Resin composition and molded article thereof

Abstract

Provided is a resin composition which has excellent impact resistance, flowability, and heat resistance, and a good molded article appearance, and which has a high effect of suppressing tape peeling on the surface of a molded article. The present invention relates to a polycarbonate resin composition comprising (A) 45-90 parts by weight of a polycarbonate resin (component A) and (B) 10-55 parts by weight of a copolymer (component B) obtained by polymerizing an aromatic vinyl monomer and a vinyl cyanide monomer, the resin composition contains (C) 0.5-10 parts by weight of an acrylic block copolymer (component C), (D) 0.01-3.0 parts by weight of a phosphorus antioxidant (component D), and (E) 0.01-3.0 parts by weight of a hindered phenol antioxidant (component E).

Description

Technical Field

[0001] The present invention relates to a resin composition and a molded product thereof, and more particularly to a resin composition and a molded product thereof having excellent impact resistance, fluidity, heat resistance and good molded product appearance and having a high effect of suppressing tape peeling on the surface of the molded product. Background Art

[0002] Polycarbonate resin is used for various purposes centered on the automotive field, OA equipment field, and electronic and electrical equipment field because of its excellent mechanical and thermal properties. In addition, for alloy resins formed by combining ABS resin or AS resin in polycarbonate resin, they are used in applications such as automotive parts, printer parts, personal computer housings, and computer parts by making use of their excellent fluidity. In recent years, especially in the automotive field, although the use of alloy resins formed by combining ABS resin in polycarbonate resin is increasing, there is a problem of damaging the excellent mechanical properties, especially impact resistance, of polycarbonate resin due to combining ABS resin. Therefore, research on improving impact resistance has been conducted so far. As a method for improving the impact resistance of resin materials, for example, a method of combining an impact modifier represented by a graft polymer in an alloy resin is disclosed, and the above-mentioned alloy resin is formed by combining ABS resin in a polycarbonate resin. (Refer to Patent Document 1) However, according to this method, although the impact resistance is improved, there is a problem of impaired fluidity. In addition, as a method for improving impact resistance and fluidity at the same time, for example, a method of blending an acrylic block copolymer in an alloy resin is disclosed, wherein the alloy resin is formed by blending an ABS resin in a polycarbonate resin (see Patent Document 2). However, in this method, there are problems such as deterioration of the appearance of the molded product and tape peeling on the surface of the molded product.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2009-203269

[0006] Patent Document 2: Japanese Patent Application Publication No. 2020-164774 Summary of the invention

[0007] An object of the present invention is to provide a resin composition having excellent impact resistance, fluidity, and heat resistance, and a good appearance of a molded product and having a high effect of suppressing tape peeling on the surface of the molded product, and a molded product thereof.

[0008] The present inventors have conducted intensive studies to solve the above-mentioned problems and have found that by adding an acrylic block copolymer, a phosphorus-based antioxidant and a hindered phenol-based antioxidant to a resin component composed of a polycarbonate resin and a copolymer obtained by polymerizing an aromatic vinyl monomer and a cyanide vinyl monomer, a resin composition having excellent impact resistance, fluidity, heat resistance and a good appearance of a molded product and a high effect of suppressing tape peeling on the surface of the molded product and a molded product thereof can be obtained.

[0009] That is, the present invention is as follows.

[0010] 1. A resin composition comprising 0.5 to 10 parts by weight of (C) an acrylic block copolymer (component C), 0.01 to 3.0 parts by weight of (D) a phosphorus-based antioxidant (component D), and 0.01 to 3.0 parts by weight of (E) a hindered phenol-based antioxidant (component E), based on 100 parts by weight of a resin component composed of 45 to 90 parts by weight of (A) a polycarbonate resin (component A) and 10 to 55 parts by weight of (B) a copolymer obtained by polymerizing an aromatic vinyl monomer and a vinyl cyanide monomer (component B).

[0011] 2. The resin composition according to the above Item 1, wherein the component C is an acrylic block copolymer containing a polymer block comprising an acrylic acid ester monomer unit and a polymer block comprising a methacrylic acid ester monomer unit.

[0012] 3. The resin composition according to the above item 2, wherein the content of the polymer block containing the methacrylate monomer unit in the component C is 25% by weight or more in the total blocks.

[0013] 4. The resin composition according to any one of the above 1 to 3, wherein the component B is an ABS resin.

[0014] 5. A molded article comprising the resin composition according to any one of 1 to 4 above.

[0015] 6. The molded article according to the above Item 5, characterized in that the molded article is an automobile part.

[0016] The resin composition of the present invention has excellent impact resistance, fluidity, heat resistance, good appearance of molded products, and a high inhibitory effect of tape peeling on the surface of the molded products. Therefore, it can be suitably used as parts in the automotive field, OA equipment field, home appliances, electrical and electronic fields, etc., especially suitable for automotive parts, and its industrial effect is remarkable. DETAILED DESCRIPTION

[0017] Hereinafter, each constituent component of the present invention will be described in detail.

[0018] (Component A: polycarbonate resin)

[0019] The polycarbonate resin used in the present invention is a polycarbonate resin obtained by reacting a dihydric phenol with a carbonate precursor. As an example of a reaction method, interfacial polymerization, melt transesterification, solid phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds can be cited.

[0020] Representative examples of the dihydric phenols used herein include hydroquinone, resorcinol, 4,4'-biphenol, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A), 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl)-3-methylphenyl)propane, 2,2-bis(4-hydroxyphenyl)- ... The preferred diphenols include bis(4-hydroxyphenyl)alkanes, ...

[0021] In the present invention, in addition to bisphenol A-based polycarbonate resins, which are general-purpose polycarbonate resins, special polycarbonate resins produced using other dihydric phenols can be used as component A. For example, polycarbonate resins (homopolymers or copolymers) using 4,4'-(m-phenylene diisopropylidene) diphenol (hereinafter sometimes referred to as "BPM"), 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter sometimes referred to as "Bis-TMC"), 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (hereinafter sometimes referred to as "BCF") as part or all of the dihydric phenol components are suitable for applications where dimensional changes due to water absorption and morphological stability are particularly strictly required. Regarding these dihydric phenols other than BPA, it is preferred to use 5 mol% or more, particularly 10 mol% or more of the total dihydric phenol components constituting the polycarbonate resin. In particular, when high rigidity and better hydrolysis resistance are required, it is particularly preferred that the A component constituting the resin composition is a copolycarbonate resin of the following (1) to (3). (1) A copolycarbonate resin in which BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, further preferably 45 to 65 mol%) and BCF is 20 to 80 mol% (more preferably 25 to 60 mol%, further preferably 35 to 55 mol%) out of 100 mol% of the dihydric phenol components constituting the polycarbonate resin.

[0022] (2) A copolymerized polycarbonate resin in which, in 100 mol % of the dihydric phenol component constituting the polycarbonate resin, 10 to 95 mol % (more preferably 50 to 90 mol %, further preferably 60 to 85 mol %) of BPA and 5 to 90 mol % of BCF (more preferably 10 to 50 mol %, further preferably 15 to 40 mol %) are present.

[0023] (3) A copolymerized polycarbonate resin in which, in 100 mol % of the dihydric phenol component constituting the polycarbonate resin, BPM accounts for 20 to 80 mol % (more preferably 40 to 75 mol %, and even more preferably 45 to 65 mol %) and Bis-TMC accounts for 20 to 80 mol % (more preferably 25 to 60 mol %, and even more preferably 35 to 55 mol %).

[0024] These special polycarbonate resins can be used alone or in combination of two or more. In addition, they can be mixed with a general bisphenol A type polycarbonate resin. The preparation methods and properties of these special polycarbonate resins are described in detail in, for example, Japanese Patent Publication No. 6-172508, Japanese Patent Publication No. 8-27370, Japanese Patent Publication No. 2001-55435, and Japanese Patent Publication No. 2002-117580.

[0025] It should be noted that among the various polycarbonate resins mentioned above, the polycarbonate resin whose copolymer composition is adjusted so that the water absorption rate and Tg (glass transition temperature) are within the following ranges is particularly suitable in fields requiring morphological stability because the polymer itself has good resistance to hydrolysis and is particularly excellent in low warpage even after molding.

[0026] (i) a polycarbonate resin having a water absorption of 0.05 to 0.15%, preferably 0.06 to 0.13%, and a Tg of 120 to 180°C, or

[0027] (ii) A polycarbonate resin having a Tg of 160 to 250°C, preferably 170 to 230°C, and a water absorption of 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27%.

[0028] Here, the water absorption of the polycarbonate resin is a value obtained by measuring the water content of a disk-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm after immersion in water at 23° C. for 24 hours in accordance with ISO 62-1980. In addition, Tg (glass transition temperature) is a value obtained by differential scanning calorimetry (DSC) in accordance with JIS K7121.

[0029] As the carbonate precursor, a carbonyl halide, a carbonic acid diester, a halogenated format, or the like is used, and specific examples thereof include phosgene, diphenyl carbonate, and a dihalogenated format of a dihydric phenol.

[0030] When utilizing above-mentioned dihydric phenol and carbonate precursor to make polycarbonate resin by interfacial polymerization, can use catalyst, end-capping agent, antioxidant that is used to prevent dihydric phenol oxidation etc. as required.In addition, polycarbonate resin of the present invention comprises: the branched polycarbonate resin that makes the copolymerization of polyfunctional aromatic compound above trifunctional, the polyester carbonate resin that makes the copolymerization of difunctional carboxylic acid of aromatic or aliphatic (comprising alicyclic), the copolymerization polycarbonate resin that makes the copolymerization of difunctional alcohol (comprising alicyclic) and the polyester carbonate resin that makes the copolymerization of above-mentioned difunctional carboxylic acid and difunctional alcohol.In addition, also can be the mixture that 2 or more of the polycarbonate resin that obtain are mixed.

[0031] The branched polycarbonate resin can impart anti-drip properties to the resin composition of the present invention. Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin include phloroglucinol, pentahydroxybiphenyl or 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2, 2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methyl Phenol, triphenols such as 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetrakis(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and acid chlorides thereof, among which 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

[0032] The structural unit derived from the polyfunctional aromatic compound of the branched polycarbonate resin is preferably 0.01 to 1 mol%, more preferably 0.05 to 0.9 mol%, and further preferably 0.05 to 0.8 mol%, in the total of 100 mol% of the structural unit derived from the dihydric phenol and the structural unit derived from the above-mentioned polyfunctional aromatic compound. In addition, in the case of the melt transesterification method, branched structural units may be generated as a side reaction. The amount of the above-mentioned branched structural units is preferably the following value in the total of 100 mol% of the structural units derived from the dihydric phenol, preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, and further preferably 0.01 to 0.8 mol%. It should be noted that the proportion of the above-mentioned branched structure can be determined by 1 The calculation was performed based on H-NMR measurement.

[0033] The aliphatic difunctional carboxylic acid is preferably α,ω-dicarboxylic acid. As the aliphatic difunctional carboxylic acid, for example, straight-chain saturated aliphatic dicarboxylic acids such as sebacic acid (decane dioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, eicosanedioic acid and alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid can be preferably mentioned. As the difunctional alcohol, alicyclic diols are more preferably used, for example, cyclohexanedimethanol, cyclohexanediol and tricyclodecane dimethanol can be exemplified.

[0034] Reaction forms such as the interfacial polymerization method, the melt transesterification method, the solid phase transesterification method of carbonate prepolymers, and the ring-opening polymerization method of cyclic carbonate compounds, which are methods for producing the polycarbonate resin of the present invention, are well known in various documents and patent publications.

[0035] When the polycarbonate resin composition of the present invention is produced, the viscosity average molecular weight (M) of the polycarbonate resin is not particularly limited, but is preferably 1.8×10 4 ~4.0×10 4 , more preferably 2.0×10 4 ~3.5×10 4 , and more preferably 2.2×10 4 ~3.0×10 4 When the viscosity average molecular weight is less than 1.8×10 4 In polycarbonate resins with a viscosity average molecular weight of more than 4.0×10 4 The resin composition obtained by using the polycarbonate resin has poor fluidity during injection molding and thus has poor versatility.

[0036] It should be noted that the polycarbonate resin may be a polycarbonate resin obtained by mixing a resin having a viscosity average molecular weight outside the above range. 4 ) increases the entropy elasticity of the resin. As a result, good molding processability is achieved in gas-assisted molding and foaming molding used when molding reinforced resin materials into structural parts. The improvement in molding processability is further improved than that of the branched polycarbonate resin. As a more preferred embodiment, component A can also use a component having a viscosity average molecular weight of 7×10 4 ~3×10 5 The polycarbonate resin (component A-1-1) and the viscosity average molecular weight 1×10 4 ~3×10 4 The aromatic polycarbonate resin (component A-1-2) has a viscosity average molecular weight of 1.6×10 4 ~3.5×10 4 A polycarbonate resin (component A-1) (hereinafter sometimes referred to as "polycarbonate resin containing a high molecular weight component").

[0037] In the polycarbonate resin containing a high molecular weight component (component A-1), the molecular weight of component A-1-1 is preferably 7×10 4 ~2×10 5 , more preferably 8×10 4 ~2×10 5 , and more preferably 1×10 5 ~2×10 5 , particularly preferably 1×10 5 ~1.6×10 5 In addition, the molecular weight of component A-1-2 is preferably 1×10 4 ~2.5×104 , more preferably 1.1×10 4 ~2.4×10 4 , and more preferably 1.2×10 4 ~2.4×10 4 , particularly preferably 1.2×10 4 ~2.3×10 4 .

[0038] The polycarbonate resin containing a high molecular weight component (component A-1) can be obtained by mixing the above-mentioned component A-1-1 and component A-1-2 in various proportions and adjusting them to meet the prescribed molecular weight range. Preferably, the component A-1-1 accounts for 2 to 40% by weight in 100% by weight of the component A-1, more preferably 3 to 30% by weight, further preferably 4 to 20% by weight, and particularly preferably 5 to 20% by weight.

[0039] In addition, examples of methods for preparing component A-1 include (1) a method of independently polymerizing component A-1-1 and component A-1-2 and mixing them; (2) a method of producing an aromatic polycarbonate resin showing a plurality of polymer peaks in a molecular weight distribution diagram obtained by a GPC method in the same system using a method represented by the method disclosed in Japanese Patent Application Laid-Open No. 5-306336, wherein the aromatic polycarbonate resin is produced in such a manner as to satisfy the conditions of component A-1 of the present invention; and (3) a method of mixing an aromatic polycarbonate resin obtained by the above-mentioned production method (production method of (2)) with component A-1-1 and / or component A-1-2 produced separately.

[0040] The viscosity average molecular weight of the present invention is calculated as follows. First, using an Ostwald viscometer, a solution prepared by dissolving 0.7 g of a polycarbonate resin in 100 ml of dichloromethane at 20° C. is used to determine the specific viscosity (η) calculated by the following formula: SP ),

[0041] Specific viscosity (η SP )=(t-t0) / t0

[0042] [t0 is the falling seconds of dichloromethane, t is the falling seconds of the sample solution]

[0043] The specific viscosity (η SP ) The viscosity average molecular weight M is calculated according to the following mathematical formula.

[0044] η SP / c=[η]+0.45×[η] 2 c (where [η] is the intrinsic viscosity)

[0045] [η] = 1.23 × 10 －4 M 0.83

[0046] c=0.7

[0047] It should be noted that the viscosity average molecular weight of the polycarbonate resin in the polycarbonate resin composition of the present invention is calculated by the following points. That is, the composition is mixed with 20 to 30 times its weight of dichloromethane to dissolve the soluble components in the composition. The above-mentioned soluble components are collected by filtration through diatomaceous earth. Then the solvent in the obtained solution is removed. The solid after the solvent is removed is fully dried to obtain a solid of the component dissolved in dichloromethane. From the solution obtained by dissolving 0.7g of the above-mentioned solid in 100ml of dichloromethane, the specific viscosity at 20°C is calculated in the same way as above, and the viscosity average molecular weight M is calculated in the same way as above from the specific viscosity.

[0048] As the polycarbonate resin of the present invention, a polycarbonate-polydiorganosiloxane copolymer resin may also be used. The polycarbonate-polydiorganosiloxane copolymer resin is preferably a copolymer resin prepared by copolymerizing a dihydric phenol represented by the following general formula (1) and a hydroxyaryl-terminated polydiorganosiloxane represented by the following general formula (3).

[0049] [Chemical formula 1]

[0050]

[0051] [In the above general formula (1), R 1 and R 2 Each independently represents a group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkyloxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group; when there are a plurality of each, they may be the same or different; e and f are each an integer of 1 to 4; and W is a single bond or at least one group selected from the groups represented by the following general formula (2).]

[0052] [Chemical formula 2]

[0053]

[0054] [In the above general formula (2), R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R17 and R 18 Each independently represents a group selected from a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, and R 19 and R 20 Each independently represents a group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkyloxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. When there are a plurality of such groups, they may be the same or different. g is an integer of 1 to 10, and h is an integer of 4 to 7.]

[0055] [Chemical formula 3]

[0056]

[0057] [In the above general formula (3), R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, R 9 and R 10 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, p is a natural number, q is 0 or a natural number, and p+q is a natural number from 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms.]

[0058] Examples of the dihydric phenol (I) represented by the general formula (1) include 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxy-3,3'-biphenyl)propane, 2,2-bis(4-hydroxy-3-isopropylphenyl)propane, 2,2-bis(4-hydroxyphenyl)-3-isopropylphenyl)propane, 2,2-bis(4-hydroxyphenyl)-1-phenylethane. 2-bis(3-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)diphenylmethane, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,1- Bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyl diphenyl ether, 4,4'-sulfonyl diphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'-dimethyl-4,4'-sulfonyl diphenol, 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfide, 2,2'-diphenyl-4,4'-sulfonyl diphenol, 4,4 '-Dihydroxy-3,3'-diphenyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfide, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis(4-hydroxyphenyl)cyclohexane, 1,3-bis(4-hydroxyphenyl)cyclohexane, 4,8-bis(4-hydroxyphenyl)tricyclo[5.2.1.02,6]decane, 4,4'-(1,3-adamantanediyl)diphenol, 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane, etc.

[0059] Among them, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-sulfonyldiphenol, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, and 1,4-bis{2-(4-hydroxyphenyl)propyl} are preferred, and 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), 4,4'-sulfonyldiphenol, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene are particularly preferred. Among them, 2,2-bis(4-hydroxyphenyl)propane is most preferred because of its excellent strength and good durability. These may be used alone or in combination of two or more.

[0060] As the hydroxyaryl-terminated polydiorganosiloxane represented by the general formula (3), for example, the following compounds are preferably used.

[0061] [Chemical formula 4]

[0062]

[0063] Hydroxyaryl-terminated polydiorganosiloxane (II) can be easily produced by subjecting phenols having olefinic unsaturated carbon-carbon bonds, preferably vinylphenol, 2-allylphenol, isopropenylphenol, 2-methoxy-4-allylphenol, to a hydrosilylation reaction at the end of a polysiloxane chain having a predetermined degree of polymerization. Among them, (2-allylphenol)-terminated polydiorganosiloxane and (2-methoxy-4-allylphenol)-terminated polydiorganosiloxane are preferred, and (2-allylphenol)-terminated polydimethylsiloxane and (2-methoxy-4-allylphenol)-terminated polydimethylsiloxane are particularly preferred. Hydroxyaryl-terminated polydiorganosiloxane (II) preferably has a molecular weight distribution (Mw / Mn) of 3 or less. In order to achieve further excellent low outgassing properties and low-temperature impact properties during high-temperature molding, the molecular weight distribution (Mw / Mn) is more preferably 2.5 or less, and more preferably 2 or less. If the upper limit of the above preferred range is exceeded, the amount of outgassing generated during high temperature molding may increase, and the low temperature impact resistance may be poor.

[0064] In order to achieve high impact resistance, the diorganosiloxane polymerization degree (p+q) of the hydroxyaryl-terminated polydiorganosiloxane (II) is preferably 10 to 300. The diorganosiloxane polymerization degree (p+q) is preferably 10 to 200, more preferably 12 to 150, and even more preferably 14 to 100. If it is less than the lower limit of the preferred range, the impact resistance that is a characteristic of the polycarbonate-polydiorganosiloxane copolymer cannot be effectively achieved, and if it exceeds the upper limit of the preferred range, the appearance is poor.

[0065] The content of polydiorganosiloxane in the total weight of the polycarbonate-polydiorganosiloxane copolymer resin used in component A is preferably 0.1 to 50% by weight. The content of the above-mentioned polydiorganosiloxane component is more preferably 0.5 to 30% by weight, and further preferably 1 to 20% by weight. If it is above the lower limit of the above-mentioned preferred range, the impact resistance and flame retardancy are excellent. If it is below the upper limit of the above-mentioned preferred range, a stable appearance that is not easily affected by molding conditions can be easily obtained. The above-mentioned degree of polymerization of polydiorganosiloxane and content of polydiorganosiloxane can be 1 The calculation was performed based on H-NMR measurement.

[0066] In the present invention, the hydroxyaryl-terminated polydiorganosiloxane (II) may be used alone or in combination of two or more.

[0067] Furthermore, other comonomers other than the dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) may be used in combination in an amount of 10% by weight or less based on the total weight of the copolymer within the range not impairing the present invention.

[0068] In the present invention, a mixed solution containing an oligomer having a terminal chloroformate group is prepared in advance by reacting a dihydric phenol (I) and a carbonate-forming compound in a mixed solution of a water-immiscible organic solvent and an alkaline aqueous solution.

[0069] When generating the oligomer of dihydric phenol (I), the total amount of dihydric phenol (I) used in the method of the present invention can be made into oligomer at one time, or a part of it can be added as a post-added monomer as a reaction raw material in the interfacial polycondensation reaction of the latter stage. The post-added monomer refers to a monomer added in order to make the polycondensation reaction of the latter stage proceed quickly, and it is not necessary to add it when it is not necessary.

[0070] The method of the oligomer formation reaction is not particularly limited, but is usually preferably a method in which the reaction is carried out in a solvent in the presence of an acid binder.

[0071] The ratio of the carbonate-forming compound to be used can be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. In addition, when a gaseous carbonate-forming compound such as phosgene is used, a method of blowing it into the reaction system can be preferably adopted.

[0072] As the above-mentioned acid binding agent, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide can be used; alkali metal carbonates such as sodium carbonate and potassium carbonate; organic bases such as pyridine or their mixtures, etc. The use ratio of the acid binding agent can also be appropriately determined by considering the stoichiometric ratio (equivalent) of the reaction in the same manner as above. Specifically, it is preferred to use an acid binding agent in an amount of 2 equivalents or slightly excessive relative to the mole number (usually 1 mole is equivalent to 2 equivalents) of the dihydric phenol (I) used for the formation of the oligomer.

[0073] As the above-mentioned solvent, a solvent inert to various reactions such as the solvent used in the manufacture of known polycarbonates can be used alone or as a mixed solvent. As representative examples, for example, hydrocarbon solvents such as xylene, methylene chloride, and chlorobenzene can be cited as halogenated hydrocarbon solvents, etc. It is particularly preferred to use halogenated hydrocarbon solvents such as methylene chloride.

[0074] The reaction pressure for oligomer formation is not particularly limited, and can be normal pressure, pressurized, or reduced pressure, but it is generally advantageous to conduct the reaction under normal pressure. The reaction temperature is selected from the range of -20 to 50°C. In most cases, water cooling or ice cooling is expected because heat is generated with polymerization. Although the reaction time is affected by other conditions and cannot be generally specified, it is usually carried out for 0.2 to 10 hours. The pH range of the oligomer formation reaction is the same as the known interfacial reaction conditions, and the pH is often adjusted to 10 or more.

[0075] The present invention obtains a mixed solution of oligomers of a dihydric phenol (I) having a terminal chloroformate group in this manner, and then, while stirring the mixed solution, a hydroxyaryl-terminated polydiorganosiloxane (II) represented by the general formula (3) which has been highly purified to have a molecular weight distribution (Mw / Mn) of 3 or less is added to the dihydric phenol (I), and a polycarbonate-polydiorganosiloxane copolymer is obtained by interfacial polycondensation of the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer.

[0076] [Chemical formula 5]

[0077]

[0078] [In the above general formula (3), R 3 , R 4 , R 5 , R 6 , R 7 and R 8are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, R 9 and R 10 Each is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, p is a natural number, q is 0 or a natural number, and p+q is a natural number from 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms.]

[0079] When performing the interfacial polycondensation reaction, an acid-binding agent may be appropriately added in consideration of the stoichiometric ratio (equivalent) of the reaction. As the acid-binding agent, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; organic bases such as pyridine or mixtures thereof, etc. may be used. Specifically, when a portion of the hydroxyaryl-terminated polydiorganosiloxane (II) or the dihydric phenol (I) as described above is added as a post-added monomer at this reaction stage, it is preferred to use a base in an amount of 2 equivalents or more relative to the total molar number of the dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) of the post-added portion (usually 1 mole is equivalent to 2 equivalents).

[0080] The polycondensation by the interfacial polycondensation reaction of the oligomer of the dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the mixed liquid.

[0081] In the above-mentioned polymerization reaction, an end-capping agent or a molecular weight regulator is usually used. As the end-capping agent, a compound having a monovalent phenolic hydroxyl group can be cited, and examples thereof include common phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, etc., and in addition thereto, examples thereof include long-chain alkylphenols, aliphatic carboxylic acid chlorides, aliphatic carboxylic acids, hydroxybenzoic acid alkyl esters, hydroxyphenyl alkyl esters, alkyl ether phenols, etc. The amount thereof used is 100 to 0.5 moles relative to 100 moles of all dihydric phenol compounds used, preferably in the range of 50 to 2 moles, and of course, two or more compounds can be used in combination.

[0082] In order to promote the polycondensation reaction, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt may be added.

[0083] The reaction time of the above polymerization reaction is preferably 30 minutes or longer, and more preferably 50 minutes or longer. A small amount of an antioxidant such as sodium sulfite or sodium dithionite may be added as needed.

[0084] A branching agent can be used together with the above-mentioned dihydric phenolic compound to form a branched polycarbonate-polydiorganosiloxane copolymer resin. Examples of the trifunctional or higher polyfunctional aromatic compound used for the above-mentioned branched polycarbonate-polydiorganosiloxane copolymer resin include phloroglucinol, pentahydroxybiphenyl or 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2, 2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)- 4-methylphenol, 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol and other triphenols, tetrakis(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and acid chlorides thereof, among which 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred. The ratio of the multifunctional compound in the branched polycarbonate-polydiorganosiloxane copolymer resin is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, further preferably 0.01 to 0.8 mol%, and particularly preferably 0.05 to 0.4 mol% of the total amount of the polycarbonate-polydiorganosiloxane copolymer resin. 1 The calculation was performed based on H-NMR measurement.

[0085] The reaction pressure may be reduced pressure, normal pressure, or pressurized pressure. Generally, it is preferably carried out under normal pressure or the self-pressure of the reaction system. The reaction temperature is selected from the range of -20 to 50°C. In most cases, water cooling or ice cooling is preferred because heat is generated with polymerization. Since the reaction time varies depending on other conditions such as the reaction temperature, it cannot be generally specified, but is usually carried out for 0.5 to 10 hours.

[0086] The obtained polycarbonate-polydiorganosiloxane copolymer resin may be subjected to appropriate physical treatment (mixing, separation, etc.) and / or chemical treatment (polymerization reaction, crosslinking treatment, partial decomposition treatment, etc.) as appropriate to obtain a desired reduced viscosity [η SP / c] polycarbonate-polydiorganosiloxane copolymer resin is obtained.

[0087] The obtained reaction product (crude product) can be subjected to various post-treatments such as known separation and purification methods to recover a polycarbonate-polydiorganosiloxane copolymer resin having a desired purity (degree of purification).

[0088] The average size of the polydiorganosiloxane domain in the polycarbonate-polydiorganosiloxane copolymer resin molded product is preferably in the range of 1 to 60 nm. The above average size is more preferably 3 to 55 nm, and further preferably 5 to 50 nm. If it is less than the lower limit of the above preferred range, the impact resistance and flame retardancy cannot be fully exerted, and if it exceeds the upper limit of the above preferred range, the impact resistance may not be stably exerted.

[0089] (Component B: a copolymer obtained by polymerizing an aromatic vinyl monomer and a vinyl cyanide monomer)

[0090] The component B of the present invention is a copolymer obtained by polymerizing an aromatic vinyl monomer and a vinyl cyanide monomer, preferably a copolymer obtained by polymerizing an aromatic vinyl monomer, a vinyl cyanide monomer and a diene rubber polymer. The component B is preferably composed of 40 to 90% by weight of an aromatic vinyl monomer, 10 to 50% by weight of a vinyl cyanide monomer, and 0 to 50% by weight of other polymers or monomers.

[0091] As the aromatic vinyl monomer, styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinyl xylene, ethylstyrene, dimethylstyrene, p-tert-butylstyrene, vinylnaphthalene, methoxystyrene, monobromostyrene, dibromostyrene, fluorostyrene, tribromostyrene, etc. can be mentioned, and styrene is particularly preferred. In 100% by weight of component B, the lower limit of the proportion of the aromatic vinyl monomer in component B is more preferably 45% by weight, further preferably 50% by weight, and particularly preferably 55% by weight, and the upper limit is more preferably 75% by weight, further preferably 70% by weight, and particularly preferably 65% ​​by weight.

[0092] Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile, and acrylonitrile is particularly preferred. The lower limit of the proportion of the vinyl cyanide monomer in component B, in 100% by weight of component B, is more preferably 12% by weight, further preferably 14% by weight, and particularly preferably 15% by weight, and the upper limit is more preferably 28% by weight, further preferably 26% by weight, and particularly preferably 25% by weight.

[0093] Furthermore, other polymers or monomers that can be copolymerized with these can be copolymerized to form component B. In this case, as the copolymerizable polymer, a diene rubber polymer using a rubber component such as polybutadiene, polyisoprene, and styrene-butadiene copolymer can be cited. As other copolymerizable monomers, for example, maleimide monomers such as maleimide, N-methylmaleimide, N-cyclohexylmaleimide, and N-phenylmaleimide; acrylamide monomers such as acrylamide and N-methylacrylamide; unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; unsaturated acids such as acrylic acid and methacrylic acid; glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, methoxy polyethylene glycol methacrylate, etc. The upper limit of the ratio of other monomers in component B is more preferably 40% by weight, and more preferably 30% by weight in 100% by weight of component B.

[0094] As specific examples of component B, preferably acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene-α-methylstyrene copolymer, acrylonitrile-butadiene-styrene-N-phenylmaleimide copolymer, etc. can be exemplified, among which acrylonitrile-butadiene-styrene copolymer is preferred. These copolymers can be used alone or in combination of two or more.

[0095] Component B may be produced by any polymerization method including bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and the copolymerization method may be one-step grafting or multi-step grafting. In addition, it may be a mixture with a copolymer formed only by a graft component generated as a by-product during production.

[0096] The content of component B is 10 to 55 parts by weight, preferably 15 to 45 parts by weight, and more preferably 20 to 35 parts by weight in 100 parts by weight of the resin component composed of components A and B. If the content of component B is less than 10 parts by weight, sufficient fluidity cannot be obtained, and if it exceeds 55 parts by weight, impact resistance and heat resistance are reduced.

[0097] (Component C: acrylic block copolymer)

[0098] The acrylic block copolymer used in the present invention is not particularly limited as long as it is an acrylic block copolymer having a copolymer having more than one type of polymer block as the main component, and the above-mentioned polymer block is obtained by polymerizing the monomer components containing methacrylic acid and their derivatives. It is preferably an acrylic block copolymer containing a polymer block containing an acrylate monomer unit and a polymer block containing a methacrylate monomer unit, and more preferably an acrylic block copolymer containing a polymer block containing a methacrylate monomer unit in the acrylic block copolymer. The content of the polymer block containing methacrylate monomer units is 25% by weight or more. When the content is less than 25% by weight, the impact resistance is sometimes reduced. The content is more preferably 30% by weight or more, and more preferably 35% by weight or more. It should be noted that the upper limit of the content is not particularly limited, but is preferably 60% by weight or less.

[0099] Examples of the acrylic acid ester monomer include acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, phenyl acrylate, and dimethylaminoethyl acrylate.

[0100] Examples of the methacrylate monomer include methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, decyl methacrylate, octadecyl methacrylate, dodecyl methacrylate, and 2-ethylhexyl methacrylate.

[0101] The content of component C is 0.5 to 10 parts by weight, preferably 0.8 to 8 parts by weight, and more preferably 1 to 6 parts by weight relative to 100 parts by weight of the resin component composed of components A and B. When the content of component C is less than 0.5 parts by weight, the impact resistance cannot be sufficiently improved, and when it exceeds 10 parts by weight, the appearance of the molded product deteriorates and the tape peel strength also decreases.

[0102] (Ingredient D: phosphorus antioxidant)

[0103] The phosphorus-based antioxidant used in the present invention is not particularly limited, and examples thereof include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and their esters, and tertiary phosphine. The above-mentioned phosphorus-based stabilizers may be used not only alone but also in combination of two or more. Examples of the phosphite compound include trialkyl phosphites such as tridecyl phosphite; dialkyl monoaryl phosphites such as didecyl monophenyl phosphite; monoalkyl diaryl phosphites such as monobutyl diphenyl phosphite; triaryl phosphites such as triphenyl phosphite and tris(2,4-di-tert-butylphenyl)phosphite; distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and di-(2,4-di-tert-butylphenyl)pentaerythritol tetrahydrofuran. Pentaerythritol phosphites such as alcohol diphosphites, bis(2,4-dicumylphenyl)pentaerythritol diphosphites and bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphites; and cyclic phosphites such as 2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphites and 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2,4-di-tert-butylphenyl)phosphites. Examples of the phosphate ester compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, triethyl phosphate, diphenylcresyl phosphate, diphenylmono-o-biphenyl phosphate, tributoxyethyl phosphate and diisopropyl phosphate, and triphenyl phosphate and trimethyl phosphate are preferred. As the phosphonite compound, tetrakis(di-tert-butylphenyl)-biphenylene diphosphonite and bis(di-tert-butylphenyl)-phenyl-phenyl phosphonite can be preferably exemplified, and tetrakis(2,4-di-tert-butylphenyl)-biphenylene diphosphonite and bis(2,4-di-tert-butylphenyl)-phenyl-phenyl phosphonite are more preferred. The above-mentioned phosphonite compound can be used in combination with the above-mentioned phosphite compound having an aryl group substituted with two or more alkyl groups, and is therefore preferred. As the phosphonate compound, dimethyl phenylphosphonate, diethyl phenylphosphonate and dipropyl phenylphosphonate can be cited. As the tertiary phosphine, for example, triphenylphosphine can be exemplified.

[0104] The content of component D is 0.01 to 3.0 parts by weight, preferably 0.05 to 2.0 parts by weight, and more preferably 0.1 to 1.0 parts by weight, relative to 100 parts by weight of the resin component composed of components A and B. When the content of component D is less than 0.01 parts by weight, the appearance of the molded product deteriorates and the tape peel strength also decreases. When the content of component D exceeds 3.0 parts by weight, the appearance of the molded product deteriorates due to contamination of the metal mold of the molding machine.

[0105] (Ingredient E: hindered phenol antioxidant)

[0106] The hindered phenol antioxidant used in the present invention is not particularly limited, and various compounds usually formulated in resins can be used. Examples of the hindered phenol antioxidant include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2,6-di-tert-butyl-4-(N,N-dimethylaminomethyl)phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'- Methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-dimethylenebis(6-α-methyl-benzyl-p-cresol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-butylidenebis(4-methyl-6-tert-butylphenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[2-tert-butyl-4-methyl 6-(3-tert-butyl-5-methyl-2-hydroxybenzyl)phenyl]terephthalate, 3,9-bis{2-[3 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol), bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4'-di-thiobis(2,6-di-tert-butylphenol), 4,4'-tri-thiobis(2,6-di-tert-butylphenol), 2,2-thiodimethylenebis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis( 1,3,5-triazine, N,N'-hexamethylenebis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid), N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 1,1,3-tri(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tri(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tri(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanate, tri(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanate, 1,3,5-tri(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanate, 1,3,5-tris-2[3(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl isocyanate, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl) acetate, 3,9-bis[2 [3-(3-tert-butyl-4-hydroxy-5-methylphenyl)acetoxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, tetrakis[methylene-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]methane, 1,3,5-trimethyl-2,4,6-tri(3-tert-butyl-4-hydroxy-5-methylbenzyl)benzene and tri(3-tert-butyl-4-hydroxy-5-methylbenzyl)isocyanate, etc. Among the above compounds, tetrakis[methylene-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]methane, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane are preferably used in the present invention. 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane is particularly preferred. The above hindered phenol antioxidants can be used alone or in combination of two or more.

[0107] The content of component E is 0.01 to 3.0 parts by weight, preferably 0.05 to 2.0 parts by weight, and more preferably 0.1 to 1.0 parts by weight relative to 100 parts by weight of the resin component composed of components A and B. When the content of component E is less than 0.01 parts by weight, the appearance of the molded product deteriorates and the tape peel strength also decreases. When the content of component E exceeds 3.0 parts by weight, the metal mold of the molding machine is contaminated, thereby deteriorating the appearance of the molded product.

[0108] (Other ingredients)

[0109] The resin composition of the present invention may further contain a heat stabilizer, a mold release agent, a UV absorber, an impact modifier, a dye pigment (carbon black, titanium dioxide, etc.), etc. in addition to the phosphorus-based and hindered phenol-based antioxidants.

[0110] (i) Heat stabilizers other than phosphorus-based and hindered phenol-based antioxidants

[0111] The resin composition of the present invention may be formulated with other heat stabilizers other than the above-mentioned phosphorus-based and hindered phenol-based antioxidants. The above-mentioned heat stabilizer is preferably used in combination with these antioxidants, and is particularly preferably used in combination with both. As the above-mentioned other heat stabilizers, for example, a lactone stabilizer represented by a reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene can be preferably exemplified (the details of the above-mentioned stabilizer are described in Japanese Patent Publication No. 7-233160). The above-mentioned compound is commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and this compound can be used. In addition, stabilizers obtained by mixing this compound with various phosphite compounds and hindered phenol compounds are also commercially available. For example, Irganox HP-2921 manufactured by the above-mentioned company can be preferably exemplified. In the present invention, the above-mentioned pre-mixed stabilizer can also be used. The amount of the lactone stabilizer to be added is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight, based on 100 parts by weight of the resin component consisting of the components A and B.

[0112] In addition, as other stabilizers, sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-lauryl thiopropionate) and glycerol-3-stearyl thiopropionate can be exemplified. The above stabilizers are particularly effective when the resin composition is applied to rotational molding. The amount of the above sulfur-containing stabilizer is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight, relative to 100 parts by weight of the resin component composed of component A and component B.

[0113] (ii) Release agent

[0114] In the range that does not impair the effect of the present invention, a mold release agent can be formulated in the resin composition of the present invention for the purpose of improving its productivity during molding and reducing the deformation of the molded product. As the above-mentioned mold release agent, a known mold release agent can be used. For example, saturated fatty acid esters, unsaturated fatty acid esters, silicone compounds, fluorine compounds (fluorine oils represented by polyfluoroalkyl ethers, etc.), paraffin, beeswax, etc. can be mentioned. Among them, as a preferred mold release agent, fatty acid esters can be mentioned. The above-mentioned fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids. The above-mentioned aliphatic alcohols can be monohydric alcohols or polyhydric alcohols with a valence of more than two hydrations. In addition, the number of carbon atoms of the alcohol is in the range of 3 to 32, and more preferably in the range of 5 to 30. As the above-mentioned monohydric alcohol, for example, dodecanol, tetradecanol, hexadecanol, octadecyl alcohol, eicosanol, tetracosanol, wax alcohol and triacontanol can be exemplified. Examples of the polyols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. Polyols are more preferred in the fatty acid esters of the present invention. On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, and particularly preferably has 10 to 22 carbon atoms. Examples of the aliphatic carboxylic acid include saturated aliphatic carboxylic acids such as decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, behenic acid, eicosanoic acid, and behenic acid; and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and docosenoic acid. Among the above, the aliphatic carboxylic acid is most preferably an aliphatic carboxylic acid having 14 to 20 carbon atoms. Among them, saturated aliphatic carboxylic acids are preferred. Stearic acid and palmitic acid are particularly preferred. The above-mentioned aliphatic carboxylic acids such as stearic acid and palmitic acid are usually made from natural oils and fats such as animal fats and fats represented by beef tallow and lard, and plant fats and fats represented by palm oil and safflower oil, so these aliphatic carboxylic acids are usually mixtures containing other carboxylic acid components with different carbon atoms. Therefore, in the manufacture of the fatty acid ester of the present invention, it is also preferred to use aliphatic carboxylic acids made from the above-mentioned natural oils and fats and composed of a mixture containing other carboxylic acid components, especially stearic acid and palmitic acid. The fatty acid ester can be any of a partial ester and a full ester (complete ester). However, in partial esters, the hydroxyl value usually becomes high and it is easy to induce the decomposition of the resin at high temperature, so it is more preferably a complete ester. From the point of view of thermal stability, the acid value of the fatty acid ester of the present invention is preferably 20 or less, more preferably in the range of 4 to 20, and further preferably in the range of 4 to 12. It should be noted that the acid value can be substantially 0. In addition, the hydroxyl value of the fatty acid ester is more preferably in the range of 0.1 to 30. Moreover, the iodine value is preferably 10 or less. It should be noted that the iodine value can be substantially 0. These properties can be obtained by the method prescribed in JIS K 0070.

[0115] The content of the release agent is preferably 0.01 to 4.0 parts by weight, more preferably 0.05 to 3.0 parts by weight, and even more preferably 0.1 to 2.5 parts by weight, based on 100 parts by weight of the resin component consisting of the components A and B.

[0116] (iii) Ultraviolet light absorber

[0117] The resin composition of the present invention may contain an ultraviolet absorber. Examples of the benzophenone series include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfonic acid benzophenone, 2-hydroxy-4-methoxy-5-sulfonic acid trihydrobenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5-sodium sulfonate, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone. Among the benzotriazole series, for example, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octyloxyphenyl)benzotriazole, 2,2'-methylenebis(4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis(1,3-benzotriazole) The invention also relates to polymers having a 2-hydroxyphenyl-2H-benzotriazole skeleton, such as 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole, copolymers of 2-(2'-hydroxy-5-methacryloyloxyethylphenyl)-2H-benzotriazole and a vinyl monomer copolymerizable with the monomer, and copolymers of 2-(2'-hydroxy-5-acryloyloxyethylphenyl)-2H-benzotriazole and a vinyl monomer copolymerizable with the monomer. Examples of hydroxyphenyltriazine-based compounds include 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-hexyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-methoxyphenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-ethoxyphenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-propoxyphenol, and 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-butoxyphenol. Examples include compounds in which the phenyl group of the above-exemplified compounds is 2,4-dimethylphenyl, such as 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5-hexyloxyphenol. Examples of cyclic iminoesters include 2,2'-p-phenylenebis(3,1-benzo Oxazine-4-one), 2,2'-(4,4'-diphenylene)bis(3,1-benzo Oxazine-4-one) and 2,2'-(2,6-naphthylene)bis(3,1-benzo Oxazine-4-one) etc.

[0118] Examples of cyanoacrylates include 1,3-bis-[(2′-cyano-3′,3′-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-diphenylacryloyl)oxy]methyl)propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene.

[0119] Furthermore, the ultraviolet absorber may be a polymer type ultraviolet absorber obtained by copolymerizing the ultraviolet absorbing monomer and / or the light stabilizing monomer having a hindered amine structure with a monomer such as (meth) alkyl acrylate by adopting the structure of a monomer compound capable of free radical polymerization. As the ultraviolet absorbing monomer, preferably, there are compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton and a cyanoacrylate skeleton in the ester substituent of the (meth) acrylate.

[0120] The content of the ultraviolet absorber is preferably 0.01 to 2.0 parts by weight, more preferably 0.02 to 1.5 parts by weight, and even more preferably 0.03 to 1.0 parts by weight, based on 100 parts by weight of the resin component consisting of the components A and B.

[0121] (iv) Other resins and elastomers

[0122] In the resin composition of the present invention, other resins or elastomers can also be used in a small proportion within the scope of exerting the effect of the present invention. As the above-mentioned other resins, for example, polypropylene resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyamide resin, polyimide resin, polyetherimide resin, polyurethane resin, silicone resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polymethacrylate resin, phenol resin, fluororesin and other resins can be cited. In addition, as elastomers, for example, isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, MBS (methyl methacrylate / styrene / butadiene) rubber as core-shell elastomer, MB (methyl methacrylate / butadiene) rubber, MAS (methyl methacrylate / acrylonitrile / styrene) rubber, etc. can be cited.

[0123] (v) Dyes and Pigments

[0124] The resin composition of the present invention can further provide a molded product containing various dyes and pigments and showing various designs. By combining a fluorescent whitening agent or a fluorescent dye that emits light other than the fluorescent whitening agent, a further good design effect utilizing the luminescent color can be given. In addition, a resin composition colored with a very small amount of dyes and pigments and having a bright color development property can also be provided.

[0125] As fluorescent dyes (including fluorescent whitening agents) used in the present invention, for example, coumarin fluorescent dyes, benzopyran fluorescent dyes, perylene fluorescent dyes, anthraquinone fluorescent dyes, thioindigo fluorescent dyes, xanthene fluorescent dyes, xanthone fluorescent dyes, thioxanthene fluorescent dyes, thioxanthene fluorescent dyes, thiazine fluorescent dyes and diaminostilbene fluorescent dyes can be cited. Among these, coumarin fluorescent dyes, benzopyran fluorescent dyes and perylene fluorescent dyes are preferred because they have good heat resistance and are less degraded during the molding of polycarbonate resins.

[0126] As dyes other than the above-mentioned bluing agents and fluorescent dyes, ferrocyanides such as perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, and Prussian blue can be cited; perinone dyes, quinoline dyes, quinacridone dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes, etc. In addition, the resin composition of the present invention can also obtain a better metallic color by matching metallic pigments. As metallic pigments, metallic pigments having a metal film or a metal oxide film in various plate-like fillers are preferred.

[0127] The content of the dye and pigment is preferably 0.00001 to 1 part by weight, more preferably 0.00005 to 0.5 part by weight, based on 100 parts by weight of the resin component consisting of the components A and B.

[0128] (vi) Flame retardant

[0129] In the resin composition of the present invention, various compounds that have been known as flame retardants for thermoplastic resins, especially polycarbonate resins, can be used, but more preferably (i) halogen flame retardants (e.g., brominated polycarbonate compounds, etc.); (ii) phosphorus flame retardants (e.g., monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphazene oligomer compounds, phosphonic acid amide compounds, and phosphazene compounds, etc.); (iii) metal salt flame retardants (e.g., organic sulfonic acid alkali (earth) metal salts, borate metal salt flame retardants, and stannate metal salt flame retardants, etc.); (iv) silicone flame retardants composed of silicone compounds. It should be noted that the combination of compounds used as flame retardants can not only improve flame retardancy, but also bring about improvements in antistatic properties, fluidity, rigidity, and thermal stability, etc., according to the properties of each compound.

[0130] The content of the flame retardant is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 28 parts by weight, and further preferably 0.08 to 25 parts by weight relative to 100 parts by weight of the resin component consisting of component A and component B. When the content of the flame retardant is less than 0.01 parts by weight, sufficient flame retardancy may not be obtained, and when it exceeds 30 parts by weight, the mechanical properties may be greatly reduced.

[0131] (vii) White pigment for high light reflection

[0132] The resin composition of the present invention may be combined with a white pigment for high light reflection to impart a light reflection effect. Examples of the white pigment include zinc sulfide, zinc oxide, barium sulfate, calcium carbonate, calcined kaolin, and the like. The content of the white pigment for high light reflection is preferably 1 to 30 parts by weight, more preferably 3 to 25 parts by weight, relative to 100 parts by weight of the resin component composed of component A and component B. It should be noted that two or more white pigments for high light reflection may be used in combination.

[0133] (viii) Other additives

[0134] In addition, in order to give various functions or improve characteristics to the molded product, the resin combination of the present invention can be matched with additives known in itself in a small amount. As long as these additives do not harm the purpose of the present invention, they are all common amounts. As the above-mentioned additives, lubricants (such as PTFE particles), colorants (such as pigments and dyes such as carbon black), light diffusing agents (such as acrylic acid cross-linked particles, silicon cross-linked particles, very thin glass sheets, calcium carbonate particles), fluorescent dyes, inorganic fluorescent bodies (such as fluorescent bodies using aluminate as mother crystals), antistatic agents, crystallization nucleating agents, inorganic and organic antibacterial agents, photocatalyst system antifouling agents (such as micro-particle titanium dioxide, micro-particle zinc oxide), free radical generators, infrared absorbers (heat absorbers) and photochromic agents etc. can be enumerated.

[0135] (Method for preparing resin composition)

[0136] The resin composition of the present invention is prepared by mixing the above-mentioned components simultaneously or in any order using a mixer such as a drum mixer, a V-type mixer, a Nauta mixer, a Banbury mixer, a mixing roll, an extruder, etc. As a mixer, it is preferred to use a twin-screw extruder for melt mixing, and it is preferred to use a side feeder etc. to supply any component from a second supply port to the other components of the melt mixing as needed. The extruded resin as described above can be directly cut for granulation, or the above-mentioned filament bundle can be cut for granulation by a granulator after forming a filament bundle. When granulating, it is preferred to clean the atmosphere around the extruder when it is necessary to reduce the influence of external dust, etc. Regarding the shape of the obtained particles, general shapes such as cylinders, square columns and spheres can be obtained, and cylinders are more preferred. The diameter of the above-mentioned cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and more preferably 2 to 3.5 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and more preferably 2.5 to 4 mm.

[0137] (Regarding the molded article composed of the resin composition of the present invention)

[0138] The resin composition of the present invention can usually be manufactured various products by injection molding the particles obtained by the above method. In the above-mentioned injection molding, not only is it a common molding method, but also it is possible to use injection molding methods such as injection compression molding, injection pressure molding, gas-assisted injection molding, foam molding (comprising a method of injecting a supercritical fluid), insert molding, in-mold coating molding, thermal insulation mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding and ultra-high speed injection molding to obtain molded products according to appropriate purposes. The advantages of these various molding methods are widely known. In addition, molding can also select any one of the cold runner method and the hot runner method.

[0139] The present inventors have implemented a method that combines the preferred ranges of the above-mentioned requirements, and representative examples thereof are described in the following Examples. Of course, the present invention is not limited to these methods.

[0140] Example

[0141] Hereinafter, the present invention will be described in further detail with reference to Examples. In addition, the following "parts" means "parts by weight" and % means "% by weight" unless otherwise specified.

[0142] (1) Preparation of resin composition

[0143] (1-1) Raw materials used

[0144] (A ingredient)

[0145] A-1: Polycarbonate resin powder with a molecular weight of 19800 obtained by the following method

[0146] A three-stage six-blade agitator and a circulating cooling tube were installed in a baffled reaction vessel. 45.6 parts of bisphenol A, 2.78 mol% of p-tert-butylphenol relative to bisphenol A, 265 parts of dichloromethane and 200 parts of water were added to the reaction vessel, and nitrogen was purged to remove oxygen in the reaction vessel. It should be noted that at the above stage, the content in the reaction vessel was less than 80% of the container capacity. Next, about 80 parts of an aqueous solution for supplying 0.09 parts of sodium dithionite and 21.8 parts of sodium hydroxide were supplied to the above suspension to dissolve bisphenol A at 15°C. Under stirring, 23.35 parts of phosgene were supplied to the mixture for 30 minutes. Then, 0.016 parts of triethylamine (0.08 mol% relative to bisphenol A) was added and stirred for 60 minutes to terminate the reaction. Then, the reaction mixture was allowed to stand and the organic phase was separated. Methylene chloride was added to the obtained dichloromethane solution of the polycarbonate resin to prepare a solution with a concentration of 14% by weight, and further, a 0.5% sodium hydroxide aqueous solution was supplied at a flow rate of 1,000 ml / min and an organic phase was supplied at a flow rate of 1000 ml / min using a centrifugal extractor with a porous plate (KCC centrifugal extractor manufactured by KAWASAKI ENGINEERING Co., Ltd.), and the organic phase was treated at 3500 rpm to make the organic phase acidic with hydrochloric acid, and then repeatedly washed with water until the conductivity of the aqueous phase became approximately the same as that of ion-exchanged water, and the dichloromethane was evaporated to obtain a polycarbonate resin powder.

[0147] (Component B)

[0148] B-1: ABS resin (MAGNUM A371 manufactured by TRISEO HOLDINGS ASIAPTTE.LTD.)

[0149] (Component C)

[0150] C-1: an acrylic block copolymer containing a polymer block containing an acrylic acid ester monomer unit and a polymer block containing a methacrylic acid ester monomer unit (content of the polymer block containing a methacrylic acid ester monomer unit in the acrylic block copolymer: 50% by weight, KURARITY LA4285 manufactured by KURARAY CO., LTD.)

[0151] C-2: an acrylic block copolymer containing a polymer block containing an acrylic acid ester monomer unit and a polymer block containing a methacrylic acid ester monomer unit (content of the polymer block containing a methacrylic acid ester monomer unit in the acrylic block copolymer: 40% by weight, KURARITY LA2270 manufactured by KURARAY CO., LTD.)

[0152] C-3: an acrylic block copolymer containing a polymer block containing an acrylic acid ester monomer unit and a polymer block containing a methacrylic acid ester monomer unit (content of the polymer block containing a methacrylic acid ester monomer unit in the acrylic block copolymer: 30% by weight, KURARITY LA2250 manufactured by KURARAY CO., LTD.)

[0153] C-4: an acrylic block copolymer containing a polymer block containing an acrylic acid ester monomer unit and a polymer block containing a methacrylic acid ester monomer unit (content of the polymer block containing a methacrylic acid ester monomer unit in the acrylic block copolymer: 20% by weight, KURARITY LA2140 manufactured by KURARAY CO., LTD.)

[0154] (Component D)

[0155] D-1: Phosphorus antioxidant (Adekastab 2112 manufactured by ADEKA Corporation)

[0156] (Ingredient E)

[0157] E-1: Hindered phenol antioxidant (Adekastab AO-50 manufactured by ADEKA Corporation)

[0158] (Other ingredients)

[0159] F-1: Release agent (fatty acid ester, RIKESTAR EW-400 manufactured by Riken Vitamin Co., Ltd.)

[0160] F-2: Carbon black (Koshigaya Chemicals Co., Ltd.: ROYAL BLACK RB90003S)

[0161] (2) Preparation of test pieces

[0162] (2-1) Production of resin composition

[0163] The components listed in Table 1 were mixed in the listed proportions, and the mixture was supplied from the first supply port of the extruder. The mixture was obtained by mixing using a V-type mixer. Extrusion was performed using a 30 mm diameter vented twin screw extruder (TEX30α-38.5BW-3V, Nippon Steel Works, Ltd.) and melt kneading was performed under the conditions of a screw speed of 230 rpm, a discharge of 25 kg / h, and a vacuum degree of 3 kPa to obtain pellets. It should be noted that the extrusion temperature from the first supply port to the die head portion was set to 260°C.

[0164] (2-2) Method for preparing test pieces for Charpy impact strength measurement and heat resistance evaluation

[0165] The obtained pellets were dried at 110°C for 6 hours using a hot air circulation dryer and then molded into ISO bending test pieces using an injection molding machine [EC130XII-4Y manufactured by Toshiba Machine Co., Ltd.] at a cylinder temperature of 260°C and a mold temperature of 70°C.

[0166] (2-3) Method for preparing test pieces for evaluation of molded product appearance and tape peeling

[0167] The pellets were dried at 110°C for 6 hours using a hot air circulation dryer and then molded into a plate of 100 mm in width × 100 mm in length × 2 mm in thickness using an injection molding machine [EC130XII-4Y manufactured by Toshiba Machine Co., Ltd.] at a cylinder temperature of 280°C and a mold temperature of 70°C.

[0168] (3) Evaluation items

[0169] The following items were evaluated. The results are shown in Table 1.

[0170] (3-1) Charpy impact strength

[0171] Using the ISO bending test piece obtained by the above method, the notched Charpy impact strength was measured in an atmosphere of a temperature of 23°C and a relative humidity of 50% RH in accordance with ISO 179. The resin composition of the present invention needs to have a Charpy impact strength of 60 kJ / m 2 above.

[0172] (3-2) Appearance of molded products

[0173] The appearance of the plate having a width of 100 mm×a length of 100 mm×a thickness of 2 mm produced by the above method was evaluated by visual observation. The evaluation was performed based on the following criteria. The resin composition of the present invention needs to be "0".

[0174] ○: No defect in appearance was observed.

[0175] ×: The molded product has poor appearance such as whitening or silver streaks.

[0176] (3-3) Tape peeling

[0177] On the surface of a plate of 100 mm in width × 100 mm in length × 2 mm in thickness produced by the above method, 11 straight lines were added at 1 mm intervals using a cutter (a cutter (trade name) Aplus (for stationery) manufactured by Olfa Co., Ltd.), and 11 more lines were added orthogonally by changing the direction by 90° to make 100 grids of 1 mm square cuts. A cellophane tape (Cellotape (registered trademark) CT-15 manufactured by Nichiban Co., Ltd.) was pasted on the produced grid, and after being pressed with a finger to make it adhere, one end of the tape was violently peeled off at an angle of 90°, and the peeling state of the cellophane tape as a sample was evaluated by visual observation. It should be noted that the evaluation was carried out according to the following criteria.

[0178] ○: No peeling was observed.

[0179] ×: Peeling was observed.

[0180] (3-4) Heat resistance

[0181] Using the ISO bending test piece obtained by the above method, the load deflection temperature (HDT) was measured under a load of 1.8 MPa using a HDT / VICAT tester [Heat Distortion Tester 6M-2 manufactured by Toyo Seiki Seisaku-sho, Ltd.] in accordance with ISO 75-1.2.

[0182] (3-5) Liquidity

[0183] The obtained pellets were dried at 110°C for 6 hours using a hot air circulation dryer, and then the melt volume rate (MVR) was measured using a semi-automatic melt flow index tester [Semi-automatic melt flow index tester 2A manufactured by Toyo Seiki Seisaku-sho Co., Ltd.] at a temperature of 250°C and a weight of 5000 g.

[0184]

Claims

1. A resin composition comprising 0.5 to 10 parts by weight of an acrylic block copolymer (component C), 0.01 to 3.0 parts by weight of a phosphorus-based antioxidant (component D), and 0.01 to 3.0 parts by weight of a hindered phenol-based antioxidant (component E), relative to 100 parts by weight of a resin component consisting of 45 to 90 parts by weight of a polycarbonate resin (component A) and 10 to 55 parts by weight of a copolymer (component B) obtained by polymerizing an aromatic vinyl monomer and a vinyl cyanide monomer.

2. The resin composition according to claim 1, characterized in that The component C is an acrylic block copolymer containing a polymer block comprising an acrylic acid ester monomer unit and a polymer block comprising a methacrylic acid ester monomer unit.

3. The resin composition according to claim 2, characterized in that The content of the polymer block containing the methacrylic acid ester monomer unit in the component C is 25% by weight or more in the total blocks.

4. The resin composition according to claim 1 or 2, characterized in that Component B is ABS resin.

5. A molded article, comprising the resin composition according to claim 1 or 2.

6. The molded article according to claim 5, characterized in that The molded products are automotive parts.

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