and most preferably about 1.0 mm or less.

[0115] The capping layer can be applied to the substrate layer using any known method. The capping layer can be formed from materials including polymers, prepolymers, monomers, or any combination thereof. Preferably, the capping layer is formed from a composition that is polymerized and / or crosslinked after being applied to the surface of the substrate layer. Preferred methods for applying the capping layer include a molding step (e.g., overmolding).

[0116] Methods for applying a cover layer may include the steps of injecting a polymerizable composition into a mold and polymerizing the polymerizable composition at least partially to form a polyurethane and / or a polyurea. The polymerizable composition may pass through a static mixer before entering a mold cavity. The mold cavity preferably comprises a base layer having gaps above the surface of the base layer. When the polymerizable composition is injected into the mold, it contacts at least a portion of the surface of the base layer. The polymerizable composition is preferably retained in the mold cavity until some or all of the material polymerizes. When the polymerizable composition contacts the surface of the base layer, the base layer is preferably at a temperature below the glass transition temperature of the polymer composition (e.g., below the glass transition temperature of polycarbonate).

[0117] The capping layer can be provided as a multi-component system having two or more components or three or more components. For example, the system may include a first component and a second component, which are individually stable and polymerize when combined. The capping layer can be prepared by injecting each of the components into a mold. The components can be mixed before injection, mixed during injection (e.g., using a mixing head), or mixed in the mold. Preferably, the components are mixed during material injection into the mold, such as by using a mixing head (e.g., a dynamic or static mixing head).

[0118] The capping layer is preferably molded as a room-temperature liquid (e.g., applied at room temperature or at a high temperature). Preferably, the polymerizable composition polymerizes rapidly in the mold so that the composite part can be removed from the mold within a reasonable time. Preferably, the polymerization time (i.e., the time it takes for the capping layer to develop sufficient strength to remove the part from the mold) is about 50 minutes or less, more preferably about 20 minutes or less, even more preferably about 7 minutes or less, even more preferably about 3 minutes or less, and most preferably about 1 minute or less. The polymerizable composition can be injected into the mold at room temperature or at a high temperature. The mold temperature should be low enough so that the polymerizable composition can substantially or completely fill the cavity of the mold. Preferably, the mold temperature is about 170°C or lower, more preferably about 130°C or lower, even more preferably about 110°C or lower, and most preferably about 100°C or lower. The mold temperature should be high enough so that polymerization occurs within a reasonable time. Preferably, the mold temperature is about 15°C or higher, more preferably about 25°C or higher, even more preferably about 35°C or higher, even more preferably about 45°C or higher, and most preferably about 55°C or higher.

[0119] Preferably, the polymerizable composition is substantially or completely free of volatile organic compounds. Preferably, the polymerizable composition is free of harmful air pollutants. Preferably, the polymerization of the polymerizable composition does not produce volatile organic compounds. Preferably, the polymerizable composition is selected such that it becomes non-sticky within about 10 minutes or less, more preferably about 4 minutes or less, even more preferably about 2 minutes or less, and most preferably about 60 seconds or less (e.g., at about 20°C to about 50°C, about 50°C to about 80°C, or about 80°C to about 110°C).

[0120] The capping layer can be a dense material or a foamed material. Preferably, the capping layer is a dense material (i.e., a dense material with a porosity of about 20% by volume or less, preferably about 10% by volume or less, and more preferably about 5% by volume or less).

[0121] The cover layer preferably comprises, or is substantially composed of, polyurethane, polyurea, or both, that contacts and adheres to the base layer.

[0122] The overlay may include polyurethane, including one or any combination of features described in, for example, paragraphs 0173 to 0240 of U.S. Patent Application Publication 2013 / 0196130 A1 (Hufen et al., published August 1, 2013, see paragraphs 0173 to 0240), which is incorporated herein by reference. The covering layer may include polyurethane or polyurea, such as those described in: U.S. Patent Application Publication 2011 / 0135934 A1 (Seidel et al., published June 9, 2011, see paragraphs 0172-0219), U.S. Patent Application Publication 2002 / 0058716 A1 (Wittmann et al., published May 16, 2002, see paragraphs 0117-0151), U.S. Patent 5,192,814A (Oshima et al., published March 9, 1993), U.S. Patent 4,764,540 (August 16, 1988, see column 2, lines 43-10, line 32 and examples), and U.S. Patent 5,331,051 (published July 19, 1994, see column 2, lines 5-6, line 42 and examples), the entire contents of which are incorporated herein by reference.

[0123] Preferred polyurea comprises one or more repeating units having the following structure:

[0124]

[0125] Polyurea can be a reaction product comprising one or more isocyanate compounds and one or more amine compounds. The isocyanate-containing compound preferably contains two or more isocyanate functional groups (e.g., the isocyanate-containing compound may include diisocyanates, polyisocyanates containing three or more isocyanate groups, or any combination thereof). The amine compound preferably contains two or more amine groups. For example, the amine compound may include diamines, polyamines containing three or more amines, or any combination thereof. Preferred isocyanates include aromatic isocyanates, aromatic isocyanates, or combinations thereof.

[0126] The polyurethane used according to the invention is obtained by reacting a polyisocyanate with an H-active polyfunctional compound (preferably a polyol). In this context, the term "polyurethane" should also be understood to mean polyurethane-urea, wherein those compounds having NH functionality (optionally a mixture with a polyol) are used as the H-active polyfunctional compound.

[0127] Suitable polyisocyanates are aromatic, arylita, aliphatic, or alicyclic polyisocyanates known to those skilled in the art having an NCO functionality preferably ≥2, and may also contain iminooxadiazine dione, isocyanurate, urea dione, urethane, urethane carbamate, biuret, urea, oxadiazine trione, oxazolidinone, acylurea, and / or carbodiimide structures. These can be used alone or in any desired mixture with each other.

[0128] In this context, the aforementioned polyisocyanates are based on diisocyanates and triisocyanates, which are known to those skilled in the art and have aliphatic, alicyclic, aryliphatic, and / or aromatic bonded isocyanate groups, and it is irrelevant whether they are prepared using phosgene or by a phosgene-free process. Examples of such diisocyanates and triisocyanates are 1,4-diisocyanobutane, 1,5-diisocyanopentane, 1,6-diisocyanohexane (HDI), 2-methyl-1,5-diisocyanopentane, 1,5-diisocyano-2,2-dimethylpentane, 2,2,4- and 2,4,4-trimethyl-1,6-diisocyanohexane, 1,10-diisocyanodecane, 1,3- and 1,4-diisocyanocyclohexane, 1,3- and 1,4-bis-(isocyanomethyl)cyclohexane, 1-isocyano-3,3,5-trimethyl-5-isocyanomethylcyclohexane (isophorone diisocyanate, IPDI), and 4,4'-diisocyanodicyclohexylmethane (Desmodur® W, Bayer AG). Leverkusen, DE), 4-isocyanomethyl-1,8-octane-diisocyanate (triisocyanononane, TIN), ω,ω′-diisocyano-1,3-dimethylcyclohexane (H6XDI), 1-isocyano-1-methyl-3-isocyanomethylcyclohexane, 1-isocyano-1-methyl-4-isocyanomethylcyclohexane, bis-(isocyanomethyl)norbornene, 1,5-naphthalene-diisocyanate, 1,3- and 1,4-bis-(2-isocyanopropyl-2-yl)-benzene (TMXDI), 2,4- and 2,6-diisocyanotoluene (TDI), especially the 2,4- and 2,6-isomers and industrial-grade mixtures of the two isomers, 2,4'- and 4,4'-diisocyanodiphenylmethane (MDI), polymeric MDI (pMDI), 1,5-diisocyanatonaphthalene, 1,3-bis(isocyanatomethyl)benzene (XDI), and any desired mixtures of the mentioned compounds.

[0129] In this context, the polyisocyanate preferably has an average NCO functionality of 2.0 to 5.0, more preferably 2.2 to 4.5, particularly preferably 2.2 to 2.7, and an isocyanate group content of 5.0 to 37.0% by weight, preferably 14.0 to 34.0% by weight.

[0130] In a preferred aspect, a polyisocyanate or mixture of polyisocyanates of the type described above is used, which has only aliphatic and / or alicyclic bonded isocyanate groups.

[0131] More preferably, the above-mentioned types of polyisocyanates are based on hexamethylene diisocyanate, isophorone diisocyanate, isomeric bis-(4,4'-isocyanocyclohexyl)-methane, and mixtures thereof.

[0132] Of particular interest among modified polyisocyanates of higher molecular weight are prepolymers known in polyurethane chemistry having terminal isocyanate groups in the molecular weight range of 400 to 15,000, preferably 600 to 12,000. These compounds are prepared, in a manner known per se, by reacting an excess of a simple polyisocyanate of the type mentioned with an organic compound (particularly an organic polyhydroxy compound) having at least two groups reactive to the isocyanate groups. Suitable such polyhydroxy compounds are simple polyfunctional alcohols in the molecular weight range of 62 to 599, preferably 62 to 200, such as ethylene glycol, trimethylolpropane, propane-1,2-diol, or butane-1,4-diol or butane-2,3-diol, but particularly higher molecular weight polyether polyols and / or polyester polyols of the type known in polyurethane chemistry in the molecular weight range of 600 to 12,000, preferably 800 to 4,000, having at least two (as a rule, 2 to 8), but preferably 2 to 6 primary hydroxyl groups and / or secondary hydroxyl groups. For example, NCO prepolymers obtained from low molecular weight polyisocyanates of the type described above and less preferably compounds having groups that are reactive to isocyanate groups, such as copolymers of polysulfide polyols, hydroxyl-containing polyacetals, polyhydroxy-polycarbonates, hydroxyl-containing polyester-amides, or hydroxyl-containing olefinic unsaturated compounds, can also be used.

[0133] Compounds having groups reactive to isocyanate groups, particularly hydroxyl groups, and suitable for preparing NCO prepolymers are, for example, the compounds disclosed in U.S. Patent No. 4,218,543. In the preparation of NCO prepolymers, these compounds having groups reactive to isocyanate groups are reacted with, for example, a simple polyisocyanate of the type described above, while maintaining an excess of NCO. NCO prepolymers typically have an NCO content of 10 to 26, preferably 15 to 26 wt%. It is thus understood that, in the context of this invention, "NCO prepolymer" or "prepolymer having terminal isocyanate groups" should be understood to mean the reaction product itself and a mixture having an excess of unreacted starting polyisocyanate (which is also commonly referred to as a "semi-prepolymer").

[0134] Aliphatic diols with an OH value >500 mg KOH / g are commonly used chain extenders in polyurethane chemistry, such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butane-1,4-diol, and propane-1,3-diol. Diols such as 2-butane-1,4-diol, buten-1,3-diol, butane-2,3-diol, and / or 2-methylpropane-1,3-diol are preferred. Of course, it is also possible to use aliphatic diols in the form of mixtures with each other.

[0135] Suitable H-active components are polyols with an average OH value of 5 to 600 mg KOH / g and an average functionality of 2 to 6. Polyols with an average OH value of 10 to 50 mg KOH / g are preferred. Suitable polyols according to the invention are, for example, polyhydroxy-polyethers, which can be obtained by alkoxylation of suitable starting molecules (such as ethylene glycol, diethylene glycol, 1,4-dihydroxybutane, 1,6-dihydroxyhexane, dimethylolpropane, glycerol, pentaerythritol, sorbitol, or sucrose). Ammonia or amines (such as ethylenediamine, hexamethylenediamine, 2,4-diaminotoluene, aniline, or amino alcohols) or phenols (such as bisphenol A) can also be used as initiators. Alkoxylation is carried out using propylene oxide and / or ethylene oxide in any desired order or as a mixture.

[0136] In addition to polyols, at least one other crosslinking agent and / or chain extender may be present, selected from the group consisting of: amines and amino alcohols, such as ethanolamine, diethanolamine, diisopropanolamine, ethylenediamine, triethanolamine, isophorone diamine, N,N'-dimethyl(diethyl)-ethylenediamine, 2-amino-2-methyl (or ethyl)-1-propanol, 2-amino-1-butanol, 3-amino-1,2-propanediol, 2-amino-2-methyl(ethyl)-1,3-propanediol; and alcohols, such as ethylene glycol, diethylene glycol, 1,4-dihydroxybutane, 1,6-dihydroxyhexane, dimethylolpropane, glycerol and pentaerythritol, as well as sorbitol and sucrose, or mixtures of these compounds.

[0137] Polyester polyols, which can be obtained by reacting low molecular weight alcohols with polyfunctional carboxylic acids (such as adipic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, or anhydrides of these acids) in a manner known per se, are also suitable, provided that the viscosity of the H-active component does not become too high. Castor oil is a preferred polyol containing ester groups. Furthermore, formulations containing castor oil, such as those obtained by modifying solvent resins (e.g., aldehyde-ketone resins) and castor oil based on other natural oils with polyols, are also suitable.

[0138] Those higher molecular weight polyhydroxy-polyethers, where the high molecular weight polyadducts or condensates or polymers exist in finely dispersed, dissolved, or grafted forms, are also suitable. Such modified polyhydroxy compounds are obtained in ways known per se, for example, when addition polymerization (e.g., the reaction between polyisocyanates and amino-functionalized compounds) or condensation polymerization (e.g., the reaction between formaldehyde and phenols and / or amines) is allowed to proceed in situ in compounds containing hydroxyl groups. However, it is also possible to mix an existing aqueous polymer dispersion with the polyhydroxy compound and then remove water from the mixture.

[0139] Polyhydroxy compounds modified with vinyl polymers (such as those obtained, for example, by polymerization of styrene and acrylonitrile in the presence of polyether or polycarbonate polyols) are also suitable for preparing polyurethanes. Plastics with exceptional flame retardancy are obtained by using polyether polyols modified according to DE-A 2 442 101, DE-A 2 844 922, and DE-A 2 646 141 via graft polymerization with vinyl phosphonates and optionally (meth)acrylonitrile, (meth)acrylamide, or OH-functional (meth)acrylates.

[0140] Representatives of the compounds mentioned for use as H-active compounds are described, for example, in High Polymers, Volume XVI, “Polyurethanes Chemistry and Technology”, Saunders-Frisch (ed.) Interscience Publishers, New York, London, Volume 1, pp. 32-42, 44, 54 and Volume II, 1984, pp. 5-6 and 198-199.

[0141] Mixtures of the listed compounds may also be used.

[0142] The limitations on the average OH value and average functionality of the H-active components arise, particularly from the increased embrittlement of the resulting polyurethane. However, the possibilities for influencing the physical polymeric properties of the polyurethane are known in principle to those skilled in the art, allowing the NCO components, aliphatic diols, and polyols to coordinate with each other in an advantageous manner.

[0143] The polyurethane layer (b) can be foamed or solid, such as as a paint or coating.

[0144] All known auxiliary substances and additives (such as mold release agents, foaming agents, fillers, catalysts and flame retardants) can be used in its production.

[0145] In this context, the optional auxiliary substances and additives to be used are:

[0146] a) Water and / or volatile inorganic or organic substances used as foaming agents

[0147] b) Catalyst

[0148] c) Surfactant additives, such as emulsifiers and foam stabilizers.

[0149] d) Reaction inhibitors

[0150] e) Additives

[0151] The paints to be used according to the present invention comprise 1-C and 2-C paint systems, preferably water-based paints. In addition to the water-based paints according to the present invention, the two-component paints (2-C) in the context of the present invention also contain a hardener.

[0152] According to one embodiment, the water-based paint according to the present invention is a single-component paint.

[0153] In another embodiment, the coating on at least one side is a water-based 2-component polyurethane varnish.

[0154] The 2-component polyurethane paints to be used according to the present invention are characterized in that, in one embodiment, they preferably contain substantially:

[0155] (a) A polyisocyanate, optionally hydrophilized in the presence of an organic solvent or a mixture of solvents.

[0156] (b) A compound having a group that is reactive to isocyanates and optionally hydrophilic in water and optionally in the presence of an organic solvent or a mixture of solvents.

[0157] (c) Other additives and auxiliary substances used by the candidate,

[0158] The amount of (a) + (b) is 20 to 100 parts by weight, and the amount of (c) is 0 to 80 parts by weight, provided that the sum of the parts by weight of the individual components (a) to (c) is 100.

[0159] In the context of this invention, a two-component system should be understood to mean a paint, wherein components (a) and (b) must or should be stored in separate containers due to their reactivity. The two components are mixed only shortly before application and then generally react without additional activation.

[0160] The (poly)isocyanate component (a) is preferably any desired organic polyisocyanate having aliphatic, alicyclic, aryliphatic, and / or aromatic bonded free isocyanate groups and is liquid at room temperature or diluted with a solvent for this purpose. The polyisocyanate component (a) advantageously has a viscosity of 10 to 15,000, preferably 10 to 5,000 mPas at 23°C. Particularly preferably, the polyisocyanate component (a) is a polyisocyanate or mixture of polyisocyanates with an (average) NCO functionality between 2.0 and 5.0 and a viscosity of 10 to 2,000 mPas at 23°C, having only aliphatic and / or alicyclic bonded isocyanate groups.

[0161] Preferably, polyisocyanates with free NCO groups are used as crosslinking agents to achieve a particularly high level of paint technology from water-based two-component polyurethane paints. Suitable crosslinking agent resins of this kind are, for example, polyisocyanates based on isophorone-diisocyanate (IPDI), hexamethylene-diisocyanate (HDI), 1,4-diisocyanocyclohexane, bis-(4-isocyanocyclohexyl)-methane, 1,3-diisocyanobenzene, 2,4- and / or 2,6-diisocyanotoluene (TDI), diisocyanodiphenylmethane (MDI), and ω,ω'-diisocyano-1,3-dimethylcyclohexane (H6XDI). Polyisocyanates based on isophorone-diisocyanate, hexamethylene-diisocyanate, bis-(4-isocyanocyclohexyl)-methane and ω,ω'-diisocyano-1,3-dimethylcyclohexane (H6XDI) are preferred.

[0162] The diisocyanates mentioned may be used as is, but derivatives of diisocyanates are generally used. Suitable derivatives are polyisocyanates containing biuret, isocyanurate, urea dione, urethane, iminooxadiazine dione, oxadiazine trione, carbodiimide, acylurea, and urethane groups.

[0163] Preferred derivatives are those having isocyanurate, iminooxadiazine dione, and urea dione structures. Low-monomer polyisocyanates having these structural elements derived from isophorone-diisocyanate (IPDI), hexamethylene-diisocyanate (HDI), 1,4-diisocyanocyclohexane, and bis-(4-isocyanocyclohexyl)-methane are particularly preferred.

[0164] Triisocyanates, such as TIN (triisocyanatononane), are also suitable.

[0165] The (poly)isocyanate component (a) may optionally be hydrophilically modified. Water-soluble or dispersible polyisocyanates may be obtained, for example, by modification with carboxylic esters, sulfonates and / or polyoxyethylene groups and / or polyoxypropylene groups.

[0166] The hydrophilization of polyisocyanates is possible, for example, by reaction with a lack of a monofunctional hydrophilic polyether alcohol. The preparation of such hydrophilized polyisocyanates is described, for example, in EP-A 0 540 985, page 3, line 55-4, line 5. Polyisocyanates containing urea carbamate groups and prepared by reaction of low-monomer polyisocyanates with polyethylene oxide polyether alcohols under ureomethanization conditions are also particularly suitable. Water-dispersible polyisocyanate mixtures based on triisocyanate nonane, as described in DE-A 10 007 821, page 2, line 66 – page 3, line 5, are also suitable, as are polyisocyanates hydrophilized with ionic groups (sulfonate groups, phosphonate groups), such as those described in DE-A 10 024 624, page 3, lines 13–33, or WO 01 / 88006. External hydrophilization by adding emulsifiers is also possible.

[0167] The NCO content of the polyisocyanate component (a) used (e.g., in the case of so-called polyether urea carbamate (by means of hydrophilization of the polyether)) can be in the range of 5-25% by weight. In the case of hydrophilization with sulfonic acid groups, an NCO content of 4-26% by weight can be achieved, wherein these figures should be understood as examples only.

[0168] The isocyanate component used can also be partially capped by components that react with isocyanates, for example, up to one-third of the isocyanate groups present. In this case, the reaction of the capped isocyanate component with another polyol can be carried out in a later step for further crosslinking.

[0169] Capping agents suitable for these polyisocyanates are, for example, monofunctional alcohols such as oximes, such as acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime; lactams such as ε-caprolactam; phenols; amines such as diisopropylamine or dibutylamine, dimethylpyrazole or triazole; and dimethyl malonate, diethyl malonate or dibutyl malonate.

[0170] The use of low-viscosity, hydrophobic, or hydrophilic polyisocyanates having free isocyanate groups based on aliphatic, alicyclic, aryliphatic, and / or aromatic isocyanates (particularly preferred aliphatic or alicyclic isocyanates) is preferred because a particularly high level of film properties can be achieved in this way. The advantages of the adhesive dispersions according to the invention are most clearly demonstrated in combination with these crosslinking agents. These polyisocyanates typically have a viscosity of 10 to 3,500 mPas at 23°C. If desired, the polyisocyanates can be used in the form of mixtures with small amounts of inert solvents to reduce the viscosity to values ​​within the stated range. Triisocyanate nonane can also be used alone or in mixtures as a crosslinking agent component.

[0171] Of course, in principle, mixtures of various polyisocyanates can also be used.

[0172] Suitable compounds (b) having groups reactive to isocyanates are, for example, polymers containing hydroxyl, sulfonate and / or carboxyl groups, preferably carboxyl groups, and optionally sulfonic acid and / or carboxyl groups, preferably carboxyl groups: olefinic unsaturated monomers (so-called polyacrylate polyols), combinations of diols and dicarboxylic acids (so-called polyester polyols), combinations of diols, dicarboxylic acids and diisocyanates (so-called polyurethane polyols), and / or mixtures of the aforementioned polyol classes, such as polyacrylate-polyester polyols, polyacrylate-polyurethane polyols, polyester-polyurethane polyols, or polyester-polyurethane polyols, preferably having a molecular weight Mn (number average), said polymer preferably having a molecular weight Mn (number average) of 500 to 50,000, particularly 1,000 to 10,000, as determined by gel permeation chromatography, a hydroxyl value of 16.5 to 264, preferably 33 to 165 mg KOH / g solid resin, and a value of 0 to 150, preferably 0 to 100. The acid value of KOH / g solid resin (based on unneutralized sulfonic acid and / or carboxyl groups), and the content of sulfonate groups and / or carboxyl groups of 5 to 417, preferably 24 to 278 milliequivalents / 100 g solids.

[0173] These anionic groups are particularly preferably carboxylic acid ester groups. An overview of various adhesives is given, for example, in EP-A 0 959115, page 3, lines 26-54. However, simple diol components may also be used. All adhesives dissolved or dispersed in water and having groups reactive with isocyanates are suitable in principle as adhesive component (b). These also include, for example, polyurethanes or polyureas dispersed in water and crosslinkable with polyisocyanates due to the active hydrogen atoms present in the urethane or urea groups. However, polyols, i.e., compounds having free OH groups, are preferred. Adhesive component (b) is generally used to prepare coating compositions in the form of aqueous solutions and / or dispersions with a strength of 10-60, preferably 20 to 50 wt%, typically having a viscosity of 10 to 105, preferably 100 to 10,000 mPa·s / 23°C and a pH of 5 to 10, preferably 6 to 9. An auxiliary solvent may optionally be used. Depending on the molecular weight of the binder component (b) and the content of its anionic or free acid groups, particularly carboxyl groups, the aqueous system containing the polymer is a true dispersion, colloidal dispersion, or molecularly dispersed dispersion, but is generally referred to as a "partial dispersion," i.e., an aqueous system with partial molecular and partial colloidal dispersions.

[0174] The ratio (NCO-OH ratio) of isocyanate groups from component (a) to isocyanate reactive groups such as hydroxyl groups from component (b) can span a wide range. Therefore, a ratio of 0.2:1.0 to 4.0:1.0 can be used for paint-related applications. A range of 0.35:1 to 2.0:1.0 is preferred, and a range of 1.0:1.0 to 1.5:1.0 is particularly preferred.

[0175] Optionally, 1 to 10,000 ppm of a commercially available catalyst may be added to the composition.

[0176] Conventional auxiliary substances and paint technology additives (d), such as defoamers, thickeners, pigments, dispersants, catalysts other than (c), skin prevention agents, antisettling agents, or emulsifiers, may be added before, during, or after the preparation of the aqueous adhesive dispersion according to the invention, as well as in the case of preparing a coating composition by adding at least one crosslinking agent.

[0177] The composite article can be prepared in a single injection molding machine or two or more injection molding machines (e.g., a first molding machine for molding the base layer and a second molding machine for molding the cover layer). Preferably, the composite article is prepared in a single molding machine such that the base layer can be molded in a mold, and the cover layer can be molded on the base layer without removing the base layer from the mold. For example, the cavity of the mold can be changed in volume after molding the base layer so that gaps exist on the surface of the base layer for introducing a polymerizable composition for forming the cover layer.

[0178] The method may include the step of injection molding the polymer composition into a mold at a temperature above the softening temperature of the polymer composition (e.g., above the glass transition temperature of the polycarbonate). The mold temperature is preferably low enough to allow the polycarbonate to cure in the mold (e.g., by cooling to below its glass transition temperature).

[0179] Two-component polyurethane systems may contain water and / or organic solvents or mixtures thereof as solvents.

[0180] Composite articles taught herein can be used in both automotive and non-automotive applications. Preferred automotive applications include interior and exterior automotive components. The composite articles are particularly useful in visible applications. Preferred components include interior trim components (e.g., dashboards and doors) and exterior trim components (e.g., for A-pillars and B-pillars).

[0181] Composite articles taught herein can be used in both automotive and non-automotive applications. Preferred automotive applications include interior and exterior automotive components. The composite articles are particularly useful in visible applications. Preferred components include interior trim components (e.g., dashboards and doors) and exterior trim components (e.g., for A-pillars and B-pillars).

[0182] Test methods

[0183] linear thermal expansion coefficient

[0184] The coefficient of linear thermal expansion (CLTE) shall be measured on an ISO tensile bar (as used in ISO 527-1) over a temperature range of -30°C to 30°C, in accordance with ISO 1359-2.

[0185] Stiffness / Modulus

[0186] The tensile modulus was measured at approximately 23°C according to ISO 527-1, -2.

[0187] Flexural modulus

[0188] Flexural modulus is measured according to ISO 178.

[0189] molecular weight

[0190] Weight-average molecular weight, number-average molecular weight, and polydispersity index were measured by gel permeation chromatography (GPC).

[0191] Adhesion

[0192] The adhesion force was measured using the PosiTest® AT-A Automated Adhesion Tester, available from DeFelsko. The trolley was glued to the cover layer, and the cover layer was cut around the perimeter of the trolley. The force used to remove the cover layer was measured. Unless otherwise specified, the trolley diameter is approximately 20 mm.

[0193] Aging durability

[0194] The aging durability was measured on aged samples using the PosiTest® AT-A automated adhesion tester as described in this article. Examples of key aging tests are described below:

[0195] Short thermal cycling test: Volkswagen PV1200 aging test

[0196] Each cycle lasts 720 minutes (12 hours) and includes: (1) heating the component from 23°C to 80°C at 80% relative humidity over a period of 60 minutes; (2) holding at 80°C and 80% relative humidity for 240 minutes; (3) cooling to -40°C over a period of 120 hours, wherein the humidity drops to approximately 30% relative humidity near the freezing point and is not adjusted below the freezing point; (4) holding at -40°C for 240 minutes; (5) heating from -40°C to 23°C for 60 minutes and adjusting the humidity (approximately 30% relative humidity when the temperature passes 0°C). Unless otherwise stated, the sample is cycled for 8 cycles (i.e., approximately 96 hours).

[0197] Thermo-Aging Test: VDA 75202

[0198] VDA 75202 was tested using the XENOTEST ALPHA testing apparatus. Test conditions were type 3. The number of exposure cycles was 4. The standard black temperature was approximately 90°C. The ambient temperature was approximately 65°C, and the relative humidity was 10%–30%. The radiation intensity was 60 W / m². 2 (Measured in the wavelength range of 300 to 400 nm).

[0199] Thermal-oxidative aging

[0200] Thermal-oxidative aging was carried out in an oven at a constant temperature of approximately 120°C for approximately 240 hours.

[0201] Solar simulation test – DIN 75220 Indoor 1T

[0202] The test was conducted for 240 hours at approximately 80°C and below 30% relative humidity. The radiation intensity was approximately 830 W / m². 2 The spectral energy is approximately 6.9% UV light (295-400 nm), approximately 59.7% visible light (400-800 nm), and approximately 48.6% infrared light (800-2450 nm).

[0203] Hydrolysis test (based on DBL 7384-8.1.18)

[0204] The test was conducted at 90°C and approximately 98% to 100% relative humidity for 72 hours.

[0205] melt flow rate

[0206] Unless otherwise specified, melt flow rates are measured according to ISO 1133 and expressed in g / 10 min. For polycarbonate polymers, melt flow rates are measured at a temperature of about 300 °C and a load of about 1.2 kg. For acrylonitrile-butadiene-styrene thermoplastics (e.g., ABS thermoplastics), melt flow rates are measured at a temperature of about 220 °C and a load of about 10.0 kg. For styrene-acrylonitrile copolymers, melt flow rates are measured at a temperature of about 230 °C and a load of about 3.8 kg. For PCABS resins, melt flow rates are measured at a temperature of about 260 °C and a load of about 5.0 kg.

[0207] Any numerical values ​​listed herein include all values ​​from lower to higher values ​​in increments of one unit, provided that there is an interval of at least two units between any lower and any higher value. As an example, if the quantity of a component or the value of a process variable, such as temperature, pressure, time, etc., is, for example, 1 to 90, preferably 20 to 80, more preferably 30 to 70, then values ​​such as 15 to 85, 22 to 68, 43 to 51, 30 to 32, etc., are explicitly listed in this specification. For values ​​less than 1, one unit is considered, where appropriate, 0.0001, 0.001, 0.01, or 0.1. These are merely embodiments of specific intent, and all possible combinations of numerical values ​​between the lowest and highest values ​​are considered to be clearly indicated in this application in a similar manner. It can be seen that the teaching of quantities expressed herein as “parts by weight” also considers the same range expressed as a weight percentage. Therefore, in specific embodiments of the present invention, the description of the range of “x” parts by weight of the obtained polymer blend composition also takes into account the teaching of the range of the same described amount of “x” as a weight percentage of the obtained polymer blend composition.

[0208] Unless otherwise stated, all ranges include all numbers between the endpoints. The use of “about” or “approximately” in relation to ranges applies to both ends of the range. Thus, “about 20 to 30” is intended to encompass “about 20 to about 30”, including at least the specified endpoints.

[0209] All publications and references (including patent applications and publications) are incorporated herein by reference for all purposes. The term “consistently of” used to describe a combination shall include the identified element, ingredient, component, or step, as well as any other such element, ingredient, component, or step that does not significantly affect the essential and novel features of the combination. The use of the terms “comprising” or “including” herein to describe a combination of elements, ingredients, components, or steps also considers embodiments that are substantially composed of said elements, ingredients, components, or steps.

[0210] Multiple elements, components, or steps may be provided by a single integrated element, component, component, or step. Alternatively, a single integrated element, component, component, or step may be divided into multiple separate elements, components, components, or steps. The disclosure of "a / one" used to describe an element, component, component, or step is not intended to exclude additional elements, components, components, or steps.

[0211] It should be understood that the above description is intended to be illustrative rather than restrictive. After reading the above description, many embodiments and applications beyond the provided examples will be apparent to those skilled in the art. Therefore, the scope of the invention should not be determined by reference to the above description, but rather by reference to the appended claims together with their equivalents. All disclosures in articles and references (including patent applications and publications) are incorporated herein by reference for all purposes. Omissions in the following claims regarding any aspect of the subject matter disclosed herein are not a disclaimer of liability for such subject matter, nor should they be construed as the inventors not considering such subject matter to be part of the disclosed inventive subject matter.

[0212] Material

[0213] ABS-A is MAGNUM® 8434 acrylonitrile-butadiene-styrene thermoplastic (commercially available from TRINSEO) with a density of approximately 1.05 g / cm³ (measured according to ISO 1183) and a melt flow rate of approximately 13 g / 10 min (measured according to ISO 1133 at 220°C / 10 kg). Magnum® 8434 is a bulk ABS and contains approximately 10-12 wt% butadiene, approximately 65-70 wt% styrene, and approximately 20-24 wt% acrylonitrile.

[0214] ABS-B is MAGNUM® 3904 acrylonitrile-butadiene-styrene thermoplastic (commercially available from TRINSEO) with a density of approximately 1.05 g / cm³ (measured according to ISO 1183) and a melt flow rate of approximately 4.5 g / 10 min (measured according to ISO 1133 at 220°C / 10 kg). Magnum® 3904 is a bulk-formed ABS. The flexural modulus is approximately 276 kpsi (measured according to ISO 178 on a 3.2 mm thick injection-molded test specimen). The tensile strain at break (yield) is approximately 2.6% (measured according to ISO 527-2 / 50 on a 3.2 mm thick injection-molded test specimen).

[0215] Grafted ABS – A is Kumho® HR 181, commercially available from KUMHO PETROCHEMICAL. The rubber content is 57%–60% by weight. The rubber particle size is 0.35–0.40 µm.

[0216] Filler A is NYGLOS® 4W 10992 wollastonite, commercially available from NYCO MINERALS. Filler A has a CaSiO3 chemical composition, comprising approximately 46.15 wt% CaO, approximately 51.60 wt% SiO2, approximately 0.77 wt% Fe2O3, approximately 0.34 wt% Al2O3, approximately 0.16 wt% MnO, approximately 0.38 wt% MgO, approximately 0.05 wt% TiO2, and approximately 0.05 wt% K2O. Filler A has a needle-like structure with an aspect ratio of approximately 11:1, such as... Figure 2 As shown in the diagram. Filler A has a Mohs hardness of approximately 4.5, a median particle size of approximately 4.5 μm (Cilas particle size analyzer), approximately 99.9% on a 325 US mesh sieve (Apline Jet Sieve), a GE brightness of approximately 92 as measured by ASTM E07, a bulk density (loose) of approximately 0.2 g / cm³ as measured by ASTM C87, a bulk density (tamped) of approximately 0.35 as measured by ASTM C87, an oil absorption of approximately 75 lbs. / 100 lbs. as measured by ASTM D281, and a specific gravity of approximately 2.9. The wollastonite is coated with an organic sizing agent.

[0217] Filler B is glass fiber. ThermoFlow® 720 chopped glass fiber is coated with a sizing agent. It is commercially available from JOHNSMANVILLE. The fiber is E-glass fiber (aluminoborosilicate glass) with a nominal filament diameter of approximately 13 μm and a length of approximately 4.7 mm.

[0218] Packing material C is talc packing material.

[0219] PC-A is a linear polycarbonate of bisphenol A with a melt flow rate (i.e., melt mass flow rate) of approximately 10 g / 10 min, measured according to ISO 1133 at 300 °C / 1.2 kg. PC-A has a tensile modulus of approximately 2300 MPa, a yield tensile strength of approximately 60.0 MPa, a tensile strength at break of approximately 71.0 MPa, a yield tensile elongation of approximately 6%, and a tensile elongation at break of approximately 150%, all measured according to ISO 527-2 / 50. PC-A has a refractive index of approximately 1.586, measured according to ISO 489, a light transmittance of approximately 89.0%, and a haze of approximately 1.0%, measured according to ASTM D1003. PC-A has a flexural modulus of approximately 2400 MPa as measured according to ISO 178, a notched Chappell impact strength of 35 kJ / m² as measured according to ISO 179 / e1A at 23°C, a notched Izod impact strength of 90 kJ / m² as measured according to ISO 180 / A at 23°C, and an unnotched Izod impact strength of "no fracture" as measured according to ISO 180 at 23°C. PC-A also has a strength of approximately 6.8 x 10⁻⁶ m² as measured according to ASTM D696 at temperatures ranging from -40°C to 82°C. -5 The linear coefficient of thermal expansion is measured in cm / cm / ℃. PC-A is commercially available from TRINSEO as CALIBRE™ 300-10 polycarbonate resin.

[0220] Ethylene copolymer A – Amplify EA 101.

[0221] Additive Packaging A is an additive package that includes heat stabilizers and processing aids. The additive package contains CCSAN Black Concentrate, Irganox 1076, and LOXIOL EP 861 in a weight ratio of approximately 10:1:2.

[0222] Polyurea System A is a highly transparent polyurea coating system.

[0223] Polyurea system B is a black polyurea system. This system includes a 2K curing agent comprising isocyanate and acetate.

[0224] Polyurethane system A is a polyurethane system that includes colorant for coloring the coating layer.

[0225]

[0226]

[0227]

[0228] Example 1 was prepared by injection molding of the polymer composition shown in Table 1. The temperature distribution from the hopper to the nozzle was 240°C / 250°C / 255°C / 260°C, and the hot runner had a temperature of approximately 275°C. The screw diameter was approximately 55 mm. The gasket was approximately 3.8 cm. 3 The plasticizing time is approximately 11 seconds. The feed rate is approximately 247.1 cm². 3 The injection time was approximately 1.45 seconds. The injection pressure was approximately 1500 bar, and the back pressure was approximately 100 bar. The injection velocity was approximately 125 cm. 3 / sec. The pressure is maintained at 450 / 400 / 350 bar for 0.5 seconds each. The mold temperature is approximately 80°C, and the cooling time is approximately 70 seconds. The thickness of the base layer is approximately 3.4 mm. The part weight is approximately 222.5 g. After the base layer cools, the cavity is enlarged to create gaps for injecting the polymerizable composition. Gaps are formed on the surface of the base layer. The polymerizable composition is injected into the cavity to fill the gaps and contact the surface of the base layer. The mold temperature during this step is approximately 80°C. After the capping layer has partially polymerized, the composite part is removed from the cavity. The total cycle time is approximately 105 seconds. The total thickness of the composite is approximately 4.76 mm.

[0229] The polymerizable composition is a 2K polyurethane RIM system.

[0230] The adhesion between the cover layer and the base layer was measured using a PosiiTest AT-A. The trolley dimensions were approximately 20 mm.

[0231] Adhesion was measured on the prepared samples. Adhesion was also measured after weathering, according to Volkswagen PV1200. Adhesion was also measured after heat aging at 90°C for 72 hours. The results are shown in Table 1.

[0232] Examples 2-4 were prepared using the same method as Example 1, except that the polymer compositions contained the fillers shown in Table 1. Example 2 included wollastonite. Example 3 included glass fiber. Example 4 included talc.

[0233] Example 5 was prepared using the same method as Example 1, except that the polymer composition contained wollastonite and ethylene copolymer as listed in Table 2.

[0234] Example 6 was prepared using the same method as Example 1, except that a different bulk ABS was used, the composition contained wollastonite, and grafted ABS was not used. The compositions are listed in Table 2.

[0235] Example 7 was prepared using the same method as Example 1, except that the polymer composition shown in Table 2 was used. This composition contains talc.

[0236] Example 8 was prepared using the same method as Example 1, except that the capping layer was polyurea system B.

[0237] Example 9 was prepared using the same method as Example 1, except that the capping layer was polyurethane system A.

[0238] Example 10 was prepared using the same method as Example 1, except that the capping layer was polyurea system A.

[0239] The adhesion of test examples 8, 9 and 10 during molding and after the following aging conditions was tested.

[0240] Hydrolytic aging: 72 hours @ 90℃ and 98%-100% relative humidity.

[0241] Thermo-photoaging - 4 days, according to VDA 75202.

[0242] Weather resistance – 8 cycles / 96 hours, according to Volkswagen PV1200.

[0243] Thermal-oxidative aging – 240 hours at 120°C.

[0244] Solar simulation – DIN 75220 – 10 days; 80℃; 830 W / m 2 .

[0245] Specifically, this invention relates to the following technical solutions.

[0246] 1. A multi-layered article comprising:

[0247] i) A base layer comprising a polymer composition, wherein the polymer composition is a blend comprising two or more polymers, the polymers comprising a polycarbonate component and a toughening component, wherein the toughening component comprises a styrene-acrylonitrile copolymer and an impact modifier; and

[0248] ii) A cover layer comprising polyurethane and / or polyurea, said cover layer being directly bonded to said base layer;

[0249] The concentrations of the two or more polymers are approximately 70% by weight or higher (preferably about 83% by weight or higher, and more preferably about 88% by weight or higher) and about 100% by weight or lower (preferably about 99% by weight or lower) based on the total weight of the polymer composition. The total weight of the polycarbonate component and the toughening component is approximately 75-100% by weight based on the total weight of the two or more polymers in the polymer composition. The weight ratio of the polycarbonate component to the toughening component is approximately 10:90 or higher (preferably about 20:80 or higher, and more preferably about 25:75 or higher) and about 55:45 or lower (preferably about 50:50 or lower, and more preferably about 45:55 or lower). The concentration of the impact modifier is approximately 3% by weight or higher (preferably about 5% by weight or higher, and more preferably about 7% by weight or higher) and about 23% by weight or lower (preferably about 18% by weight or lower, more preferably about 15% by weight or lower, and most preferably about 13% by weight or lower) based on the total weight of the two or more polymers.

[0250] 2. The multilayer article according to technical solution 1, wherein the amount of polyester in the polymer composition is about 0 or less than about 5% by weight.

[0251] 3. The multilayer product according to technical solution 1 or 2, wherein the impact modifier is polybutadiene rubber.

[0252] 4. The multilayer article according to any one of technical solutions 1-3, wherein the toughening component comprises bulk ABS.

[0253] 5. The multilayer article according to any one of technical solutions 1-4, wherein the toughening component comprises a grafted ABS impact modifier (preferably having i) about 45% by weight or higher, more preferably about 55% by weight or higher and ii) about 85% by weight or lower, more preferably about 75% by weight or lower polybutadiene concentration based on the total weight of the grafted ABS impact modifier).

[0254] 6. The multilayer article according to any one of technical solutions 1-5, wherein the polycarbonate component is present in an amount of about 20-55% by weight (preferably about 20-50% by weight, more preferably about 25-45% by weight and most preferably about 30-45% by weight) based on the total weight of the polymer composition.

[0255] 7. A multilayer article according to any one of technical solutions 1-6, wherein the polymer composition comprises ABS thermoplastic (i.e., acrylonitrile-butadiene-styrene thermoplastic), the ABS thermoplastic comprising a polybutadiene-containing phase dispersed in a styrene-containing phase comprising a styrene-acrylonitrile copolymer, wherein the styrene-acrylonitrile copolymer comprises about 60% by weight or more styrene (and preferably about 82% by weight or less styrene) and about 15% by weight or more acrylonitrile (and preferably about 33% by weight or less acrylonitrile) based on the total weight of the acrylonitrile-styrene copolymer.

[0256] 8. The multilayer article according to any one of technical solutions 1-7, wherein the styrene-acrylonitrile copolymer is a random copolymer, the random copolymer being substantially composed of (for example, of about 90% by weight or more, about 95% by weight or more, about 97% by weight or more, or about 99% by weight or more, and preferably entirely composed of) acrylonitrile and styrene.

[0257] 9. The multilayer article according to any one of claims 1-8, wherein the polymer composition comprises a reinforcing filler in an amount of about 3-30% by weight (preferably about 5-23% by weight and most preferably about 7-15% by weight) based on the total weight of the polymer composition.

[0258] 10. The multilayer article according to technical solution 9, wherein the reinforcing filler comprises glass fiber, wollastonite, or both.

[0259] 11. The multilayer article according to any one of technical solutions 1-10, wherein the base layer has a thickness of about 0.3-10 mm (preferably about 0.5-5 mm), and / or the cover layer has a thickness of about 0.2-1.5 mm (preferably about 0.3-1.0 mm and more preferably about 0.3-0.8 mm).

[0260] 12. The multilayer article according to any one of technical solutions 1-11, wherein the covering layer is a dense layer having a porosity of about 20% by volume or less (preferably about 10% by volume or less, more preferably about 5% by volume or less, and most preferably about 2% by volume or less).

[0261] 13. The multilayer article according to any one of technical solutions 1-12, wherein the polymer composition comprises about 0.2-9% by weight (preferably about 1-7% by weight, even more preferably about 1.5-5% by weight and most preferably about 2-4% by weight) of one or more ethylene copolymers, wherein the ethylene copolymers comprise functionalized monomers.

[0262] 14. A multilayer article according to any one of technical solutions 1-13, wherein the base layer is colored by pigments or other colorants, and the cover layer is substantially clear and / or substantially transparent; and the base layer comprises one or more additives selected from the group consisting of antioxidants, processing aids, light stabilizers, heat stabilizers, release agents, and flow modifiers.

[0263] 15. The multilayer article according to any one of technical solutions 1-14, wherein the substrate layer is a dense substrate layer with a porosity of about 10% by volume or less.

[0264] 16. A multilayer article according to any one of claims 1-15, wherein the amount of any styrene copolymer in the base layer is about 0.9% by weight or less based on the total weight of the polymer composition (e.g., based on the total weight of the base layer), and the styrene copolymer contains maleic anhydride, maleic acid, or other monomers that provide carboxyl groups to the styrene copolymer.

[0265] 17. A multilayer article according to any one of technical solutions 1-16, wherein the total amount of the filler (preferably the wollastonite or glass, more preferably the wollastonite), the toughening component (preferably the bulk ABS and any other styrene-acrylonitrile copolymer) and the polycarbonate in the base layer is about 95% by weight or more based on the total weight of the base layer.

[0266] 18. The multilayer article according to any one of technical solutions 1-17, wherein the filler comprises wollastonite having an organic sizing agent.

[0267] 19. A method comprising the following steps:

[0268] i) Create a gap in the mold cavity on the surface of a base layer having a surface, wherein the base layer comprises polycarbonate having a glass transition temperature;

[0269] ii) Injecting the polymerizable composition into the mold cavity to form polyurethane and / or polyurea;

[0270] iii) Contacting the surface with the polymerizable composition, wherein the surface has a temperature below the glass transition temperature; and

[0271] iv) To polymerize the polyurethane and / or the polyurea at least partially when the mold cavity is closed;

[0272] The base layer comprises a polymer composition, wherein the polymer composition is a blend comprising two or more polymers, the polymers comprising the polycarbonate and a toughening component, wherein the toughening component comprises a styrene-acrylonitrile copolymer and an impact modifier; wherein the concentration of the two or more polymers is based on the total weight of the polymer composition, about 70% by weight or higher (preferably about 83% by weight or higher, and more preferably about 88% by weight or higher) and about 100% by weight or lower (preferably about 99% by weight or lower), and the total weight of the polycarbonate and the toughening component is based on the concentration of the two or more polymers in the polymer composition. The total weight of the polymer is about 75-100% by weight, and the weight ratio of the polycarbonate to the toughening component is about 10:90 or higher (preferably about 20:80 or higher, and more preferably about 25:75 or higher) and about 55:45 or lower (preferably about 50:50 or lower, and more preferably about 45:55 or lower), and the concentration of the impact modifier is based on the total weight of the two or more polymers, about 3% by weight or higher (preferably about 5% by weight or higher, and more preferably about 7% by weight or higher) and about 23% by weight or lower (preferably about 18% by weight or lower, more preferably about 15% by weight or lower, and most preferably about 13% by weight or lower).

[0273] 20. The method according to claim 19, wherein the method is used to form a multilayer article according to any one of claims 1-18.

Claims

1. A multi-layered article comprising: i) A base layer comprising a polymer composition, wherein the polymer composition is a blend comprising two or more polymers, the polymers comprising a polycarbonate component and a toughening component, wherein the toughening component comprises a styrene-acrylonitrile copolymer and an impact modifier, wherein the impact modifier is polybutadiene rubber; and ii) A cover layer comprising polyurethane and / or polyurea, said cover layer being directly bonded to said base layer; The concentration of the two or more polymers is 70-100% by weight based on the total weight of the polymer composition; the total weight of the polycarbonate component and the toughening component is 75-100% by weight based on the total weight of the two or more polymers in the polymer composition; the weight ratio of the polycarbonate component to the toughening component is 10:90 to 45:55; and the concentration of the impact modifier is 5-15% by weight based on the total weight of the two or more polymers. The amount of polyester in the polymer composition is 0-1.9% by weight.

2. The multilayer article according to claim 1, wherein the weight ratio of the polycarbonate component to the toughening component is 20:90 to 45:55; and the concentration of the two or more polymers is 88-99% by weight.

3. The multilayer article of claim 2, wherein the polymer composition comprises 10% by weight or less of one or more fillers, based on the total weight of the polymer composition.

4. The multilayer article according to claim 3, wherein the toughening component comprises bulk ABS.

5. The multilayer article of claim 3, wherein the toughening component comprises a grafted ABS impact modifier, and the grafted ABS impact modifier has a polybutadiene concentration of 45-85% by weight based on the total weight of the grafted ABS impact modifier.

6. The multilayer article according to any one of claims 1-5, wherein the polycarbonate component is present in an amount of 20-45% by weight based on the total weight of the polymer composition.

7. The multilayer article of claim 6, wherein the polymer composition comprises ABS thermoplastic, the ABS thermoplastic comprising a polybutadiene-containing phase dispersed in a styrene-containing phase comprising a styrene-acrylonitrile copolymer, wherein the styrene-acrylonitrile copolymer comprises 60% by weight or more styrene and 15% by weight or more acrylonitrile based on the total weight of the acrylonitrile-styrene copolymer.

8. The multilayer article of claim 7, wherein the styrene-acrylonitrile copolymer is a random copolymer comprising 97% by weight or more of acrylonitrile and styrene.

9. The multilayer article according to any one of claims 1-5, wherein the polymer composition comprises 3-30% by weight of reinforcing filler based on the total weight of the polymer composition.

10. The multilayer article of claim 9, wherein the reinforcing filler comprises glass fiber, wollastonite, or both.

11. The multilayer article according to any one of claims 1-5, wherein the base layer has a thickness of 0.3-10 mm, and / or the cover layer has a thickness of 0.2-1.5 mm.

12. The multilayer article according to any one of claims 1-5, wherein the covering layer is a dense layer having a porosity of 10% by volume or less.

13. The multilayer article according to any one of claims 1-5, wherein the polymer composition comprises 0.2-9% by weight of one or more ethylene copolymers, wherein the ethylene copolymers comprise functionalized monomers.

14. The multilayer article according to any one of claims 1-5, wherein the base layer is colored by pigments or other colorants, and the cover layer is substantially clear and / or substantially transparent; and the base layer comprises one or more additives selected from the group consisting of antioxidants, processing aids, light stabilizers, heat stabilizers, release agents, and flow modifiers.

15. The multilayer article according to any one of claims 1-5, wherein the substrate layer is a dense substrate layer with a porosity of 10% by volume or less.

16. The multilayer article according to any one of claims 1-5, wherein the amount of any styrene copolymer in the base layer is 0.9% by weight or less based on the total weight of the polymer composition, and the styrene copolymer comprises maleic anhydride, maleic acid, or other monomers that provide carboxyl groups to the styrene copolymer.

17. The multilayer article of claim 9, wherein the reinforcing filler is wollastonite, and the total amount of wollastonite, the toughening component, and the polycarbonate in the base layer is 95% by weight or more based on the total weight of the base layer.

18. The multilayer article of claim 17, wherein the filler wollastonite has an organic sizing agent.

19. A method for forming a multilayer article, comprising the following steps: i) Create a gap in the mold cavity on the surface of a base layer having a surface, wherein the base layer comprises polycarbonate having a glass transition temperature; ii) Injecting the polymerizable composition into the mold cavity to form polyurethane and / or polyurea; iii) Contacting the surface with the polymerizable composition, wherein the surface has a temperature lower than the glass transition temperature of the polycarbonate; and iv) To polymerize the polyurethane and / or the polyurea at least partially when the mold cavity is closed; The base layer comprises a polymer composition, wherein the polymer composition is a blend comprising two or more polymers, the polymers comprising the polycarbonate and a toughening component, wherein the toughening component comprises a styrene-acrylonitrile copolymer and an impact modifier; wherein the concentration of the two or more polymers is 70-100% by weight based on the total weight of the polymer composition, the total weight of the polycarbonate and the toughening component is 75-100% by weight based on the total weight of the two or more polymers in the polymer composition, and the weight ratio of the polycarbonate to the toughening component is 10:90 to 45:55, and the concentration of the impact modifier is 5-15% by weight based on the total weight of the two or more polymers. The amount of polyester in the polymer composition is 0-1.9% by weight.

20. The method of claim 19, wherein the method is used to form a multilayer article according to any one of claims 1-18.

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