Flame-retardant polycarbonate compositions and molded articles manufactured therefrom, as well as articles

Abstract

The present application relates to flame-retardant polycarbonate compositions and molded articles made therefrom, as well as articles. The polycarbonate composition comprises the following components: an aromatic polycarbonate, a rubber-modified vinyl (co)polymer, an aromatic polyester, a reinforcing material, a phosphorus-containing flame retardant, and a chain extender. A molded article made from a polycarbonate composition according to the present invention has improved adhesion to a polyurethane-based coating system.

Description

Technology Field

[0001] The present invention relates to a polycarbonate composition. In particular, the present invention relates to a flame-retardant polycarbonate composition, a molded article and an article made therefrom. Background Technology

[0002] Flame-retardant polycarbonate (PC) materials possess balanced mechanical properties (especially ductility), thermal stability, as well as processability, and thus have become one of the major types of housing materials widely used for ITA and E&E applications, such as front / rear covers for laptops, netbooks, and display modules.

[0003] US20130131241A describes a flame-retardant thermoplastic composition having excellent flame-retardant effects for thin-walled molded articles, while also having excellent flow characteristics, impact resistance, and elastic modulus. A polycarbonate composition is described comprising polycarbonate, a flame retardant, talc, glass fiber, and an acid stabilizer in synergistic amounts.

[0004] JP 2007-070468A describes a glass-fiber-reinforced flame-retardant resin composition that provides excellent mechanical stability, as well as low anisotropy, excellent fluidity, and also advantageously flame-retardant effects by using flat glass fibers and also another additional layered material.

[0005] In the manufacturing process of final housing parts, injection molding is typically applied first, and then the part still requires the application of spray coating or other surface treatment processes to achieve specific surface appearance effects, tactile properties, and improved scratch resistance. Injection molding and spray coating processes are widely known technologies and are distinct processes.

[0006] In recent years, a new process called "Direct Coating (DC)" has been developed to manufacture composites with excellent surface appearance effects. This DC manufacturing process integrates the injection molding of plastic substrates and the reaction injection molding of polyurethane coatings into a single step.

[0007] For example, US2013196130 A1 discloses a composite material comprising a non-flame-retardant polycarbonate composition as a substrate and a polyurethane coating applied via an online molding process, i.e., "direct coating (DC)". The composite material may be used in automotive applications, for example, for interior decorative parts.

[0008] To apply the DC process, the substrate must have sufficient / excellent adhesion strength with the coating layer.

[0009] To expand DC technology and explore new opportunities in IT and home appliance applications, it is necessary to develop a novel flame-retardant polycarbonate composition that enables DC processing with improved adhesion strength to the polyurethane coating layer while maintaining other properties as a housing material.

[0010] Generally, it is widely known that in the case of polycarbonate compositions, the more ABS (acrylonitrile-butadiene-styrene rubber) is added, the better the adhesive properties become, and that when BDP (bisphenol-A bis(diphenyl phosphate)) is used as a flame retardant in polycarbonate compositions, it has a negative effect on the adhesion between the polycarbonate substrate and the polyurethane coating layer. In order to achieve excellent flame retardant properties in flame-retardant polycarbonate products, it is generally not permissible to add too much ABS (impact modifier), and at the same time, a specific amount of flame retardant, such as a phosphorus-containing flame retardant, must be added. Consequently, it is difficult for flame-retardant polycarbonate products to achieve excellent adhesion with the coating layer.

[0011] There is still a demand for flame-retardant polycarbonate compositions that have excellent adhesion to polyurethane coatings.

[0012] The object of the present invention is to provide a flame-retardant polycarbonate composition having excellent adhesion to a polyurethane coating.

[0013] Another objective of the present invention is to provide a part comprising a flame-retardant polycarbonate composition.

[0014] Another additional objective of the present invention is to provide an article comprising a part comprising a flame-retardant polycarbonate composition.

[0015] Accordingly, according to the first aspect, the present invention provides a flame-retardant polycarbonate composition comprising the following components, all of which are based on the total weight of the composition:

[0016] A) 30-70 wt% aromatic polycarbonate;

[0017] B) 3-10 wt% rubber-modified vinyl (co)polymer;

[0018] C) 3-11 wt% aromatic polyester;

[0019] D) 10-30 wt% of reinforcing material;

[0020] E) 10-20 wt% phosphorus-containing flame retardant; and

[0021] F) 0.5-3 wt% chain extender.

[0022] According to a second aspect, the present invention provides a molded article made from a flame-retardant polycarbonate composition according to a first aspect of the present invention.

[0023] According to a third aspect, the present invention provides an article comprising a substrate made from a flame-retardant polycarbonate composition according to a first aspect of the present invention and a polyurethane layer on at least one side of the substrate.

[0024] According to a fourth aspect, the present invention provides a method for manufacturing an article according to a third aspect of the present invention, comprising the following steps:

[0025] (i) a step of forming a substrate by injecting a molten composition according to the first aspect of the present invention into a first mold cavity,

[0026] (ii) a step of expanding the cavity of the injection mold to create a gap between the substrate and the mold surface of the expanded cavity,

[0027] (iii) a step of forming a polyurethane layer by injecting a polyurethane coating into the gap, and

[0028] (iv) Step of removing the obtained composite member from the mold cavity.

[0029] The flame-retardant polycarbonate composition according to the present invention has excellent toughness, melt fluidity, high heat distortion temperature, and high rigidity, and can be used as a housing material for ITA and E&E applications, such as front / rear covers for notebooks, netbooks, and display modules.

[0030] A molded article produced from a flame-retardant polycarbonate composition according to the present invention has excellent adhesion to a polyurethane coating.

[0031] Other objects, features, aspects, and advantages of the present invention will become much more clearly apparent when reading the following detailed description and examples. Specific details for implementing the invention

[0032] According to a first aspect, the present invention provides a flame-retardant polycarbonate composition comprising the following components, wherein all contents are based on the total weight of the composition:

[0033] A) 30-70 wt% aromatic polycarbonate;

[0034] B) 3-10 wt% rubber-modified vinyl (co)polymer;

[0035] C) 3-11 wt% aromatic polyester;

[0036] D) 10-30 wt% of reinforcing material;

[0037] E) 10-20 wt% phosphorus-containing flame retardant; and

[0038] F) 0.5-3 wt% chain extender.

[0039] As used herein, any amount or value used to indicate the content of ingredients, processing parameters, etc. is understood to be modified by the term "about."

[0040] As used herein, the limit values ​​of the range of values, particularly in expressions such as “between” and “...to ...range,” are included within such ranges unless otherwise indicated.

[0041] As used herein, the expression “at least one” used in this specification corresponds to the expression “one or more”.

[0042] As used herein, the term "comprising" should be interpreted to encompass all specifically mentioned features as well as any additional unspecified features.

[0043] As used herein, the use of the term "comprising" also discloses an embodiment in which no other features other than those specifically mentioned exist (i.e., "made").

[0044] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by a person skilled in the art to which this invention pertains.

[0045] Ingredient A

[0046] According to the first aspect of the present invention, an aromatic polycarbonate is used as component A in a polycarbonate composition.

[0047] Suitable aromatic polycarbonates used according to the present invention may be known from the literature or may be prepared by methods known from the literature (for the preparation of aromatic polycarbonates, see, for example, the literature [Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964] and DE-AS 1 495 626, DE-OS 2 232 877, DE-OS 2 703 376, DE-OS 2 714 544, DE-OS 3 000 610, DE-OS 3 832 396).

[0048] Aromatic polycarbonates are prepared, for example, by a melting process or by reacting a diphenol with a carbonate halide, preferably phosgene and / or an aromatic dicarboxylic acid dihalide, preferably a benzene dicarboxylic acid dihalide, by a phase interface process, optionally using a chain stopper, for example monophenol, and optionally using a trifunctional or non-trifunctional branching agent, for example triphenol or tetraphenol.

[0049] The diphenols for the manufacture of aromatic polycarbonates are preferably those of formula (I):

[0050]

[0051] Here

[0052] A is a C6-C alkylene, C1-C5-alkylidene, C2-C5-alkylidene, C5-C6-cycloalkylidene, -O-, -SO-, -CO-, -S-, -SO2-, and a C6-C alkylene in which an additional aromatic ring optionally containing a heteroatom can be condensed. 12 - Arylene, or a group of chemical formula (II) or (III):

[0053]

[0054] B is C1-C in each case 12-alkyl, preferably methyl, halogen, preferably chlorine and / or bromine, and

[0055] x is independently 0, 1, or 2 in each case, p is 1 or 0, and,

[0056] R 5 and R 6 For each X', individually, hydrogen or C1-C6-alkyl, preferably hydrogen, methyl, or ethyl, can be selected independently of each other, and

[0057] X' is carbon, and

[0058] m is an integer from 4 to 7, preferably 4 or 5, provided,

[0059] R on at least one X' atom 5 and R 6 Both of these are alkyl.

[0060] Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenol, 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)-diisopropyl-benzene and their cyclic-brominated and / or cyclic-chlorinated derivatives.

[0061] Particularly preferred diphenols are 4,4'-dihydroxydiphenyl, 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 sulfide, 4,4'-dihydroxydiphenyl-sulfone and their brominated and sabrominated or chlorinated derivatives, such as, for example, 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.

[0062] 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A) is particularly preferred.

[0063] Diphenol can be used individually or in any mixture.

[0064] Diphenol can be obtained by methods known from the literature or by methods known from the literature.

[0065] Suitable chain stoppers for the manufacture of thermoplastic aromatic polycarbonates are, for example, phenol, p-chlorophenol, p-tert.-butylphenol or 2,4,6-tribromophenol, as well as long-chain alkyl phenols such as 4-(1,3-tetramethylbutyl)-phenol according to DE-OS 2 842 005, or monoalkylphenols or dialkyl phenols containing a total of 8 to 20 C atoms in alkyl substituents such as 3,5-di-tert.-butylphenol, p-iso-octylphenol, p-tert.-octylphenol, p-dodecylphenol, and 2-(3,5-dimethylheptyl)-phenol and 4-(3,5-dimethylheptyl)-phenol. The amount of chain stopper used is generally 0.5 mol.% to 10 mol.% relative to the molar total of the diphenols used in each case.

[0066] Thermoplastic aromatic polycarbonates can be branched in a known manner, preferably by incorporating trifunctional or excess trifunctional compounds, for example those having three or more phenolic groups, at a rate of 0.05 to 2.0 mol.% relative to the total amount of diphenol used.

[0067] Both homopolycarbonates and copolycarbonates are suitable. For the preparation of the copolycarbonate according to component A of the present invention, a polydiorganosiloxane having 1 to 25 wt%, preferably 2.5 to 25 wt% (relative to the total amount of diphenol used) of hydroxyaryloxy terminal groups may also be used. These may be prepared by methods known (see, for example, U.S. Patent No. 3,419,634) or known from the literature. The preparation of a copolycarbonate containing polydiorganosiloxane is described, for example, in DE-A 3 334 782.

[0068] In addition to bisphenol A homopolycarbonate, the preferred polycarbonate is a bisphenol A copolycarbonate containing other diphenols mentioned as preferred or particularly preferred, particularly 2,2-bis(3,5-dibromo-4-hydroxyphenyl)-propane, in an amount of up to 15 mol.% with respect to the molar total of the diphenols.

[0069] The aromatic dicarboxylic acid dihalides for the manufacture of aromatic polyester carbonates are preferably dichlorides of isophthalic acid, terephthalic acid, diphenyl ether-4,4'-dicarboxylic acid, and naphthalene-2,6-dicarboxylic acid.

[0070] A mixture of dichloride of isophthalic acid and terephthalic acid in a ratio of 1:20 to 20:1 is particularly preferred.

[0071] When manufacturing polyester carbonates, carbonate halides, preferably phosgene, are also used as difunctional acid derivatives.

[0072] In addition to the already mentioned monophenols, his chlorocarbonate esters and C1-C 22 Acid chlorides of aromatic monocarboxylic acids that can be optionally substituted by alkyl groups or halogen atoms, as well as aliphatic C2-C 22Monocarboxylic acid chloride is also a possible chain stopper for the manufacture of aromatic polyester carbonates.

[0073] The amount of chain stopper is 0.1 to 10 mol.% in each case, relative to the moles of diphenol in the case of phenolic chain stoppers, and relative to the moles of dicarboxylic acid dichloride in the case of monocarboxylic acid chain stoppers.

[0074] Aromatic polyester carbonates may also have aromatic hydroxycarboxylic acids incorporated therein.

[0075] Aromatic polyester carbonates can be linear or branched in a known manner (see also DE-A 2 940 024 and DE-A 3 007 934).

[0076] It is possible to use, for example, a trifunctional or polyfunctional carboxylic acid chloride as a branching agent, such as trimethic 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 in an amount of 0.01 to 1.0 mol.% (relative to the dicarboxylic acid dichloride used), or as a branching agent, a trifunctional or polyfunctional phenol, such as phloroglucinol, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptene-2,4,4-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptane, 1,3,5-tri-(4-hydroxyphenyl)-benzene, 1,1,1-tri-(4-hydroxyphenyl)-ethane, tri-(4-hydroxyphenyl)-phenylmethane, 2,2-bis[4,4-bis(4-hydroxyphenyl)-cyclohexyl]-propane, 2,4-bis(4-hydroxyphenyl-isopropyl)-phenol, tetra-(4-hydroxyphenyl)-methane, 2,6-bis(2-hydroxy-5-methyl-benzyl)-4-methyl-phenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-propane, tetra-(4-[4-hydroxyphenylisopropyl]-phenoxy)-methane, and 1,4-bis[4,4'-dihydroxytriphenyl]-methyl-benzene may be used in an amount of 0.01 to 1.0 mol.% relative to the diphenol used. Phenolic branching agents can be added together with diphenol, and acid chloride branching agents can be introduced together with acid chloride.

[0077] Preferably, the aromatic polycarbonate used according to the present invention has a weight average molecular weight (Mw) of at least 10,000 g / mol, preferably 20,000 g / mol to 300,000 g / mol.

[0078] As an example of an aromatic polycarbonate, Makrolon@2600, available from Covestro Polymers Co. Ltd, may be mentioned as a linear bisphenol A polycarbonate having a relative solution viscosity of 1.28 (ii) (measured with a solution of 0.5 g of polycarbonate in 100 ml of methylene chloride at 25°C) and a weight-average molecular weight of 26000 g / mol.

[0079] Thermoplastic aromatic polycarbonates can be used alone or in any mixture.

[0080] Advantageously, polycarbonate is present in the polymer composition in an amount ranging from 35 wt% to 65 wt%, preferably from 40 wt% to 60 wt%, based on the total weight of the composition.

[0081] Ingredient B

[0082] According to the first aspect of the present invention, a rubber-modified vinyl (co)polymer is used as component B in a polycarbonate composition.

[0083] Preferably, the rubber-modified vinyl (co)polymer

[0084] B1) at least one vinyl monomer in an amount of 5 to 95, preferably 8 to 90, particularly 20 to 85 wt%

[0085] B2) on one or more graft substrates having a glass transition temperature of < 10°C, preferably < 0°C, particularly preferably < -20°C, in an amount of 95 to 5, preferably 92 to 10, particularly 80 to 15 wt%

[0086] Includes, and wt% is calculated based on the weight of the rubber-modified vinyl (co)polymer.

[0087] The glass transition temperature was determined by differential dynamic calorimetry (DSC) according to the standard DIN EN 61006 at a heating rate of 10 K / min, and T as the midpoint temperature. g is defined (tangent method).

[0088] Graft substrate B2 generally has an average particle size (d) of 0.05 to 10 μm, preferably 0.1 to 5 μm, and more preferably 0.2 to 1 μm. 50 It has a value.

[0089] Average particle size d 50 is the diameter at which 50 wt% of the particles exist above and below it in each case. This can be determined by ultracentrifugation measurement (W. Scholtan, H. Lange, Kolloid, Z. und Z. Polymere 250 (1972), 782-1796).

[0090] At least one type of vinyl monomer B1 is preferably a mixture of the following:

[0091] B1.1) 50 to 99, preferably 65 to 85, particularly 75 to 80 wt% of vinyl aromatics and / or vinyl aromatics substituted on the nucleus (e.g., styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene) and / or methacrylic acid (C1-C8)-alkyl esters (e.g., methyl methacrylate, ethyl methacrylate), and

[0092] B1.2) 1 to 50, preferably 15 to 35, particularly 20 to 25 wt% of vinyl cyanide (unsaturated nitriles, e.g., acrylonitrile and methacrylonitrile) and / or (meth)acrylic acid (C1-C8)-alkyl esters, e.g., methyl methacrylate, n-butyl acrylate, t-butyl acrylate and / or derivatives of unsaturated carboxylic acids (e.g., anhydrides and imides), e.g., maleic anhydride and N-phenyl-maleimide,

[0093] wt% is calculated based on the weight of vinyl monomer B1.

[0094] Preferred monomer B1.1 is selected from monomers styrene, α-methylstyrene, and methyl methacrylate. Preferred monomer B1.2 is selected from monomers acrylonitrile, maleic anhydride, and methyl methacrylate. More preferably, monomer B1.1 is styrene and monomer B1.2 is acrylonitrile.

[0095] Examples of graft substrate B2 may include diene rubber, EP(D)M rubber, that is, those based on ethylene / propylene and optionally diene, and acrylate, polyurethane, silicone, chloroprene and ethylene / vinyl acetate rubber and silicone / acrylate composite rubber.

[0096] The preferred graft substrate B2 is selected from diene rubber, for example, butadiene and isoprene, or a mixture of diene rubber, or a copolymer of diene rubber and additional copolymerizable monomers (for example, according to B1.1 and B1.2) or a mixture thereof, provided that the glass transition temperature of component B2 is < 10°C, preferably < 0°C, particularly preferably < -20°C (less than).

[0097] Pure polybutadiene rubber is particularly preferred as graft substrate B2.

[0098] Particularly desirable rubber-modified vinyl (co)polymers are, for example, ABS or MBS polymers, such as, for example, DE-OS 2 035 390 (= US 3 644 574) or DE-OS 2 248 242 (= GB 1 409 275) and those described in the literature [Ullmanns, Enzyklopaedie der Technischen Chemie, vol. 19 (1980), p. 280 et seq.].

[0099] Rubber-modified vinyl (co)polymers can be produced by free radical polymerization, for example by emulsion, suspension, solution, or bulk polymerization, preferably by emulsion or bulk polymerization, particularly by emulsion polymerization.

[0100] Advantageously, the rubber-modified vinyl (co)polymer is present in the polymer composition in an amount ranging from 4 wt% to 10 wt%, preferably from 4 wt% to 8 wt%, based on the total weight of the composition.

[0101] Ingredient C

[0102] According to the first aspect of the present invention, an aromatic polyester is used as component C in a polycarbonate composition.

[0103] The term polyester includes homo-polyester and co-polyester resins, which are resins whose molecular structure comprises at least one bond derived from a carboxylic acid, preferably excluding a link derived from a carbonate. These are known resins and can be prepared by condensation of a diol component and a diacid or ester exchange polymerization according to known methods. An example thereof is an ester derived from the condensation of cyclohexanedimethanol and ethylene glycol with terephthalic acid or a combination of terephthalic acid and isophthalic acid.

[0104] Suitable resins include poly(alkylene dicarboxylate). Suitable methods for producing such resins are disclosed in U.S. Patent Nos. 2,465,319, 3,953,394 and 3,047,539, all of which are incorporated herein by reference.

[0105] Preferably, the aromatic polyester is selected from polyalkylene terephthalate.

[0106] Suitable polyalkylene terephthalates are characterized by an intrinsic viscosity of at least 0.2, preferably about at least 0.4 deciliters / gram, as measured by the relative viscosity of a 1% solution in dichloroacetic acid at about 25°C. Although the upper limit is not critical, it generally does not exceed about 2.5 deciliters / gram. Particularly preferred polyalkylene terephthalates are those having an intrinsic viscosity in the range of 0.4 to 1.3 deciliters / gram.

[0107] The alkylene units of a suitable polyalkylene terephthalate for use in the present invention contain 2 to 5, preferably 2 to 4, carbon atoms. The alkylene units may be straight chains or branched chains.

[0108] Examples of suitable polyalkylene terephthalates for use in the present invention may include poly(ethylene terephthalate) (PET), poly(1,4-butylene terephthalate) (PBT), and poly(trimethylene terephthalate) (PTT).

[0109] In a preferred embodiment, poly(ethylene terephthalate) is used as component C.

[0110] Advantageously, aromatic polyester is present in the polymer composition in an amount ranging from 5 wt% to 10 wt%, preferably from 6 wt% to 10 wt%, based on the total weight of the composition.

[0111] Ingredient D

[0112] According to the first aspect of the present invention, a reinforcing material is used in a polycarbonate composition as component D.

[0113] Preferably, the reinforcing material is glass fiber.

[0114] The glass fiber may be composed of a glass composition selected from the group of M-, E-, A-, S-, R-, AR-, ECR-, D-, Q-, or C-glass.

[0115] Glass fibers can be used in the form of continuous filament fibers (roving), cut glass fibers, crushed fibers, glass fiber fabrics, or mixtures thereof, preferably cut glass fibers and crushed fibers, more preferably cut glass.

[0116] The length of the cut glass fibers prior to mixing is preferably in the range of 0.5 to 10 mm, more preferably in the range of 1.0 to 8 mm, and most preferably in the range of 1.5 to 6 mm.

[0117] The cut glass fibers used can have various cross-sections. Circular, elliptical, ovate, octagonal, and flat cross-sections are preferred, and circular, ovate, and also flat cross-sections are more preferred.

[0118] The diameter of the circular fiber is preferably in the range of 5 to 25 μm, more preferably in the range of 6 to 20 μm, and even more preferably in the range of 7 to 17 μm.

[0119] Preferred flat and oval glass fibers have a cross-sectional height-to-width ratio of about 1.0:1.2 to 1.0:8.0, preferably 1.0:1.5 to 1.0:6.0, more preferably 1.0:2.0 to 1.0:4.0.

[0120] Flat and oval glass fibers preferably have an average fiber height of 4 μm to 17 μm, more preferably 6 μm to 12 μm, and even more preferably 6 μm to 8 μm, and also an average fiber width of 12 μm to 30 μm, more preferably 14 μm to 28 μm, and even more preferably 16 μm to 26 μm.

[0121] In a preferred embodiment, the reinforcing material used is an E-glass fiber having a length of 1.5 to 6 mm and a circular cross-section with a diameter of 7 to 17 μm.

[0122] Advantageously, the reinforcing material is present in the polymer composition in an amount ranging from 10 wt% to 28 wt%, preferably from 12 wt% to 25 wt%, with respect to the total weight of the composition.

[0123] Ingredient E

[0124] According to the first aspect of the present invention, a phosphorus-containing flame retardant is used as component E in a polycarbonate composition.

[0125] Phosphorus-containing flame retardants are preferably selected from monomeric and oligomeric phosphoric acid and phosphonic acid esters, phosphonate amines, and phosphazenes.

[0126] Desirable monomeric and oligomeric phosphate and phosphonic acid esters are phosphorus compounds of formula (IV):

[0127]

[0128] Here

[0129] R 1 , R 2 , R 3 and R 4 are independently C1-C8 alkyl, C5-C6 cycloalkyl, and C6-C 20 Aryl or C7-C 12 Representing aralkyl groups, each of which is optionally alkyl-substituted, preferably C1-C4 alkyl-substituted, and

[0130] n represents 0 or 1 independently of each other, and

[0131] q represents 0 to 30, and

[0132] X represents a mononuclear or polynuclear aromatic residue having 6 to 30 carbon atoms or a linear or branched aliphatic residue having 2 to 30 carbon atoms, which can be OH-substituted and may contain 8 or fewer ether bonds.

[0133] Preferably, R 1 , R 2 , R 3 and R4 represents C1-C4 alkyl, phenyl, naphthyl, or phenyl C1-C4 alkyl groups independently of each other. Aromatic group R 1 , R 2 , R 3 and R 4 It itself can be substituted with an alkyl group, preferably a C1-C4 alkyl. Particularly preferred aryl residues are cresyl, phenyl, xylenyl, propylphenyl, or butylphenyl.

[0134] Preferably, X in formula (IV) is a mononuclear or polynuclear aromatic residue having 6 to 30 carbon atoms. This is preferably derived from the diphenol of formula (I).

[0135] n in formula (IV) can be 0 or 1 independently of each other; n is preferably equal to 1.

[0136] q represents an integer from 0 to 30, preferably from 0 to 20, particularly preferably from 0 to 10, and in the case of a mixture, represents an average value from 0.8 to 5.0, preferably from 1.0 to 3.0, more preferably from 1.05 to 2.00, particularly preferably from 1.08 to 1.60.

[0137] X is derived particularly from resorcinol, hydroquinone, bisphenol A, or diphenylphenol. Particularly preferably, X is derived from bisphenol A.

[0138] The phosphorus compounds of formula (IV) are, in particular, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, diphenylcresyl phosphate, diphenyl octyl phosphate, diphenyl 2-ethylcresyl phosphate, tri(isopropylphenyl)phosphate, resorcinol-crosslinked oligophosphate, and bisphenol A-crosslinked oligophosphate. The use of oligomeric phosphate esters of formula (IV) derived from bisphenol A is particularly preferred.

[0139] As component E, a bisphenol A-based oligophosphate according to chemical formula (V) is most preferred.

[0140]

[0141] Phosphorus compounds according to component E are known (see, e.g., EP-A 0 363 608, EP-A 0 640 655) or can be prepared in a similar manner by known methods (e.g., Ullmanns Enzyklopadie der technischen Chemie, vol. 18, pp. 301 ff. 1979; Houben-Weyl, Methoden der organischen Chemie, vol. 12 / 1, p. 43; Beilstein vol. 6, p. 177).

[0142] As component E according to the present invention, it is also possible to use a mixture of phosphates having different chemical structures and / or the same chemical structure and different molecular weights. The flame retardants may be used individually, as any mixture with each other, or as a mixture with other phosphorus-containing flame retardants.

[0143] Advantageously, the phosphorus-containing flame retardant is present in the polymer composition in an amount ranging from 10 wt% to 18 wt%, preferably from 12 wt% to 18 wt%, based on the total weight of the composition.

[0144] Ingredient F

[0145] According to the first aspect of the present invention, a chain extender is used as component F in a polycarbonate composition.

[0146] Preferably, the chain extender used is a polyfunctional chain extender having at least two reactive epoxy groups. The polyfunctional epoxy material may contain aromatic and / or aliphatic residues. Examples thereof include epoxy novolak resins, cycloaliphatic epoxy resins, reaction products of epoxidized vegetable (e.g., soybean, linseed) oils, bisphenol A-based epoxy resins, tetraphenylethylene epoxides, styrene-acrylic copolymers containing pendant glycidyl groups, glycidyl methacrylate-containing polymers and copolymers, and difunctional epoxy compounds such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate.

[0147] In some embodiments, the polyfunctional chain extender is an epoxy-functional polymer comprising an oligomer. An exemplary polymer having multiple epoxy groups comprises one or more ethylene-based unsaturated compounds (e.g., styrene, ethylene, etc.) and an epoxy-containing ethylene-based unsaturated monomer (e.g., glycidyl C 1-4 It includes reaction products of (alkyl)acrylates, allyl glycidyl ethacrylates, and glycidyl itaconate.

[0148] In some embodiments, the polyfunctional chain extender is a styrene-acrylate copolymer (including oligomers) containing glycidyl groups incorporated as side chains. Several useful examples are described in International Patent Application WO 03 / 066704 A1 assigned to Johnson Polymer, LLC, the full text of which is incorporated herein by reference. These materials are based on copolymers having styrene and acrylate building blocks, to which glycidyl groups are incorporated as side chains. A higher number of epoxy groups per polymer chain is preferred, for example, at least 10, or more than 15, or more than 20. These polymeric materials generally have a weight-average molecular weight (Mw) in the range of 3,000 to 15,000 daltons, preferably 4,000 to 12,000 daltons, and more preferably 6,000 to 10,000 daltons. These are commercially available, for example, from Johnson Polymer, LLC (now BASF) under the trade name JONCRYL, more specifically JONCRYL ADR 4368, which has a weight average molecular weight of 7250 and an epoxy equivalent weight of 310 g / mol.

[0149] Advantageously, the chain extender is present in the polycarbonate composition in an amount ranging from 0.5 wt% to 2.5 wt%, preferably from 0.8 wt% to 2.5 wt%, and more preferably from 0.8 wt% to 2 wt%, based on the total weight of the composition.

[0150] Additional polymer additives

[0151] The polycarbonate composition according to the present invention may additionally include one or more additional polymer additives as component G.

[0152] Preferably, additional polymer additives are selected from anti-slip agents (e.g., compounds belonging to the class of fluorinated polyolefins, e.g., PTFE), internal and external lubricants and mold release agents (e.g., pentaerythritol tetrastearate, montan wax or polyethylene wax), flow aids, antistatic agents, conductive additives, stabilizers (e.g., UV / light stabilizers, heat stabilizers, antioxidants, transesterification inhibitors, agents that prevent hydrolysis), additives that improve scratch resistance (e.g., silicone oil), IR absorbers, optical brighteners, fluorescent additives, and dyes and pigments (e.g., carbon black, titanium dioxide or iron oxide), or mixtures thereof.

[0153] The composition according to the present invention particularly preferably contains at least one mold release agent, preferably pentaerythritol tetrastearate.

[0154] A person of ordinary skill in the relevant technical field can adjust the amount of polymer additives as needed.

[0155] The flame-retardant polycarbonate composition according to the present invention can be manufactured by various methods involving an intimate mixing of materials required for the composition.

[0156] For example, the materials required for the composition are first blended in a high-speed mixer. Other low-shear processes, including but not limited to manual mixing, may also achieve this blending. Subsequently, the blend is fed through a hopper to the neck of a twin-screw extruder. Alternatively, at least one of the components may be incorporated into the composition by being fed directly into the extruder from the neck and / or downstream through an attached stuffer. Additives may also be formulated as a masterbatch with the desired polymeric resin and fed into the extruder. The extruder is generally operated at a temperature higher than necessary to allow the composition to flow. The extruded material is immediately quenched in a water bath and pelletized. The pellets may have a length of 1 / 4 inch or less as described. These pellets may be used for subsequent molding, shaping, or shape processing.

[0157] The melt blending method is desirable because melt blending equipment can be used in commercial polymer processing facilities.

[0158] Exemplary examples of equipment used in these melt processing methods include co-rotating and reverse-rotating extruders, single-screw extruders, co-kneaders, and various other types of extrusion equipment.

[0159] During processing, the temperature of the melt is preferably minimized to avoid excessive decomposition of the polymer. While it is often desirable to maintain a melt temperature of 260°C to 300°C in the molten polycarbonate composition, a higher temperature may be used under the condition that the residence time of the resin in the processing equipment is kept short.

[0160] In some embodiments, the melt-processed composition is discharged from processing equipment, such as an extruder, through a small discharge hole of a die. The resulting strand of molten resin is cooled by passing the strand through a water bath. The cooled strand can be cut into small pellets for packaging and further handling.

[0161] According to a second aspect, the present invention provides a molded article made from a flame-retardant polycarbonate composition according to a first aspect of the present invention.

[0162] The flame-retardant polycarbonate composition according to the present invention can be molded into useful shaped articles by various means such as injection molding, extrusion, rotational molding, blow molding, and thermoforming, and can form articles such as personal computers, laptops and portable computers, mobile phone antennas, and other communication equipment.

[0163] The molded article can have any shape as needed. For example, it can be a flat molded article.

[0164] In some embodiments, the article is injection molded.

[0165] According to a third aspect, the present invention provides an article comprising a substrate made from a flame-retardant polycarbonate composition according to a first aspect of the present invention and a polyurethane layer on at least one side of the substrate.

[0166] polyurethane

[0167] Preferably, the polyurethane layer is formed by the complete polymerization of a reactive polyurethane raw material mixture comprising the following:

[0168] At least one type of polyisocyanate component,

[0169] At least one polyfunctional H-active compound, and

[0170] Optional polyurethane additives and / or process aids.

[0171] Depending on the reactivity of the components of the reactive polyurethane raw material mixture, the components may be pre-mixed or mixed in a known manner during application. Application may be performed particularly by direct coating (DC).

[0172] Preferably, the H-active polyfunctional compound is a polyol.

[0173] As used herein, the term "polyurethane" is also understood to mean polyurethaneurea, wherein a compound having an NH functional group is used as a polyfunctional H-active compound, optionally as a mixture with a polyol.

[0174] polyisocyanate

[0175] Suitable polyisocyanates are aromatic, ar aliphatic, aliphatic, or cycloaliphatic polyisocyanates known to those skilled in the art, having NCO functional groups, preferably iminooxadiazinedione, isocyanurate, urethdione, urethane, allophanate, biuret, urea, oxadiazinetrione, oxazolidinone, acylurea, and / or carbodiimide structures. These may be used individually or in any desired mixture with one another.

[0176] In this regard, the aforementioned polyisocyanates are based on di- and triisocyanates that are known in themselves to a person skilled in the art, and have aliphatic, cycloaliphatic, araliphatic and / or aromatic bonded isocyanate groups, regardless of whether they were manufactured using phosgene or by a phosgene-free process. Examples of these di- and triisocyanates include 1,4-diisocyanatobutane, 1,5-diisocyanatopentane, 1,6-diisocyanatohexane (HDI), 2-methyl-1,5-diisocyanatopentane, 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- and 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,10-diisocyanatodecane, 1,3- and 1,4-diisocyanatocyclohexane, 1,3- and 1,4-bis-(isocyanatomethyl)-cyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone-diisocyanate, IPDI), 4,4'-Diisocyanatodicyclohexylmethane, 4-Isocyanatomethyl-1,8-octane-diisocyanate (triisocyanatononan, TIN), w,w'-Diisocyanato-1,3-dimethylcyclohexane (H6XDI), Isocyanato-1-methyl-3-isocyanatomethylcyclohexane, Isocyanato-1-methyl-4-isocyanatomethylcyclohexane, Bis-(isocyanatomethyl)-norbornane, 1,5-Naphthalene-Diisocyanate, 1,3- and 1,4-Bis-(2-isocyanatoprop-2-yl)-benzene (TMXDI), 2,4- and 2,6-Diisocyanatotoluene (TDI), particularly 2,4 and 2,6 isomers and industrial-grade mixtures of these two isomers, 2,4'- and 4,4'-diisocyanato-diphenylmethane (MDI), polymeric MDI (pMDI), 1,5-diisocyanatonaphthalene, 1,3-bis(isocyanatomethyl)benzene (XDI) and any desired mixture of the mentioned compounds.

[0177] In this regard, preferably, the polyisocyanate has an average NCO functional value of 2.0 to 5.0, preferably 2.2 to 4.5, particularly preferably 2.2 to 2.7, and an isocyanate group content of 5.0 to 37.0 wt%, preferably 14.0 to 34.0 wt%.

[0178] In a preferred embodiment, polyisocyanates of the aforementioned type or polyisocyanate mixtures having an aliphatic and / or cycloaliphatic bonded isocyanate group exclusively are used.

[0179] Very particularly preferably, the polyisocyanates of the type mentioned above are based on hexamethylene-diisocyanate, isophorone-diisocyanate, isomer bis-(4,4'-isocyanatetocyclohexyl)-methane and mixtures thereof.

[0180] Among more high molecular weight modified polyisocyanates, prepolymers known from polyurethane chemistry having terminal isocyanate groups in a molecular weight range of 400 to 15,000, preferably 600 to 12,000, are particularly important. These compounds are prepared in a manner known in themselves by reacting an excess amount of a simple polyisocyanate of the type mentioned as an example with an organic compound having at least two groups reactive to the isocyanate groups, in particular an organic polyhydroxy compound. Suitable polyhydroxy compounds are simple polyfunctional alcohols with a 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, as well as both polyether polyols and / or polyester polyols of a type known in itself from polyurethane chemistry, particularly having a molecular weight of 600 to 12,000, preferably 800 to 4,000, which have at least two, generally two to eight, but preferably two to six primary and / or secondary hydroxyl groups. For example, NCO prepolymers obtained from low molecular weight polyisocyanates of the types mentioned as examples and less desirable compounds having groups reactive to isocyanate groups, such as polythioether polyols, polyacetals containing hydroxyl groups, polyhydroxy-polycarbonates, polyester-amides containing hydroxyl groups, or copolymers containing hydroxyl groups of olefinic unsaturated compounds, may also be used.

[0181] Compounds having groups reactive to isocyanate groups, particularly hydroxyl groups, and suitable for the preparation of NCO prepolymers are, for example, 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 simple polyisocyanates of the type mentioned above, for example, while maintaining an excess amount of NCO. The NCO prepolymers generally have an NCO content of 10 to 26, preferably 15 to 26 wt%.

[0182] As used herein, "NCO prepolymer" or "prepolymer having terminal isocyanate groups" should be understood to mean both the reaction product itself and a mixture having an excess amount of unreacted starting polyisocyanate, often referred to as a "semi-prepolymer."

[0183] Polyfunctional H-active compounds

[0184] A suitable H-active component is a polyol having an average OH value of 5 to 600 mg KOH / g and an average functional value of 2 to 6. A polyol having an average OH value of 10 to 50 mg KOH / g is preferred. A suitable polyol according to the present invention is, for example, a polyhydroxy-polyether accessible by alkoxylation of a suitable starting molecule, 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 alcohol, or phenols, such as bisphenol A, may likewise function as starting materials. Alkoxylation is carried out using propylene oxide and / or ethylene oxide in any desired order or as a mixture.

[0185] In addition to polyols, at least one additional crosslinking agent and / or chain extender selected from the group comprising amines and amino alcohols, e.g., ethanolamine, diethanolamine, diisopropanolamine, ethylenediamine, triethanolamine, isophoronediamine, 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, e.g., ethylene glycol, diethylene glycol, 1,4-dihydroxybutane, 1,6-dihydroxyhexane, dimethylolpropane, glycerol and pentaerythritol, and sorbitol and sucrose, or mixtures of these compounds may additionally be present.

[0186] Polyester polyols, such as those accessible by the reaction of a low molecular weight alcohol with a polyfunctional carboxylic acid, such as adipic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, or anhydrides of these acids, in a manner known in itself, are additionally suitable, provided that the viscosity of the H-active component does not become too high. A preferred polyol containing an ester group is castor oil. Additionally, formulations containing castor oil, such as those obtainable by the dissolution of a resin, for example, an aldehyde-ketone resin, and the modification of castor oil, and polyols based on other natural oils are also suitable.

[0187] Higher molecular weight polyhydroxy-polyethers, in which high molecular weight heavy adducts, polycondensates, or polymers exist in a finely dispersed, dissolved, or grafted form, are also suitable. These modified polyhydroxy compounds are obtained in a manner known in themselves, for example, by allowing a heavy addition reaction (e.g., reaction between a polyisocyanate and an amino-functional compound) or a polycondensation reaction (e.g., reaction between formaldehyde and a phenol and / or amine) to proceed in-situ in a compound containing a hydroxyl group. However, it is also possible to mix a pre-prepared aqueous polymer dispersion with the polyhydroxy compound and then remove water from the mixture.

[0188] Polyhydroxy compounds modified by vinyl polymers, such as those obtained by the polymerization of styrene and acrylonitrile in the presence of polyether or polycarbonate polyols, are also suitable for the manufacture of polyurethanes. If polyether polyols modified by graft polymerization with vinylphosphonic acid esters and optionally (meth)acrylonitrile, (meth)acrylamide, or OH-functional (meth)acrylic acid esters are used according to DE-A 2 442 101, DE-A 2 844 922 and DE-A 2 646 141, plastics of special flame resistance are obtained.

[0189] Representative examples of the mentioned compounds used as H-active compounds are listed, for example, in the literature [High Polymers, vol. XVI, "Polyurethanes Chemistry and Technology", Saunders-Frisch (ed.) Interscience Publishers, New York, London, vol. 1, p. 32-42, 44, 54 and vol. II, 1984, p. 5-6 and p. 198-199].

[0190] A mixture of the listed compounds may also be used.

[0191] Limitations on the average OH value and average functional value of the H-active component are particularly due to the increasing embrittlement of the polyurethane produced. However, since the potential to affect the physical polymer properties of the polyurethane is known in principle to those skilled in the art, the NCO component, aliphatic diol, and polyol can be adjusted to one another in an advantageous way.

[0192] The ratio of isocyanate groups from polyisocyanates to isocyanate-reactive groups, such as hydroxyl groups, from polyfunctional H-active compounds (NCO / OH ratio) can be over a wide range. Thus, a ratio of 0.2:1.0 to 4.0:1.0 can be used for coating technology 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.

[0193] All auxiliary materials and additives known by themselves, such as release agents, foaming agents, fillers, catalysts, and flame retardants, can be used for the manufacture of polyurethane layers.

[0194] In this regard, optional auxiliary substances and additives are as follows:

[0195] a) Water and / or volatile inorganic or organic materials as blowing agents

[0196] Useful organic blowing agents include, for example, acetone, ethyl acetate, halogen-substituted alkanes such as methylene chloride, chloroform, ethylidene chloride, vinylidene chloride, monofluorotrichloromethane, chlorodifluoromethane, dichlorodifluoromethane, and also butane, hexane, heptane, or diethyl ether, and useful inorganic blowing agents include air, CO2, or N2O. The blowing effect can also be achieved by adding compounds that decompose at temperatures above room temperature, releasing a gas, for example, nitrogen, such as azo compounds, for example, azodicarbonamide and azoisobutyronitrile.

[0197] b) catalyst

[0198] The catalyst is, for example, tertiary amines (e.g., triethylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, N,N,N',N'-tetramethylethylenediamine, pentamethyldiethylenetriamine and higher homologues, 1,4-diazabicyclo[2.2.2]octane, N-methyl-N'-dimethylaminoethylpiperazine, bis(dimethylaminoalkyl)piperazine, N,N-dimethylbenzylamine, N,N-dimethylcyclohexylamine, N,N-diethylbenzylamine, bis(N,N-diethylaminoethyl)adipate, N,N,N',N'-tetramethyl-1,3-butanediamine, N,N-dimethyl-β-phenylethylamine, 1,2-dimethylimidazole, 2-methylimidazole), monocyclic and bicyclic amides, bis(dialkylamino)alkyl ethers, Mannich bases formed from tertiary amines having an amide group (preferably a formamide group), secondary amines (e.g., dimethylamine), aldehydes (preferably formaldehyde or ketones such as acetone, methyl ethyl ketone, or cyclohexanone), and phenols (e.g., phenol, nonylphenol, or bisphenol), tertiary amines having a hydrogen atom active to an isocyanate group (e.g., triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N,N-dimethylethanolamine), and reaction products thereof with alkylene oxides such as propylene oxide and / or ethylene oxide, secondary / tertiary amines having carbon-silicon bonds, silamines (2,2,4-trimethyl-2-silamorfolin and 1,3-diethylaminomethyltetramethyldisiloxane), Nitrogen-containing bases (e.g., tetraalkylammonium hydroxide), alkali metal hydroxides (e.g., sodium hydroxide, alkali metal phenoxide, e.g., sodium phenoxide), alkali metal alkoxides (e.g., sodium methoxide), and / or hexahydrotriazines.

[0199] The reaction between the NCO group and the Zerewitinoff-active hydrogen atom is, in itself known, significantly accelerated by lactams and azalactams, where the association between the lactam and the compound having acidic hydrogen occurs first.

[0200] It is also possible to use organometallic compounds, in particular organotin and / or bismuth compounds, as catalysts. Useful organotin compounds include sulfur compounds such as di-n-octyltin mercaptide, as well as preferably tin(II) salts of carboxylic acids such as tin(II) acetate, tin(II) octoate, tin(II) ethylhexoate and tin(II) laurate, and tin(IV) compounds, such as dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate or dioctyltin diacetate. Organotin bismuth catalysts are described, for example, in patent application WO 2004 / 000905.

[0201] It is also, of course, possible to use any of the catalysts mentioned above as a mixture. In this regard, combinations of organometallic compounds with amidine, aminopyridine, or hydrazinopyridine are particularly important.

[0202] The catalyst is generally used in an amount of about 0.001 weight% to 10 weight% based on the total amount of a compound having at least two hydrogen atoms that is reactive to the isocyanate.

[0203] c) Surface-active additives, e.g., emulsifiers and foam stabilizers

[0204] Useful emulsifiers include, for example, the sodium salt of castor oil sulfonate or the salt of a fatty acid with an amine, such as diethylammonium oleate or diethanolammonium stearate. As a surface-active additive, it is also possible to use a sulfonic acid, for example dodecylbenzenesulfonic acid or dinaphthylmethanedisulfonic acid, or an alkali metal or ammonium salt of a fatty acid, such as ricinoleic acid or a polymeric fatty acid.

[0205] Useful foam stabilizers include polyethersiloxanes, particularly water-soluble representatives. The structure of these compounds is generally such that copolymers of ethylene oxide and propylene oxide are bonded to polydimethylsiloxane radicals. Polysiloxane-polyoxyalkylene copolymers multi-branched via allophanate groups are particularly important.

[0206] d) Reaction retardant

[0207] Useful reaction retardants include, for example, acidic substances (e.g., hydrochloric acid or organic acid halides).

[0208] e) Additives

[0209] Useful PU additives include, for example, cell regulators of a type known in themselves (e.g., paraffin or fatty alcohols) or dimethylpolysiloxanes, and also pigments or dyes of a type known in themselves and flame retardants (e.g., tris(chloroethyl) phosphate, tricresyl phosphate or ammonium phosphate and polyphosphates), and also stabilizers, plasticizers and antifungal and antibacterial materials against the effects of aging and weathering, and also fillers (e.g., barium sulfate, diatomite, carbon black or precipitated chalk).

[0210] Examples of additional uses for optional additional applications according to the present invention, including surface-active additives and foam stabilizers, and also cell regulators, reaction retardants, stabilizers, flame retardant materials, plasticizers, dyes and fillers, and also fungicidal and bacterial materials, are known to those skilled in the art and are described in the literature.

[0211] Advantageously, the polyurethane layer may have a thickness of, for example, 30 μm to 1500 μm, preferably 200 μm to 1000 μm, more preferably 300 μm to 1000 μm.

[0212] In a preferred embodiment, the polyurethane coating layer has a thickness of 100-1,500 μm, preferably 200-1,000 μm, and particularly preferably 300-1,000 μm.

[0213] According to a fourth aspect, the present invention provides a method for manufacturing an article according to a third aspect of the present invention, comprising the following steps:

[0214] (i) a step of forming a substrate by injecting a molten composition according to the first aspect of the present invention into a first mold cavity,

[0215] (ii) a step of expanding the cavity of the injection mold to create a gap between the substrate and the mold surface of the expanded cavity,

[0216] (iii) a step of forming a polyurethane layer by injecting a polyurethane coating into the gap, and

[0217] (iv) Step of removing the obtained composite member from the mold cavity.

[0218] The polyurethane coating may be a mixture of reactive polyurethane raw materials defined above.

[0219] In a specific embodiment, the method comprises the following steps:

[0220] (i) a step of forming a substrate by injecting a molten thermoplastic composition into a first mold cavity,

[0221] (ii) a step of expanding the cavity of the injection mold to create a gap between the substrate and the mold surface of the expanded cavity,

[0222] (iii) at least one polyisocyanate component,

[0223] At least one polyfunctional H-active compound, and

[0224] Optionally at least one polyurethane additive and / or process aid

[0225] A step of injecting a reactive polyurethane raw material mixture comprising [subject part] into a gap, wherein the polyurethane raw material mixture is completely polymerized while in direct contact with the surface of a substrate to provide a polyurethane layer, and

[0226] (iv) Step of removing the obtained composite member from the mold cavity.

[0227] Before demolding the workpiece in steps (ii) and (iv), the workpiece is cooled until it becomes dimensionally stable.

[0228] In order to create a gap in step (ii) of the method, it is possible to open the injection mold and subsequently replace half of the injection mold cavity with a new half having larger cavity dimensions, or move a member from the first mold cavity to a second cavity or second mold that is larger in terms of cavity dimensions, or open the first cavity to create a gap.

[0229] The movement of the substrate in method step (ii) can be carried out by a known process, for example, as used in multicolor injection molding. Typical methods include, first, movement using a turntable, turning plate, sliding cavity, or index plate, or a similar method in which the substrate remains on the core. When the substrate to be moved remains on the core, it has the advantage that its position is precisely defined even after the movement. Second, a method of moving the substrate is disclosed in the prior art in which the substrate is removed from the cavity, for example, with the assistance of a handling system, and placed in another cavity. Movement involving the removal of the substrate provides a more flexible configuration in coating operations, for example, in the creation of edge folds or masking regions.

[0230] The following examples are presented to provide a complete disclosure and description to those skilled in the art regarding how the compositions, articles, and methods claimed herein are constructed and evaluated, and are intended merely to be illustrative and not to limit the scope of the disclosure.

[0231] Examples

[0232] Materials used

[0233] Ingredient A

[0234] Macrolon@2600, a linear bisphenol A polycarbonate available from Covestro, having a relative solution viscosity of 1.28 (ii) (measured with a solution of 0.5 g of polycarbonate in 100 ml of methylene chloride at 25°C) and a weight-average molecular weight of 26000 g / mol.

[0235] Ingredient B

[0236] Core-shell impact modifier ABS (P60) copolymer prepared by emulsion polymerization of a mixture of 24 wt% acrylonitrile and 76 wt% styrene based on ABS polymer in the presence of 42 wt% linear polybutadiene rubber based on ABS polymer.

[0237] Ingredient C

[0238] Polyethylene terephthalate having an intrinsic viscosity of 0.665 dl / g measured in dichloroacetic acid at a concentration of 1 wt% at 25°C (e.g., RT6020, Invista, Gersthofen, Germany).

[0239] Ingredient D

[0240] Boron-aluminum glass fiber (E glass fiber) having an average diameter of 13 μm and a cut length of 2.5-3.5 mm.

[0241] Ingredient E

[0242] The flame retardant is bisphenol-A bis(diphenyl phosphate) (BDP).

[0243] Ingredient F

[0244] Johnkrill® Chain Extender from BASF ADR 4368.

[0245] Ingredient G

[0246] G1 is a PTFE masterbatch used as an anti-slip agent.

[0247] G2 is pentaerythritol tetrastearate, which is used as a lubricant / mold release agent.

[0248] G3 is Irganox® B900 (a mixture of 80% Irgafos® 168 and 20% Irganox® 1076; Irgafos® 168: (tris(2,4-di-tert-butylphenyl)phosphite) / Irganox® 1076: (2,6-di-tert-butyl-4-(octadecaneoxy-carbonylethyl)-phenol) used as a heat stabilizer (BASF AG, Ludwigshafen, Germany).

[0249] Preparation of flame-retardant polycarbonate composition

[0250] A flame-retardant polycarbonate composition was prepared in the form of granules at a melt temperature of 270°C to 300°C using a ZSK26 twin-screw extruder from Coperion, Werner and Pfleiderer (Germany).

[0251] Preparation and testing of test specimens

[0252] The obtained granules were processed in an injection molding machine (Arburg) at a melt temperature of 260°C and a mold temperature of 80°C to provide test specimens.

[0253] An article comprising a substrate and a polyurethane layer made from a flame-retardant polycarbonate composition was manufactured by a direct coating (DC) process.

[0254] The coating used is a 2-component PU coating system comprising SDB_puroclear_3351 IT (polyol) and Puronate 960 / 1 (diisocyanate) from Ruhl Puromer GmbH.

[0255] Molten fluidity is evaluated by the molten volumetric flow rate (MVR) measured with a plunger load of 5 kg at a temperature of 260°C according to ISO 1133-1:2011.

[0256] The Vicat softening temperature is determined according to ISO 306:2013 for a bar with dimensions of 80x10x4 mm.

[0257] The determination of notched impact strength (ak) is performed by 10 determinations on a test bar with dimensions of 80 mm x 10 mm x 3 mm at room temperature (23℃) according to ISO 180 / 1A:2000.

[0258] The determination of non-notched impact strength (an) is performed at room temperature (23℃) according to ISO 180 / 1U:2000 on a test rod with dimensions of 80 mm x 10 mm x 4 mm by 10 determinations.

[0259] The tensile modulus, tensile stress at break, and tensile strain at break are determined by tensile testing at room temperature (23℃) according to ISO 527-2:2012 for a shoulder bar with dimensions of 170 mm x 10 mm x 4 mm.

[0260] Combustion behavior is evaluated according to UL94:2013.

[0261] To evaluate adhesive properties, the article must be aged for 2 days under conditions of 85°C and 85% relative humidity (the above aging conditions are defined by PPG and Amazon as an evaluation method for DC), and then a peel test is performed on the aged part to obtain a peel strength value for comparison. The limit of the average adhesive peel strength value after aging must be higher than 0.5 N / mm, which means that adhesion between the substrate and the PU layer is acceptable.

[0262] The following examples are intended to further explain the present invention.

[0263] Examples 1-7 and Comparative Examples 1-5 of the present invention

[0264] Flame-retardant polycarbonate compositions of Examples 1-7 (IE1-IE7) and Comparative Examples (CE1-CE5) of the present invention containing the components as shown in Table 1 were prepared in the form of granules at a melt temperature of 270°C to 300°C using a ZSK26 twin-screw extruder from Coperion, Werner & Flederer (Germany).

[0265] The MVR of the obtained granules was characterized, and the results are summarized in Table 1.

[0266] Test rods with dimensions of 80 mm x 10 mm x 4 mm and 80 mm x 10 mm x 3 mm and shoulder rods with dimensions of 170 mm x 10 mm x 4 mm were manufactured using an injection molding machine with the granules obtained for each composition.

[0267] The tensile modulus, tensile stress at break, tensile strain at break, Izod notch impact strength, Izod non-notch impact strength, Vicat softening temperature, and combustion behavior of the rod were characterized, and the results are summarized in Table 1.

[0268] For each composition, an article was manufactured comprising a substrate made from a flame-retardant polycarbonate composition and a polyurethane layer having a thickness of 100 μm on one side of the substrate.

[0269] The adhesion between the substrate and the PU layer of all articles was characterized, and the results are summarized in Table 1.

[0270]

[0271] NA* means that peel strength is not obtainable.

[0272] As shown in Table 1, molded articles prepared from Composition IE1 containing 4 wt% ABS have an average adhesion to the PU coating layer of up to 0.719 N / mm. When the ABS content was increased to 8 wt% as presented in Composition IE2, the adhesion became much higher (~1.066 N / mm). However, when the ABS content was further increased to 15 wt% as presented in Composition CE1, the molded articles of CE1 failed to meet the UL 94 V0 rating at a thickness of 1.5 mm.

[0273] Furthermore, it was found that the addition of a chain extender had a very positive effect on adhesive strength. While composition CE2, which did not contain a chain extender, could not achieve acceptable adhesive strength, the addition of 0.5 wt% of a chain extender to composition IE4 increased the adhesive strength to 0.75 N / mm. When the chain extender content was increased from 0.8 wt% to 2 wt%, the adhesive strength increased to 1.374 N / mm. However, when the chain extender content was further increased to 3.5 wt%, the melt volume flow rate was 10.3 cm³ 3 It is 10 min, and this low melt volume flow rate made the injection molding process difficult.

[0274] When the flame retardant BDP content was increased from 12 wt% (IE2) to 18 wt% (IE3), the average adhesive strength value decreased to a limit level (0.51 N / mm), but it could still be acceptable. On the other hand, the Vicat temperature was also acceptable.

[0275] When the PET content in composition IE4 was 10 wt%, good adhesive strength, tensile modulus, heat resistance, and flame retardancy properties were achieved and balanced. However, when the PET content was increased to 12 wt% in composition CE3, the adhesive strength dropped significantly to 0.3 N / mm, which is lower than the acceptable level.

[0276] As design trends for ultrabooks and tablets are becoming increasingly thinner and lighter, housing materials are required to possess excellent mechanical properties, superior flame retardancy, and high heat resistance, as well as excellent injection molding processability. Accordingly, reinforced polycarbonate materials are becoming increasingly popular and have recently been used as the dominant material with high elastic modulus / stiffness, excellent thermal stability, and high flame retardancy. Generally, to satisfy application requirements, it is required that the tensile modulus of the reinforced material exceed 3500 MPa, the Vicat temperature exceed 85°C, and that a molded sample of the reinforced polycarbonate composition achieves a UL94 V0 rating at a thickness of 1.5 mm.

[0277] Composition IE1, containing 14 wt% glass fiber, was shown to possess excellent adhesive strength and necessary mechanical properties. Among the samples of Compositions IE6, IE7, and CE5, the glass fiber content was increased to 20 wt%, 25 wt%, and 35 wt%, respectively. Although their average adhesive strength values ​​were still greater than 0.5 N / mm, the adhesive strength decreased relatively. In the case of Composition CE5, containing 35 wt% glass fiber, the Vicat temperature was clearly lower than 85°C. Furthermore, the flame retardancy was also poor, achieving only a UL94 V1 rating at a thickness of 1.5 mm.

[0278] Although illustrative embodiments are presented and described, such embodiments are not to be interpreted as limiting the present disclosure, and it will be recognized by those skilled in the art that changes, substitutions, and modifications may be made to the embodiments without departing from the spirit, principles, and scope of the present disclosure.

Claims

Claim 1 A flame-retardant polycarbonate composition comprising the following components, all contents based on the total weight of the composition: A) 30-70 wt% aromatic polycarbonate; B) 3-10 wt% rubber-modified vinyl (co)polymer; C) 3-11 wt% aromatic polyester; D) 10-30 wt% reinforcing material; E) 10-20 wt% phosphorus-containing flame retardant; and F) 0.5-3 wt% chain extender. Claim 2 A composition according to claim 1, wherein the rubber-modified vinyl (co)polymer comprises B1) 5 to 95 wt% of at least one vinyl monomer and B2) 95 to 5 wt% of one or more graft substrates having a glass transition temperature of < 10°C, < 0°C, or < -20°C, wherein wt% is calculated based on the weight of the rubber-modified vinyl (co)polymer. Claim 3 In paragraph 2, at least one vinyl monomer B1 is a mixture of the following: B1.1) 50 to 99 wt% of vinyl aromatic and / or vinyl aromatic and / or methacrylic acid (C1-C8)-alkyl esters substituted on the nucleus, and B1.2) 1 to 50 wt% of vinyl cyanide and / or (meth)acrylic acid (C1-C8)-alkyl esters and / or derivatives of unsaturated carboxylic acids, where wt% is calculated based on the weight of vinyl monomer B1; a composition in which the graft substrate B2 is selected from diene rubber, provided that the glass transition temperature of component B2 is < 10°C, < 0°C, or < -20°C. Claim 4 A composition according to any one of claims 1 to 3, wherein the aromatic polyester is selected from poly(ethylene terephthalate), poly(1,4-butylene terephthalate) and poly(trimethylene terephthalate). Claim 5 A composition according to any one of claims 1 to 3, wherein the reinforcing material is a glass fiber made of a glass composition selected from the group of M-, E-, A-, S-, R-, AR-, ECR-, D-, Q-, or C-glass. Claim 6 A composition according to any one of claims 1 to 3, wherein the phosphorus-containing flame retardant is selected from a phosphorus compound of formula (IV): Here R 1 , R 2 , R 3 and R 4 Each independently represents a C1 to C8 alkyl, a C5 to C6 cycloalkyl, a C6 to C20 aryl, or a C7 to C12 aralkyl, each optionally alkyl-substituted, n independently represents 0 or 1, q represents 0 to 30, and X represents a mononuclear or polynuclear aromatic residue having 6 to 30 carbon atoms or a linear or branched aliphatic residue having 2 to 30 carbon atoms, which may be OH-substituted and may contain 8 or fewer ether bonds. Claim 7 In any one of claims 1 to 3, the chain extender comprises one or more ethylene-based unsaturated compounds selected from styrene and ethylene and glycidyl C 1-4 A composition selected from the reaction product of an epoxy-containing ethylene-based unsaturated monomer selected from (alkyl)acrylate, allyl glycidyl ethacrylate, and glycidyl itaconate. Claim 8 A composition according to claim 7, selected from a styrene-acrylic copolymer containing a glycidyl group incorporated as a side chain, wherein the chain extender is incorporated. Claim 9 A composition according to claim 8, wherein the number of epoxy groups per polymer chain of the styrene-acrylic copolymer is at least 10, more than 15, or more than 20. Claim 10 A composition according to claim 7, wherein the chain extender has a weight-average molecular weight in the range of 3,000 to 15,000 daltons, 4,000 to 12,000 daltons, or 6,000 to 10,000 daltons. Claim 11 A composition according to any one of claims 1 to 3, wherein the chain extender is present in an amount ranging from 0.8 wt% to 2.5 wt% or from 0.8 wt% to 2 wt% with respect to the total weight of the composition. Claim 12 In claim 1, the rubber-modified vinyl (co)polymer comprises B1) 20 to 85 wt% of at least one vinyl monomer and B2) 80 to 10 wt% of one or more graft substrates having a glass transition temperature of < -20°C, wherein wt% is calculated based on the weight of the rubber-modified vinyl (co)polymer, and at least one vinyl monomer B1 is a mixture of the following: B1.1) 75 to 80 wt% of styrene, α-methylstyrene, p-methylstyrene or p-chlorostyrene and / or methyl methacrylate or ethyl methacrylate, and B1.2) 20 to 25 wt% of acrylonitrile and methacrylonitrile and / or methyl methacrylate, n-butyl acrylate or t-butyl acrylate and / or derivatives of unsaturated carboxylic acids, wt% A composition calculated based on the weight of vinyl monomer B1; wherein the graft substrate B2 is selected from diene rubber, provided that the glass transition temperature of component B2 is < -20°C (less than); the aromatic polyester is selected from poly(ethylene terephthalate), poly(1,4-butylene terephthalate) and poly(trimethylene terephthalate); the reinforcing material is a glass fiber made of a glass composition selected from the group of M-, E-, A-, S-, R-, AR-, ECR-, D-, Q- or C-glass; and the phosphorus-containing flame retardant is selected from a phosphorus compound of formula (IV): Here R 1 , R 2 , R 3 and R 4 Each independently represents a C1 to C8 alkyl, a C5 to C6 cycloalkyl, a C6 to C20 aryl, or a C7 to C12 aralkyl, each optionally C1 to C4 alkyl-substituted; n independently represents 0 or 1; q represents 0 to 30; X represents a mononuclear or polynuclear aromatic residue having 6 to 30 carbon atoms or a linear or branched aliphatic residue having 2 to 30 carbon atoms, which may be OH-substituted and may contain 8 or fewer ether bonds; the chain extender is selected from a styrene-acrylic copolymer containing a glycidyl group incorporated as a side chain, the number of epoxy groups per polymer chain of the styrene-acrylic copolymer is greater than 20, the chain extender has a weight-average molecular weight in the range of 6,000 to 10,000 daltons, and the chain extender is based on the total weight of the composition A composition present in an amount ranging from 0.8 wt% to 2 wt%. Claim 13 A molded article manufactured from a composition according to any one of paragraphs 1 to 3 and 12. Claim 14 An article comprising a substrate manufactured from a polycarbonate composition according to any one of claims 1 to 3 and 12, and a polyurethane layer on at least one side of the substrate. Claim 15 Article of claim 14, wherein the polyurethane layer has a thickness of 30 μm to 1500 μm, 200 μm to 1000 μm, or 300 μm to 1000 μm. Claim 16 A method for manufacturing an article according to claim 14, comprising the following steps: (i) injecting a molten composition into a first mold cavity to form a substrate; (ii) expanding the cavity of the injection mold to create a gap between the substrate and the mold surface of the expanded cavity; (iii) injecting a polyurethane coating into the gap to form a polyurethane layer; and (iv) removing the obtained composite member from the mold cavity.

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