JP2014181279A - Natural rubber-containing thermoplastic resin composition and its molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a natural rubber-containing thermoplastic resin composition consisting of a natural rubber, a polycarbonate resin, a rubber reinforced styrenic resin, a styrenic resin and a nitrile-based resin, and having both of high flowability and high shock resistance.SOLUTION: There is provided a natural rubber-containing thermoplastic resin composition containing a polycarbonate resin (I) of 40 to 75 pts.wt., a graft copolymer (II) obtained by graft copolymerizing a vinyl-based monomer mixture with a natural rubber having a specific grain diameter and a synthetic rubber grain of 10 to 25 pts.wt., and a vinyl-based copolymer (III) satisfying following (A) and (B) of 15 to 35 pts.wt. (A) It is manufactured by copolymerizing an aromatic vinyl-based monomer (d) of 74 to 85 wt.% and a vinyl cyanide monomer (e) of 15 to 26 wt.%. (B) There is a copolymer having a composition with 2 wt.% or more higher than average vinyl cyanide percentage content in a composition distribution of vinyl cyanide in the vinyl-based copolymer (III) at 10 to 50 wt.% in the vinyl-based copolymer (III).

Description

  The present invention relates to a thermoplastic resin composition comprising a polycarbonate resin and a rubber-reinforced styrene resin, which contains natural rubber and has both high fluidity and high impact resistance.

  Since polycarbonate resin is excellent in heat resistance and impact resistance, it is widely used in various fields including the automobile field, the home appliance field, the OA equipment field, and the building material field. On the other hand, rubber-reinforced styrene resin represented by ABS resin has excellent processability and mechanical properties, so it can mold various components in a wide range of fields such as automobile, home appliance, and OA equipment. Used as a material.

  Polycarbonate resin is inferior in moldability and secondary processability at the time of injection molding compared to rubber-reinforced styrene resin, so an alloy that melt-mixed polycarbonate resin and rubber-reinforced styrene resin is used to compensate for the disadvantages of polycarbonate resin. It is common that However, the polycarbonate resin / rubber reinforced styrene resin alloy serves the purpose of further improving the impact resistance of the rubber reinforced styrene resin. However, the compatibility between the polycarbonate resin and the rubber reinforced styrene resin is low, so that the molding processability is enhanced by the rubber. It is known that it is significantly reduced compared to styrene resin.

  As a technique for improving fluidity without impairing the impact resistance of past polycarbonate resin / rubber reinforced styrene resin alloys, Patent Document 1 discloses a specific graft copolymer and specific cyanation in polycarbonate resin / ABS resin alloy. By blending a rubber-reinforced styrene resin containing a vinyl copolymer and a polycarbonate, high fluidity and high impact resistance are achieved.

In recent years, there has been an increasing need for resin compositions using natural raw materials typified by polylactic acid from the viewpoint of carbon neutral, and the application of natural raw materials to thermoplastic resin compositions containing rubbery polymers. As an example, there is a technique of replacing synthetic rubber such as polybutadiene used as a rubbery polymer with natural rubber. As a specific example, Patent Document 2 discloses a rubber obtained by copolymerization of at least one compound selected from a vinyl cyanide compound, an acrylic ester and a methacrylic ester and an aromatic vinyl compound in the presence of a rubbery polymer. 40 to 97% by weight of a modified thermoplastic resin or a mixture of the rubber-like polymer or rubber-modified thermoplastic resin and a copolymer of the above monomer, an aromatic vinyl compound, a vinyl cyanide compound, and a copolymer thereof A copolymer obtained by polymerizing a possible polyfunctional compound and, if necessary, a monomer mixture composed of another polymerizable vinyl compound with an organic hydroperoxide as an initiator, the composition Q value by a flow tester is composed of a copolymer of 3 to 60% by weight or less ^{10 × 10 -3 cm 3 / sec} , matte Can provide high capacity styrenic thermoplastic resin composition, natural rubber is described that can be used as the rubber-like polymer. However, Patent Document 8 does not disclose an example in which natural rubber is actually applied.

  Patent Document 3 contains another monomer copolymerizable with an aromatic vinyl compound in the presence of a rubbery polymer containing deproteinized natural rubber having a nitrogen content of 0.1% by mass or less. A graft copolymer obtained by polymerizing a vinyl monomer having a graft ratio of 10 to 65% by mass and an intrinsic viscosity of acetone-soluble component of 0.2 to 1.5 dl / g. It is described that a certain resin modifier can be used for improving the impact resistance of various resins such as aromatic vinyl resins and the surface appearance of molded products.

  In Patent Document 4, an aromatic vinyl compound and a rubbery polymer composed of 3 to 90% by mass of deproteinized natural rubber having a nitrogen content of 0.1% by mass or less and 10 to 97% by mass of synthetic rubber are used. A rubber-modified aromatic vinyl resin composition containing a graft copolymer obtained by polymerizing a vinyl monomer containing another monomer copolymerizable with the aromatic vinyl compound as desired. It is described that the product is excellent in impact resistance and molded article surface appearance.

  Further, Patent Document 5 is a rubber-modified vinyl resin composition containing the following component (A1) and the following component (A2), and the component (A1) has a nitrogen content of 0.1% by mass or less. Graft copolymer obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound and optionally another monomer copolymerizable with the aromatic vinyl compound in the presence of a proteinated natural rubber In the presence of a synthetic rubber, a vinyl monomer containing an aromatic vinyl compound and optionally another monomer copolymerizable with the aromatic vinyl compound is polymerized. It is described that the impact resistance and the appearance of the surface of the molded product can be improved by using the graft copolymer obtained in this manner.

  In Patent Documents 3 to 5, impurities existing in natural rubber, in particular, proteins inhibit the graft polymerization reaction, so that deproteinization of natural rubber latex by a known deproteinization method is required. It is described that the natural rubber latex not subjected to the treatment did not provide a high impact resistance improving effect.

JP 2012-177088 A JP 59-161459 A JP 2011-225790 A JP 2011-225791 A JP 2011-225792 A

  An object of the present invention is to provide a thermoplastic resin composition containing a polycarbonate resin and a rubber-reinforced styrene resin, which contains natural rubber and has both high fluidity and high impact resistance.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor has obtained a natural rubber-containing rubber-reinforced styrene resin composition containing a specific graft copolymer and a specific vinyl cyanide copolymer. And the polycarbonate resin was found to be able to ensure outstandingly high fluidity while having the same impact resistance as that of the polycarbonate resin, and reached the present invention.

That is, this invention is comprised by the following (1)-(3).
(1) Polycarbonate resin (I) natural containing 40 to 75 parts by weight of natural rubber particles having a particle diameter of 1.0 μm or more in an amount of 5% by weight or more and having a weight average particle diameter in the range of 0.3 to 1.2 μm At least aromatic vinyl in the presence of rubber-like polymer (a) comprising 10 to 70% by weight of rubber and 30 to 90% by weight of synthetic rubber having a weight average particle size in the range of 0.2 to 0.4 μm. Graft copolymer which is obtained by graft copolymerization of a vinyl monomer mixture containing a monomeric monomer (A), and the internal graft ratio of rubbery polymer particles having a particle diameter of 1.0 μm or more is 20% or more. A natural rubber-containing thermoplastic resin composition comprising 10 to 25 parts by weight of the union (II) and 15 to 35 parts by weight of a vinyl copolymer (III) satisfying the following (A) and (B).
(A) Aromatic vinyl monomer (D) 74 to 85% by weight and vinyl cyanide monomer (e) 15 to 26% by weight are copolymerized.
(B) In the vinyl cyanide (III) composition distribution of vinyl cyanide, a copolymer having a composition 2 wt% or more higher than the average vinyl cyanide content is 10% in the vinyl copolymer (III). -50% by weight present.
(2) The vinyl copolymer (III) has an intrinsic viscosity measured by a methyl ethyl ketone solvent, 30 ° C. and an Ubbelohde viscometer in a range of 0.35 to 0.50 dl / g, (1 ) -Containing thermoplastic resin composition.
(3) A molded product formed by molding the natural rubber-containing thermoplastic resin composition according to any one of (1) to (2).

  According to the present invention, while using a naturally-derived raw material, it has both high fluidity and high impact resistance. Since it can be obtained, it can be adapted not only to increase the size of the product and the complexity of the shape, but also to reduce the cost of the product by reducing the thickness.

  Hereinafter, the natural rubber-containing thermoplastic resin composition of the present invention and its molded product will be specifically described.

  The polycarbonate resin (I) used in the present invention is a resin having a repeating structural unit represented by the general formula 1.

(In the formula, Z represents a substituted or unsubstituted alkylidene group, cyclohexylidene group, oxygen atom, sulfur atom or sulfonyl group having 2 to 5 carbon atoms. R ₁ , R ₂ , R ₃ and R ₄ are hydrogen atoms. An atom or an alkyl group having 1 to 6 carbon atoms, which may be the same or different.

  The polycarbonate resin (I) is an aromatic dihydroxy compound typically exemplified by 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane. And obtained by reaction with a carbonate precursor typically exemplified by phosgene.

  As the aromatic dihydroxy compound, 2,2-bis (4-hydroxyphenyl) propane (hereinafter sometimes referred to as bisphenol A), 1,1-bis (4-hydroxyphenyl) ethane, 2,2- Bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (3-tert-butyl) -4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis ( 3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4- Bis (hydroxyaryl) alkanes exemplified by droxyphenyl) diphenylmethane and the like; 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis Bis (hydroxyaryl) cycloalkanes exemplified by (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and the like; 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4- Cardio structure-containing bisphenols exemplified by hydroxy-3-methylphenyl) fluorene and the like; dihydroxydiaryl ethers exemplified by 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether and the like ; 4,4'-dihydroxydiphenylsulfur Dihydroxydiaryl sulfides such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide; 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethyl Dihydroxy diaryl sulfoxides exemplified by diphenyl sulfoxide and the like; dihydroxy diaryl sulfones exemplified by 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone and the like; hydroquinone, resorcin, 4,4′-dihydroxydiphenyl and the like.

  Of these, bis (4-hydroxyphenyl) alkanes are preferred, and bisphenol A is particularly preferred. These aromatic dihydroxy compounds may be used singly or in combination of two or more kinds and copolymerized.

  As the carbonate precursor to be reacted with the aromatic dihydroxy compound, carbonyl halide, carbonate ester, haloformate and the like are used. Specifically, phosgene; diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dimethyl carbonate, diethyl carbonate and the like Dialkyl carbonates; dihaloformates of dihydric phenols and the like. Of these, phosgene is often used preferably. These carbonate precursors may also be used alone or in combination of two or more.

  The production method of the polycarbonate resin (I) used in the present invention is not particularly limited, and can be produced by a conventionally known method. Examples of the production method include an interfacial polymerization method (phosgene method), a melt transesterification method, a solution polymerization method (pyridine method), a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer.

  A production method by an interfacial polymerization method is exemplified as a typical production method. In the presence of an organic solvent inert to the reaction and an aqueous alkaline solution, the pH is usually kept at 9 or higher, and an aromatic dihydroxy compound, and if necessary, a molecular weight regulator (terminal terminator) and an antioxidant for the aromatic dihydroxy compound After the reaction with phosgene using an antioxidant for the purpose, a polymerization catalyst such as a tertiary amine or a quaternary ammonium salt is added and interfacial polymerization is performed to obtain a polycarbonate resin. The addition of the molecular weight regulator is not particularly limited as long as it is from the time of phosgenation to the start of the polymerization reaction. The reaction temperature is, for example, 0 to 40 ° C., and the reaction time is, for example, 2 to 5 hours.

  Here, any organic solvent can be used as the organic solvent applicable to the interfacial polymerization as long as it is inert to the interfacial polymerization reaction, does not mix with water, and can dissolve the polycarbonate resin. Examples thereof include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, tetrachloroethane, chloroform, monochlorobenzene and dichlorobenzene, and aromatic hydrocarbons such as benzene, toluene and xylene. Examples of the alkali compound used in the alkaline aqueous solution include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.

  Examples of the molecular weight regulator include a compound having a monovalent phenolic hydroxyl group and phenyl chloroformate. Examples of the compound having a monovalent phenolic hydroxyl group include m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol and p-long chain alkyl-substituted phenol. The amount of the molecular weight regulator used is preferably 0.1 to 1 mol with respect to 100 mol of the aromatic dihydroxy compound.

  Polymerization catalysts include tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine, pyridine; trimethylbenzylammonium chloride, tetrabutylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium chloride, trimethylamine. And quaternary ammonium salts such as octylmethylammonium chloride.

  The polycarbonate resin (I) used in the present invention is in the range of 40 to 75 parts by weight, preferably 50 to 70 parts by weight, more preferably 55 to 65 parts by weight, when the total essential resin component is 100 parts by weight. It is. When the addition amount of the polycarbonate resin (I) is less than 40 parts by weight, although fluidity is excellent, impact resistance and heat resistance are lowered, which is not preferable. On the other hand, when the added amount exceeds 75 parts by weight, although impact resistance and heat resistance are excellent, fluidity at the time of injection molding is insufficient, and a product that cannot be molded is generated.

The melt volume rate of the polycarbonate resin (I) used in the present invention is not particularly limited, and any one can be used. However, it is preferable that the melt volume rate of 300 ° C. × load 1.2Kg conforming to ISO 1133 is in the range of 8~13cm ^3/10 min, more preferably, a melt volume rate 8~12cm ^3/10 min, More preferably, it is 8-11 cm < ³ > / 10 minutes. When the melt volume rate of 300 ° C. × load 1.2Kg to use a 8 cm ^3/10 minutes or less, impact resistance, it heat resistance that insufficient flowability during injection molding are excellent, products that can not be molded is generated is there. On the other hand, although the melt volume rate is excellent in fluidity and to use a more than 13cm ^3/10 minutes, impact resistance and heat resistance may be decreased.

  The graft copolymer (II) blended in the natural rubber-containing thermoplastic resin composition of the present invention contains 5% by weight or more of natural rubber particles having a particle size of 1.0 μm or more and has a weight average particle size of 0.8. A rubbery polymer (a) comprising 10 to 70% by weight of natural rubber in the range of 3 to 1.2 μm and 30 to 90% by weight of synthetic rubber having a weight average particle diameter in the range of 0.2 to 0.4 μm. ) And a vinyl monomer mixture containing at least the aromatic vinyl monomer (i) is obtained by graft copolymerization.

  The natural rubber used for the graft copolymer (II) refers to a substance whose main component is cis-poly 1,4-isoprene, which is contained in rubber tree sap. The sap is produced by addition polymerization in vivo and contains impurities such as a small amount of protein and fatty acid in addition to natural rubber. In the present invention, sap (natural rubber concentration is about 30% by weight) is known purification. -Use natural rubber contained in natural rubber latex with a natural rubber concentration of 60% by weight or more by a solid-liquid separation technique. The natural rubber here is not pre-deproteinized, but the natural rubber may be deproteinized in the process of producing the natural rubber-containing thermoplastic resin composition of the present invention. Any such is acceptable as part of an aspect of the present invention.

  Synthetic rubbers used in the graft copolymer (II) are polybutadiene, poly (butadiene-styrene) (SBR), poly (butadiene-acrylonitrile) (NBR), polyisoprene, poly (butadiene-butyl acrylate), poly (Butadiene-methyl methacrylate), poly (butyl acrylate-methyl methacrylate), poly (butadiene-ethyl acrylate), ethylene-propylene rubber, poly (ethylene-isoprene) or poly (ethylene-methyl acrylate), etc. Can be mentioned. Among these, use of polybutadiene, poly (butadiene-styrene) (SBR), poly (butadiene-acrylonitrile) (NBR) or ethylene-propylene rubber is preferable from the viewpoint of impact resistance, and polybutadiene is more preferable.

  The rubber-like polymer (a) used in the graft copolymer (II) is characterized by comprising 10 to 70% by weight of natural rubber and 30 to 90% by weight of synthetic rubber. When the natural rubber is less than 10% by weight and the synthetic rubber exceeds 90% by weight, the impact resistance against the fluidity of the thermoplastic resin composition containing the graft copolymer (II) is lowered, while the natural rubber Is more than 70% by weight and the synthetic rubber is less than 30% by weight, the impact resistance to fluidity of the thermoplastic resin composition containing the graft copolymer (II) is remarkably lowered, and the color tone and surface gloss It is because it is not preferable because the property is lowered.

  The natural rubber used in the graft copolymer (II) has a particle diameter of 1.0 μm or more and 5% by weight or more of the whole natural rubber particles, and the weight average particle diameter is 0.3 to 1. It is characterized by being in the range of 2 μm, preferably 0.6-1.0 μm.

  The particle size content of 1.0 μm or more contained in natural rubber is based on the whole natural rubber particles from the viewpoint of impact resistance and surface gloss of the thermoplastic resin composition containing the graft copolymer (II). Preferably it is 5 to 50 weight%, More preferably, it is 20 to 45 weight%. When the particle size of 1.0 μm or more is less than 5% by weight of the whole natural rubber particles, the impact resistance is lowered, and the particle size of 1.0 μm or more is 50% by weight of the whole natural rubber particles. If it exceeds 50%, the surface gloss is remarkably lowered.

  If the natural rubber has a weight average particle size of less than 0.3 μm, it is difficult to collect as natural rubber, and it takes time for secondary processing. In addition, if it is less than 0.3 μm, the impact resistance of the thermoplastic resin composition May decrease. On the other hand, when the weight average particle diameter of the natural rubber exceeds 1.2 μm, the impact resistance to the fluidity of the thermoplastic resin composition may be remarkably lowered, and the color tone and surface gloss may be lowered. is there.

  The weight average particle diameter of the synthetic rubber is characterized by being in the range of 0.2 to 0.4 μm, and preferably in the range of 0.2 to 0.3 μm. This is because when the weight average particle diameter is less than 0.2 μm, the impact resistance of the thermoplastic resin composition containing the graft copolymer (II) is lowered, whereas when it exceeds 0.4 μm, the graft copolymer is reduced. This is because a decrease in surface gloss is recognized in addition to a decrease in impact resistance of the thermoplastic resin composition containing the polymer (II), which is not preferable.

  The graft copolymer (II) is obtained by graft polymerizing a rubber-like polymer having the above-defined weight average particle diameter with a vinyl monomer mixture containing at least an aromatic vinyl monomer. Yes, a rubber-like polymer grafted with a vinyl copolymer and an ungrafted vinyl copolymer are included.

  The weight fraction of the rubber-like polymer (a) in the graft copolymer (II) is preferably adjusted to 40 to 60% by weight, and the more preferred weight fraction of the rubber-like polymer (a) is 40 to 60%. It is 55 weight%, More preferably, it is 40-50 weight%. If the weight fraction is less than 40% by weight, the impact of the material is reduced. On the other hand, if it exceeds 60% by weight, the dispersibility of the rubber-like polymer in the graft copolymer (II) is reduced, and the graft copolymer (II ) May decrease the impact resistance of the thermoplastic resin composition.

  Examples of the aromatic vinyl monomer (A) contained in the vinyl monomer mixture include styrene, α-methyl styrene, p-methyl styrene, m-methyl styrene, o-methyl styrene, vinyl toluene, t -Butyl styrene, chlorostyrene, bromostyrene and the like are mentioned, and styrene is particularly preferable. These can be used alone or in combination of two or more. The aromatic vinyl monomer (A) in the graft copolymer (II) and the aromatic vinyl monomer (D) in the vinyl copolymer (III) described later are the same substance. Even different materials may be used, but the same material is preferable.

  Examples of the vinyl cyanide monomer (c) contained in the vinyl monomer mixture include acrylonitrile, methacrylonitrile, ethacrylonitrile, and the like, and acrylonitrile is particularly preferable. These can be used alone or in combination of two or more. The vinyl cyanide monomer (c) in the graft copolymer (II) and the vinyl cyanide monomer (e) in the vinyl copolymer (III) are the same substance. Also, different materials may be used, but the same material is preferable.

  In addition, other copolymerizable monomers may be used in the vinyl monomer mixture to such an extent that the effects of the present invention are not lost. Specifically, it is a monomer selected from an unsaturated carboxylic acid alkyl ester monomer, an unsaturated fatty acid, an acrylamide monomer, and a maleimide monomer, and should be selected according to each purpose. Can do. These can be used alone or in plural.

  Examples of unsaturated carboxylic acid alkyl ester monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic acid. Examples include t-butyl, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, and chloromethyl (meth) acrylate, and methyl (meth) acrylate is preferred. These can be used alone or in combination of two or more.

  Examples of the unsaturated fatty acid include itaconic acid, maleic acid, fumaric acid, butenoic acid, acrylic acid, and methacrylic acid.

  Examples of the acrylamide monomer include acrylamide, methacrylamide, N-methylacrylamide and the like.

  Examples of maleimide monomers include N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide and the like. It is done.

  If there is an intention to improve heat resistance and flame retardancy, N-phenylmaleimide is preferred. Further, methyl methacrylate is preferably used if importance is attached to hardness improvement and transparency.

  The total weight fraction of the vinyl monomer mixture is preferably adjusted to 40 to 60% by weight, more preferably 45 to 60% by weight, and still more preferably 50 to 60% by weight. It is. When the total weight fraction of the vinyl-based monomer mixture is less than 40% by weight, the fluidity is lowered, so that the molding processability may be impaired, and the surface appearance of the molded product may be lowered. On the other hand, if it exceeds 60% by weight, the impact properties of the resin composition may be lowered.

  The composition ratio of the aromatic vinyl monomer (a) and the vinyl cyanide monomer (c) contained in the vinyl monomer mixture is determined from the viewpoint of molding processability. It is preferable that the monomer (A) is 60 to 80% by weight and the vinyl cyanide monomer (U) is 20 to 40% by weight.

  The method for producing the graft copolymer (II) is not particularly limited, and after blending natural rubber and synthetic rubber, it may be graft polymerized with a vinyl monomer mixture. After graft polymerization with the body mixture, the respective graft copolymers may be blended.

  As the graft polymerization method of the rubber polymer (a) and the vinyl monomer mixture, any method such as an emulsion polymerization method, a suspension polymerization method, a continuous bulk polymerization method and a solution continuous polymerization method can be used. Preferably, an emulsion polymerization method or a bulk polymerization method is used. Among these, the emulsion polymerization method is most preferred because it is easy to control the particle size of the rubber-like polymer (a) and it is easy to control by removing heat during polymerization.

  Various surfactants can be used in the emulsion polymerization method, and anionic surfactants such as carboxylate type, sulfate ester type and sulfonate type are particularly preferably used.

  Specific examples of emulsifiers include caprylate, caprate, laurate, misty phosphate, palmitate, stearate, oleate, linoleate, linolenate, rosinate, behenate , Castor oil sulfate, lauryl alcohol sulfate, dodecylbenzenesulfonate, alkylnaphthalenesulfonate, alkyldiphenyl ether disulfonate, naphthalenesulfonate condensate, dialkylsulfosuccinate, polyoxyethylene lauryl sulfate, Examples include polyoxyethylene alkyl ether sulfate and polyoxyethylene alkyl phenyl ether sulfate. Examples of the salt herein include alkali metal salts, ammonium salts, sodium salts, lithium salts, and the like. These emulsifiers are used alone or in combination of two or more.

  As the initiator used for the graft polymerization, a peroxide or an azo compound and water-soluble potassium persulfate are used. Specific examples of the peroxide include benzoyl peroxide, cumene hydroperoxide, dicumyl peroxide, diisopropylbenzene hydroperoxide, t-butyl hydroperoxide, t-butyl peroxyacetate, t-butyl peroxybenzoate, t-butyl isopropyl carbonate, di-t-butyl peroxide, t-butyl peroctate, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (T-butylperoxy) cyclohexane, t-butylperoxy-2-ethylhexanoate, and the like.

  Specific examples of the azo compound include azobisisobutyronitrile, azobis (2,4-dimethylvaleronitrile, 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2-cyano-2-propylazo. Formamide, 1,1′-azobiscyclohexane-1-carbonitrile, azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate, 1-t-butylazo-2 -Cyanobutane, 2-t-butylazo-2-cyano-4-methoxy-4-methylpentane, etc. When these initiators are used, they are used alone or in combination of two or more. However, for emulsion polymerization, potassium persulfate, cumene hydroperoxide, etc. are preferably used, and the initiator is a redox system. It can be used.

  Chain transfer agents such as mercaptans and terpenes may be used for the purpose of adjusting the degree of polymerization and graft ratio of the graft copolymer (II). Specific examples thereof include n-octyl mercaptan and t-dodecyl mercaptan. N-dodecyl mercaptan, n-tetradecyl mercaptan, n-octadecyl mercaptan, terpinolene and the like. When these chain transfer agents are used, they are used alone or in combination of two or more. Of these, n-octyl mercaptan and t-dodecyl mercaptan are preferably used.

  From the graft copolymer latex produced by emulsion polymerization, a coagulant is then added to recover the graft copolymer (II). Acid or water-soluble salt is used as the coagulant, and examples thereof include sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, calcium chloride, magnesium chloride, barium chloride, aluminum chloride, magnesium sulfate, aluminum sulfate, aluminum ammonium sulfate, and aluminum sulfate. Examples include potassium and sodium aluminum sulfate. These coagulants are used alone or in combination of two or more. In order to obtain a resin having an excellent color tone, it is preferable not to leave an emulsifier in the resin, and it is preferable to use an alkali fatty acid salt as the emulsifier and to perform acid coagulation.

  In the monomer charging method, initial batch charging is performed, a part of the monomer is continuously charged in order to control the distribution of the copolymer composition, or part or all of the monomer is divided. Although it may be charged, it is necessary to charge a vinyl monomer mixture of 10% by weight or more of all monomers before the start of emulsion polymerization.

  By introducing a vinyl monomer mixture of 10% by weight or more of all monomers before the start of emulsion polymerization, the vinyl monomer mixture enters and is impregnated into the natural rubber covered with protein. The graft copolymer (II) having a structure can be produced.

  The time for charging 10% by weight or more of the total vinyl-based monomer mixture before the start of emulsion polymerization is not particularly limited. However, in order to promote the impregnation of the vinyl-based monomer mixture into natural rubber, 30 to 90 minutes. It is better to add over a degree.

  The temperature at which 10% by weight or more of the total vinyl-based monomer mixture is charged before the start of emulsion polymerization is not particularly limited, but is preferably 40 to 70 ° C. When the charging temperature is less than 40 ° C., the impregnation of the vinyl monomer mixture into the natural rubber is not sufficient, while when it exceeds 70 ° C., the emulsion stability of the latex may deteriorate.

  In addition, the pH during the emulsion polymerization is not particularly limited, but is preferably in the range of 10 to 12. By setting the pH in the range of 10 to 12, the emulsified state of the latex can be stabilized. In addition, hydrolysis of some proteins is promoted and graft polymerization easily proceeds. To adjust the pH to the range of 10 to 12, potassium hydroxide, sodium hydroxide, or the like is used, but potassium hydroxide having good emulsion stability is preferred and used.

  Although there is no restriction | limiting in particular in the graft rate of graft copolymer (II), It is preferable that it is 30% or more, More preferably, it is 35% or more, More preferably, it is 40% or more. A graft ratio of less than 30% is not preferred because a decrease in impact resistance may be observed due to a decrease in the compatibility of the rubber-like polymer present in the thermoplastic resin composition. On the other hand, the upper limit of the graft ratio is not particularly limited, but if the graft ratio exceeds 70%, the impact resistance improving effect by the rubber-like polymer may be insufficient, and therefore it is preferably 70% or less.

  However, the graft polymer (II) contained in the natural rubber-containing thermoplastic resin composition of the present invention is characterized in that the internal graft ratio of rubber-like polymer particles having a particle diameter of 1.0 μm or more is 20% or more. And preferably 30% or more. The internal graft ratio indicates the ratio of the content of the vinyl copolymer present in the rubber-like polymer to the total amount of the rubber-like polymer and the vinyl copolymer present in the rubber-like polymer. The rubbery polymer does not distinguish between natural rubber and synthetic rubber. When the internal graft ratio of the rubbery polymer particles having a particle diameter of 1.0 μm or more is less than 20%, the rubbery polymer present in the thermoplastic resin composition containing the graft copolymer (II), mainly Since the compatibility of the natural rubber is deteriorated, the impact resistance of the thermoplastic resin composition is lowered. In addition, although there is no restriction | limiting in particular about the upper limit of the internal graft rate of the rubber-like polymer of 1.0 micrometer or more of particle diameter, It is preferable that it is 50% or less.

  The graft copolymer (II) used in the present invention is in the range of 10 to 25 parts by weight, preferably 13 to 22 parts by weight, more preferably 15 to 20 parts, based on 100 parts by weight of the entire essential resin component. Parts by weight. When the added amount of the graft copolymer is less than 10 parts by weight, the flowability of the resin composition is excellent, but the impact resistance is lowered, which is not preferable. On the other hand, when it exceeds 25 weight part, fluidity | liquidity may fall and it is unpreferable.

  The vinyl copolymer (III) used in the present invention is a copolymer of 74 to 85% by weight of an aromatic vinyl monomer (d) and 15 to 26% by weight of a vinyl cyanide monomer (e). (Feature (A)). When the aromatic vinyl monomer (d) is less than 74% by weight, the compatibility with the polycarbonate resin (I) is reduced. On the other hand, when it exceeds 85% by weight, the graft copolymer (II ) Is not preferable because the impact resistance is lowered due to a decrease in compatibility with (A). Preferably, the aromatic vinyl monomer (D) 74 to 83% by weight and the vinyl cyanide monomer (E) 17 to 26% by weight, more preferably the aromatic vinyl monomer (D) 74. -80 wt% and vinyl cyanide monomer (e) 20-26 wt%.

  The aromatic vinyl monomer (d) that is a constituent of the vinyl copolymer (III) is the same as the aromatic vinyl monomer (b) in the graft copolymer (II) described above. , Styrene, α-methylstyrene, vinyltoluene, o-ethylstyrene, p-methylstyrene, chlorostyrene, bromostyrene and the like. Styrene is preferably used. These are not necessarily used alone, and can be used in combination of two or more. Of these, styrene is particularly preferably employed.

  As the vinyl cyanide monomer (e), which is a constituent component of the vinyl copolymer (III), in the same manner as the vinyl cyanide monomer (c) in the graft copolymer (II) described above. Examples thereof include acrylonitrile, methacrylonitrile and ethacrylonitrile, and acrylonitrile is particularly preferably employed. These are not necessarily used alone, and can be used in combination of two or more. Of these, styrene is particularly preferably employed.

  Further, similarly to the graft copolymer (II), the aromatic vinyl monomer (d) and the vinyl cyanide monomer to the extent that the effects of the present invention are not lost in the vinyl copolymer (III). Other vinyl monomers copolymerizable with (e) may be used. Specific examples of other vinyl monomers include N-phenylmaleimide, N-methylmaleimide, methyl methacrylate, and the like, which can be selected according to their purpose. It is possible. N-phenylmaleimide is preferable if there is an intention to further improve heat resistance and flame retardancy. Further, methyl methacrylate is preferably used if emphasis is on improving hardness.

  In the vinyl copolymer (III) used in the present invention, the copolymer having a composition higher by 2 wt% or more than the average vinyl cyanide content in the composition distribution of the vinyl cyanide monomer is a vinyl copolymer. It is necessary that 10 to 50% by weight is present in (III) (feature (B)), preferably 15 to 45% by weight, more preferably 25 to 40% by weight. In the composition distribution of the vinyl cyanide monomer of the vinyl copolymer (III), the copolymer having a composition higher by 2% by weight or more than the average vinyl cyanide content is less than 10% by weight. When it is contained in the coalescence (III), the compatibility with the graft copolymer (II) is lowered. On the other hand, when it exceeds 50% by weight, the compatibility with the polycarbonate is lowered. This is not preferable because the impact resistance of the resin may decrease.

  The composition distribution of the vinyl cyanide monomer in the vinyl copolymer (III) was determined by adding cyclohexane to the methyl ethyl ketone solution of the vinyl copolymer (III), and separating the precipitated vinyl cyanide copolymer. After drying and measuring the weight, it is obtained by determining the vinyl cyanide monomer content with an infrared spectrophotometer. More than 2% by weight from the average vinyl cyanide content in the vinyl copolymer (III) The abundance ratio of the copolymer having a high composition can be determined from the composition distribution obtained with an infrared spectrophotometer (see Examples).

  The vinyl copolymer (III) used in the present invention preferably has a methyl ethyl ketone solvent, 30 ° C., and an intrinsic viscosity measured by an Ubbelohde viscometer of 0.35 to 0.50 dl / g, more preferably 0. .37 to 0.48 dl / g, more preferably 0.40 to 0.45 dl / g. When the intrinsic viscosity is less than 0.35 dl / g, the impact resistance may be lowered, whereas when it exceeds 0.50 dl / g, the fluidity may be lowered.

  The vinyl copolymer (III) used in the present invention is in the range of 15 to 35 parts by weight, preferably 17 to 28 parts by weight, more preferably 20 to 20 parts when the total essential resin component is 100 parts by weight. 25 parts by weight. When the added amount of the vinyl copolymer (III) is less than 15 parts by weight, the fluidity is lowered, which is not preferable. On the other hand, when the amount exceeds 35 parts by weight, the impact is lowered, which is not preferable.

  In the present invention, there is no particular limitation on the method for producing the graft copolymer (II) and the vinyl copolymer (III). Bulk polymerization, suspension polymerization, bulk suspension polymerization, solution polymerization, emulsion polymerization, precipitation polymerization And combinations thereof. There is no particular limitation on the monomer charging method, and it may be added all at once in the initial stage, or the addition method may be divided into several times in order to impart or prevent the composition distribution of the copolymer. .

  In the present invention, as the initiator used for the polymerization of the graft copolymer (II) and the vinyl copolymer (III), a peroxide or an azo compound is preferably used.

  Specific examples of the peroxide include, for example, benzoyl peroxide, cumene hydroperoxide, dicumyl peroxide, diisopropylbenzene hydroperoxide, t-butyl hydroperoxide, t-butyl cumyl peroxide, and t-butyl peroxide. Acetate, t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, di-t-butyl peroxide, t-butyl peroctate, 1,1-bis (t-butylperoxy) 3, 3, 5 -Trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, t-butylperoxy-2-ethylhexanoate and the like. Of these, cumene hydroperoxide and 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane are particularly preferably used.

  Specific examples of the azo compound include azobisisobutyronitrile, azobis (2,4dimethylvaleronitrile), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2-cyano- 2-propylazoformamide, 1,1'-azobiscyclohexane-1-carbonitrile, azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate, 1-t -Butylazo-1-cyanocyclohexane, 2-t-butylazo-2-cyanobutane, 2-t-butylazo-2-cyano-4-methoxy-4-methylpentane, and the like. Of these, azobisisobutyronitrile is particularly preferably used.

  When using these initiators, they are used alone or in combination of two or more.

  In carrying out the polymerization, a chain transfer agent such as mercaptan or terpene can be used for the purpose of adjusting the degree of polymerization of the graft copolymer (II) and vinyl copolymer (III). Specific examples of the chain transfer agent include n-octyl mercaptan, t-dodecyl mercaptan, n-dodecyl mercaptan, n-tetradecyl mercaptan, n-octadecyl mercaptan and terpinolene. Of these, n-octyl mercaptan, t-dodecyl mercaptan and n-dodecyl mercaptan are preferably used. When using these chain transfer agents, they are used alone or in combination of two or more.

  In addition, for the vinyl copolymer (III) used in the present invention, as a production method when satisfying the above-mentioned features (A) and (B), for example, an aqueous system disclosed in Japanese Patent No. 3141707 A suspension polymerization method may be mentioned.

  In the natural rubber-containing thermoplastic resin composition of the present invention, the graft copolymer (II) may exhibit weak alkalinity, and for the purpose of preventing alkali decomposition and thermal decomposition of the polycarbonate resin (I) as a component of the present invention. The acidic compound can be added at the time of producing the graft polymer or at the time of melt kneading for producing the resin composition. The acidic compound that can be used in the present invention is not particularly limited, but specific examples of usable compounds include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, malonic acid, succinic acid, maleic acid, adipine Acid, sebacic acid, dodecanedioic acid, maleic anhydride, succinic anhydride, itaconic acid, benzoic acid, methyl benzoate, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, diphenic acid, phosphoric acid, dihydrogen phosphate Sodium and the like can be mentioned, and maleic anhydride, succinic anhydride, phosphoric acid, and sodium dihydrogen phosphate are preferable, and phosphoric acid and sodium dihydrogen phosphate are more preferable. The acidic compounds exemplified above are not necessarily used alone, and can be used in combination of two or more.

  The addition amount of the acidic compound is preferably within 1.0 part by weight with respect to a total of 100 parts by weight of (I) to (III) as a guide. When 1.0 part by weight or more is used, the alkali component is sufficiently neutralized, but the surface of the injection-molded product may be roughened and the appearance may be impaired.

  In the natural rubber-containing thermoplastic resin composition of the present invention, different resin components can be blended and used as long as the characteristics of the present invention are not impaired. For example, polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, polycyclohexylene dimethylene ethylene terephthalate, polyarylate, liquid crystal polymer, polylactic acid, polyester resin represented by polycaprolactone, nylon 6, nylon 6,6, nylon 6,10 Polyamide resin such as nylon 4,6, nylon 6T, nylon 9T, nylon 11, etc., other PPS resin, polyacetal resin, crystalline styrene resin, PPE resin, etc. can be used according to the purpose.

  Moreover, a well-known impact resistance improving material can be used in the range which does not impair the characteristic of this invention. Examples of impact modifiers that can be used include polyethylenes such as low density polyethylene and high density polyethylene, polypropylene, ethylene / propylene copolymers, ethylene / methyl acrylate copolymers, ethylene / ethyl acrylate copolymers, ethylene / Vinyl acetate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / butyl acrylate copolymer, ethylene / ethyl acrylate / carbon monoxide copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / methyl acrylate / glycidyl methacrylate copolymer Polymer, ethylene / butyl acrylate / glycidyl methacrylate copolymer, ethylene / octene-1 copolymer, ethylene elastomer such as ethylene / butene-1 copolymer, polyethylene terephthalate Examples include polyester elastomers such as polyethylene / tetra (methylene oxide) glycol block copolymer, polyethylene terephthalate / isophthalate / poly (tetramethylene oxide) glycol block copolymer, MBS or acrylic core-shell elastomer, and styrene elastomer. The These are not necessarily used alone, and two or more kinds can be used in combination.

  Moreover, it is also possible to add an inorganic filler in the range which does not impair the characteristic of this invention. As the kind of inorganic filler, glass fiber can be preferably used. In addition, the shape of the inorganic filler may be any shape such as a fiber shape, a plate shape, a powder shape, and a granular shape. Specifically, PAN-based and pitch-based carbon fibers, stainless steel fibers, metal fibers such as aluminum fibers and brass fibers, organic fibers such as aromatic polyamide fibers, gypsum fibers, ceramic fibers, asbestos fibers, zirconia fibers, alumina fibers Fiber, whisker-like filler, mica, talc, silica fiber, titanium oxide fiber, silicon carbide fiber, glass fiber, rock wool, potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker, etc. Kaolin, silica, calcium carbonate, glass flakes, glass beads, glass microballoons, clay, molybdenum disulfide, wollastonite, montmorillonite, titanium oxide, zinc oxide, barium sulfate, calcium polyphosphate, graphite, etc. Or plate-like fillers. In particular, the type of glass fiber is not particularly limited as long as it is generally used for reinforcing a resin, and can be selected from, for example, a long fiber type, a short fiber type chopped strand, a milled fiber, or the like. In addition, the said inorganic filler can also be used by processing the surface with a well-known coupling agent (For example, a silane coupling agent, a titanate coupling agent, etc.) and another surface treating agent. The glass fiber may be coated or bundled with a thermoplastic resin such as an ethylene / vinyl acetate copolymer, or a thermosetting resin such as an epoxy resin. The inorganic filler may be coated or focused with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, or treated with a coupling agent such as aminosilane or epoxysilane. May be.

  In addition, a known matte improving material can be used as long as the characteristics of the present invention are not impaired. Matte improving materials that can be used include unsaturated nitrile-conjugated diene copolymer rubbers such as acrylonitrile-butadiene copolymer rubber, acrylonitrile-isoprene copolymer rubber, and acrylonitrile-butadiene-isoprene copolymer rubber. And acrylonitrile-butadiene-acrylic acid copolymer rubber and the like, and rubbers obtained by hydrogenating conjugated diene units in these rubbers. Other rubbers that may be used in combination with unsaturated nitrile-conjugated diene copolymer rubbers are rubbers that can be crosslinked with crosslinking agents commonly used in the rubber industry such as sulfur vulcanization systems and organic peroxide vulcanization systems. It is. Specific examples thereof include conjugated diene polymer rubbers such as polybutadiene rubber, styrene-butadiene copolymer rubber (random, block), natural rubber, polyisoprene rubber, polychloroprene rubber, and hydrides thereof, EPDM, and the like. .

  Further, as long as it does not impair the characteristics of the present invention, heat such as hindered phenolic antioxidants, sulfur-containing compound-based antioxidants, phosphorus-containing organic compound-based antioxidants, phenol-based, acrylate-based, etc. Antioxidants, UV absorbers such as benzotriazole, benzophenone, and succinate, decabromobiphenyl ether, tetrabromobisphenol A, chlorinated polyethylene, brominated epoxy oligomer, brominated polycarbonate, antimony trioxide, condensed phosphate Flame retardants and flame retardant aids such as antibacterial agents typified by silver antibacterial agents, antifungal agents, carbon black, titanium oxide, mold release agents, lubricants, pigments and dyes can also be added.

  The natural rubber-containing thermoplastic resin composition of the present invention can be obtained by melt mixing the constituent resin components. Although there is no restriction | limiting in particular regarding the melt mixing method, The method of melt-mixing using a monoaxial or biaxial screw with a heating apparatus and the cylinder which has a vent is employable. The heating temperature at the time of melt mixing is usually selected from the range of 230 to 320 ° C. However, it is also possible to freely set the temperature gradient at the time of melt mixing within a range that does not impair the object of the present invention. Further, when a biaxial screw is used, it may be in the same rotational direction or in a different rotational direction.

  The molding method of the natural rubber-containing thermoplastic resin composition of the present invention is not particularly limited, but it is suitably molded by injection molding. The injection molding can be preferably carried out in a temperature range for normal molding of 240 to 300 ° C. Moreover, the mold temperature at the time of injection molding is preferably a temperature range used for normal molding at 30 to 80 ° C.

  Since the natural rubber-containing thermoplastic resin composition of the present invention has both fluidity and impact resistance, it is suitable for large-sized or complex molded products. That is, the resin composition of the present invention can be suitably used for power window panels, center consoles, center clusters, console shutters, lever controllers, console boxes and the like for automobile interiors, and has not been studied so far. It can also be applied to exterior materials such as rear spoilers, door mirrors, roofs, fenders, and bumpers. Moreover, it can be used suitably also for an electrical and electronic use, an OA apparatus use, and a house and building materials use.

  In order to describe the present invention more specifically, examples will be given below, but these examples do not limit the present invention in any way, and various modifications are possible.

  The analysis method of the resin characteristic of a thermoplastic resin composition is as follows.

(1) Weight average particle size measurement of natural rubber and synthetic rubber Natural rubber and synthetic rubber latex are diluted and dispersed in an aqueous medium, and measured by a laser scattering diffraction particle size distribution analyzer “LS 13 320” (Beckman Coulter, Inc.). The particle size distribution was measured. From the particle size distribution, the weight average particle size of natural rubber and synthetic rubber was calculated. Moreover, about the natural rubber, it calculated about the ratio which the thing which has a particle diameter of 1.0 micrometer or more accounts for the whole natural rubber particle | grains from particle size distribution.

(2) Graft ratio measurement 200 ml of acetone was added to a predetermined amount (m; about 1 g) of the graft copolymer and refluxed in a hot water bath at a temperature of 70 ° C. for 3 hours. p. m. After centrifuging at (10000 G) for 40 minutes, the insoluble matter was filtered, this insoluble matter was dried under reduced pressure at a temperature of 60 ° C. for 5 hours, and the weight (n) was measured. The graft ratio was calculated from the following formula. Here, L is the rubber content of the graft copolymer.
Graft rate (%) = {[(n) − (m) × L] / [(m) × L]} × 100.

(3) Calculation of internal graft ratio The ratio of the vinyl copolymer content (internal graft amount) present in the rubber polymer to the total amount of the rubber polymer and vinyl copolymer present in the internal polymer Calculated as a rate. Specifically, from a photograph taken by magnifying the sample prepared by the osmic acid staining method at an magnification of 20,000 by observation with an electron microscope (TEM), five rubbery polymers having a particle diameter of 1.0 μm or more are selected. It was converted as a ratio of the cross-sectional area of the rubber-like polymer and the area of the vinyl copolymer existing inside the cross-sectional area, and calculated as an average value. For the calculation of the area ratio, the TEM image is determined as black and white by automatic two-color conversion of “WinROOF” image analysis software manufactured by Mitani Shoji Co., Ltd. The double value was used as a boundary value, the white side ratio was calculated as the internal graft amount (X), and the black side as the rubbery polymer amount (Y).
Internal graft ratio (%) = (X) / [(X) + (Y)] × 100.

(4) Graft Polymerization Mode The latex mode during graft polymerization of the graft copolymer (II) was visually observed and evaluated according to the following criteria.
○: Aggregates are not observed in the latex.
X: A large amount of aggregates is observed in the latex.

(5) Intrinsic viscosity The intrinsic viscosity of the vinyl copolymer (III) was measured using a Ubbelohde viscometer from a methyl ethyl ketone solution having a measurement temperature of 30 ° C. and a sample concentration of 0.2 g and 0.4 g / dl. Was derived.

(6) Average vinyl cyanide content The vinyl copolymer (III) was formed into a film of about 40 μm by a hot press, and a Fourier transform infrared spectrophotometer (Nippon Optical Co., Ltd., “FT / IR4100”) was used. Asked.

(7) Vinyl cyanide composition distribution Vinyl copolymer (III) 2 g of each sample was dissolved in 80 ml of methyl ethyl ketone, cyclohexane was added thereto, and the precipitated vinyl cyanide copolymer was vacuum dried. The weight was measured, and the vinyl cyanide content of the vinyl cyanide copolymer was determined from the absorbance ratio of infrared spectroscopic analysis in the same manner as (3) above. Then, the cumulative weight% and vinyl cyanide content were plotted, and a ratio (%) of 2% by weight or more was determined from the average vinyl cyanide content.

(8) Melt volume rate The melt volume rate of polycarbonate was measured in accordance with ISO 1133 (measured at a temperature of 300 ° C. and a 1.2 kg load condition).

(9) Fluidity Melt flow rate: Measured according to ISO 1133 (measured at a temperature of 240 ° C. and a 98N load condition).

(10) Impact property Charpy impact strength: Measured according to ISO 179 (notched).

  (11) Deflection temperature under load: Measured according to ISO75 (1.8 MPa load).

(Reference Example 1) Polycarbonate resin (I)
(I-1) Melt volume rate of 300 ° C. × load 1.2Kg conforming to ISO 1133 was used ^{8 cm} 3/10 min Teijin Chemicals Ltd. of "Panlite" L-1250.

(I-2) melt volume rate of 300 ℃ × load 1.2Kg that conforms to the ISO 1133 was used 10cm ^3/10 minutes of Mitsubishi Engineering Plastics Co., Ltd. "Iupilon" S-2000.

(I-3) melt volume rate of 300 ° C. × load 1.2Kg conforming to ISO 1133 was used 12cm ^3/10 minutes manufactured by Idemitsu Kosan Co., Ltd. "Toughlon" A2200.

(I-4) melt volume rate of 300 ° C. × load 1.2Kg conforming to ISO 1133 was used ^{6 cm} 3 / made 10 minutes Mitsubishi Engineering-Plastics Corporation "Iupilon" S-1000.

(I-5) melt volume rate of 300 ° C. × load 1.2Kg conforming to ISO 1133 was used 19cm ^3/10 minutes manufactured by Idemitsu Kosan Co., Ltd. "Toughlon" A1900.

(Reference Example 2) Graft copolymer (II)
As graft copolymers (II) used in the examples, graft copolymers (II-1) to (II-4) were prepared as follows.

Graft copolymer (II-1)
As rubber-like polymer (R-1), natural rubber (r1) (weight average particle diameter 0.6 μm, content of particle diameter of 1.0 μm or more is 24% by weight) 25% by weight, synthetic rubber (r2) ( Blended at 75% by weight (weight average particle size 0.3 μm) (in terms of solid content). Subsequently, in the presence of 50 parts by weight of rubber-like polymer (R-1) (in terms of solid content), pure water 130% by weight, sodium formaldehyde sulfoxylate 0.4% by weight, ethylenediaminetetraacetate sodium 0.1% by weight, sulfuric acid First, 0.01% by weight of ferrous iron and 0.1% by weight of sodium pyrophosphate were charged into a reaction vessel, and after nitrogen substitution, the temperature was adjusted to 60 ° C., and 5.84% by weight of styrene, 2.16% by weight of acrylonitrile and A monomer mixture of t-dodecyl mercaptan 0.03% by weight (16% by weight of the total monomer mixture) was initially added over 0.5 hours. Next, an initiator mixture of cumene hydroperoxide 0.25 wt%, emulsifier sodium laurate 1.5 wt% and pure water 25 wt% was started to initiate polymerization. The initiator mixture was continuously dropped over 6 hours, and at the same time, a mixture of 30.66% by weight of styrene, 11.34% by weight of acrylonitrile and 0.16% by weight of t-dodecyl mercaptan was added in a single amount over 4 hours. The body mixture was continuously added dropwise. After dropping of the monomer mixture, only the initiator mixture was continuously dropped for 2 hours to complete the polymerization. The latex after completion of polymerization was coagulated with 1.5% by weight sulfuric acid, then neutralized with sodium hydroxide, washed, centrifuged and dried to obtain a natural rubber-containing graft copolymer (B-1). The graft ratio was 39%, the internal graft ratio was 25%, and the weight-average molecular weight of the methyl ethyl ketone-soluble component was 83,000.

Graft copolymer (II-2)
As rubber-like polymer (R-2), natural rubber (r1) (weight average particle diameter 0.6 μm, content of particle diameter of 1.0 μm or more is 24% by weight) 50% by weight, synthetic rubber (r2) ( Blended at 50% by weight (weight average particle diameter 0.3 μm) (in terms of solid content). Thereafter, the same procedure as in (II-1) was performed to obtain a natural rubber-containing graft copolymer (B-2). The graft ratio was 35%, the internal graft ratio was 24%, and the weight average molecular weight of the methyl ethyl ketone-soluble component was 83,000.

Graft copolymer (II-3)
As rubber-like polymer (R-3), natural rubber (r1) (weight average particle diameter of 0.9 μm, content of particle diameter of 1.0 μm or more is 40.5% by weight), 25% by weight, synthetic rubber (r2) ) (Weight average particle diameter 0.3 μm) Blended at 75% by weight (in terms of solid content). Thereafter, a natural rubber-containing graft copolymer (II-3) was obtained in the same manner as (II-1) described above. The graft ratio was 36%, the internal graft ratio was 21%, and the weight average molecular weight of the methyl ethyl ketone-soluble component was 83,000.

Graft copolymer (II-4)
As rubber-like polymer (R-4), natural rubber (r1) (weight average particle size 0.6 μm, content of particle size of 1.0 μm or more is 24% by weight) 25% by weight, synthetic rubber (r2) ( Blended at 75% by weight (weight average particle size 0.2 μm) (in terms of solid content). Next, in the presence of 50 parts by weight (in terms of solid content) of the rubber-like polymer (R-4), the monomer mixture liquid initially added was 18.25% by weight of styrene, 6.75% by weight of acrylonitrile, and 0% of t-dodecyl mercaptan. 0.1% by weight (50% by weight of the total monomer mixture), and continuously added monomer mixture was 18.25% by weight of styrene, 6.75% by weight of acrylonitrile and 0.1% by weight of t-dodecyl mercaptan Except that, natural rubber containing graft copolymer (II-4) was obtained in the same manner as (II-1). The graft ratio was 46%, the internal graft ratio was 32%, and the weight-average molecular weight of the methyl ethyl ketone-soluble component was 83,000.

  As graft copolymers (II) used in the comparative examples, graft copolymers (II-5) to (II-10) were prepared as follows.

Graft copolymer (II-5)
As rubber-like polymer (R-5), natural rubber (r1) (weight average particle size 0.6 μm, content of particle size of 1.0 μm or more is 24% by weight) 80% by weight, synthetic rubber (r2) ( Blended at a weight average particle size of 0.3 μm) at 20% by weight (in terms of solid content). Thereafter, the same procedure as in (II-1) was performed to obtain a natural rubber-containing graft copolymer (II-5). The graft ratio was 38%, the internal graft ratio was 23%, and the weight-average molecular weight of the methyl ethyl ketone-soluble component was 83,000.

Graft copolymer (II-6)
As rubber-like polymer (R-6), natural rubber (r1) (weight average particle diameter of 1.5 μm, content of particle diameter of 1.0 μm or more is 48% by weight), 25% by weight, synthetic rubber (r2) ( Blended at 75% by weight (weight average particle size 0.3 μm) (in terms of solid content). Thereafter, the same procedure as in (II-1) was performed to obtain a natural rubber-containing graft copolymer (II-6). The graft ratio was 34%, the internal graft ratio was 16%, and the weight average molecular weight of the methyl ethyl ketone-soluble component was 83,000.

Graft copolymer (II-7)
As rubber-like polymer (R-7), natural rubber (r1) (weight average particle size 0.6 μm, content of particle size of 1.0 μm or more is 24% by weight) 25% by weight, synthetic rubber (r2) ( Blended at 75% by weight (weight average particle size 0.08 μm) (in terms of solid content). Thereafter, the same procedure as in (II-1) was performed to obtain a natural rubber-containing graft copolymer (II-7). The graft ratio was 37%, the internal graft ratio was 24%, and the weight average molecular weight of the methyl ethyl ketone-soluble component was 83,000.

Graft copolymer (II-8)
As rubber-like polymer (R-8), natural rubber (r1) (weight average particle diameter 0.6 μm, content of particle diameter of 1.0 μm or more is 24 wt%) and 100 wt% (solid content conversion). . Next, in the presence of 50 parts by weight (converted to solid content) of a rubber-like polymer (R-8), pure water 130% by weight, sodium formaldehyde sulfoxylate 0.4% by weight, ethylenediaminetetraacetate sodium 0.1% by weight, sulfuric acid Ferrous powder 0.01% by weight, sodium pyrophosphate 0.1% by weight and potassium hydroxide 0.25% by weight were charged into a reaction vessel, and after nitrogen substitution, the temperature was adjusted to 60 ° C., and styrene 18.25% by weight with stirring. %, Acrylonitrile 6.75% by weight and t-dodecyl mercaptan 0.1% by weight monomer mixture (50% by weight of total monomer mixture) was initially added over 1 hour. Next, an initiator mixture of cumene hydroperoxide 0.25 wt%, emulsifier sodium laurate 1.5 wt% and pure water 25 wt% was started to initiate polymerization. The initiator mixture was continuously dropped over 6 hours, and at the same time, a mixture of 18.25% by weight of styrene, 6.75% by weight of acrylonitrile and 0.1% by weight of t-dodecyl mercaptan was added in a single amount over 4 hours. The body mixture was continuously added dropwise. After dropping of the monomer mixture, only the initiator mixture was continuously dropped for 2 hours to complete the polymerization. The polymerized latex was coagulated with 1.5% by weight sulfuric acid, then neutralized with sodium hydroxide, washed, centrifuged and dried to obtain a natural rubber-containing graft copolymer (II-8). The graft ratio was 43%, the internal graft ratio was 27%, and the weight average molecular weight of the methyl ethyl ketone-soluble component was 83,000.

Graft copolymer (II-9)
The rubber-like polymer (R-9) was 100% by weight (in terms of solid content) of synthetic rubber (r2) (weight average particle diameter 0.3 μm). Next, in the presence of 50 parts by weight (converted to solid content) of a rubber-like polymer (R-8), pure water 130% by weight, sodium formaldehyde sulfoxylate 0.4% by weight, ethylenediaminetetraacetate sodium 0.1% by weight, sulfuric acid First, 0.01% by weight of ferrous iron and 0.1% by weight of sodium pyrophosphate were charged in a reaction vessel, and after nitrogen substitution, the temperature was adjusted to 60 ° C. A 0.046% by weight mixture of t-dodecyl mercaptan (18.4% by weight of the total monomer mixture) was initially added over 0.5 hours. Next, an initiator mixture of cumene hydroperoxide 0.32 wt%, emulsifier sodium laurate 1.5 wt% and pure water 25 wt% was started to initiate polymerization. The initiator mixture was continuously dropped over 5 hours, and at the same time, a mixture of 29.8% by weight of styrene, 11% by weight of acrylonitrile and 0.15% by weight of t-dodecyl mercaptan was added to the monomer mixture over 3 hours. Was continuously added dropwise. After the monomer mixture was dropped, only the initiator mixture was continuously dropped for 1 hour to complete the polymerization. The latex after completion of polymerization was coagulated with 1.5% by weight sulfuric acid, then neutralized with sodium hydroxide, washed, centrifuged and dried to obtain a graft copolymer (II-9). The graft ratio was 40%, the internal graft ratio was 42%, and the weight average molecular weight of the methyl ethyl ketone-soluble component was 83,000.

Graft copolymer (II-10)
As rubber-like polymer (R-1), natural rubber (weight average particle size 0.6 μm, content of particle size of 1.0 μm or more is 24% by weight) (r1) 25% by weight, synthetic rubber (r2) ( Blended at 75% by weight (weight average particle size 0.3 μm) (in terms of solid content). Subsequently, in the presence of 50 parts by weight of rubber-like polymer (R-1) (in terms of solid content), pure water 130% by weight, sodium formaldehyde sulfoxylate 0.4% by weight, ethylenediaminetetraacetate sodium 0.1% by weight, sulfuric acid First, 0.01% by weight of ferrous iron and 0.1% by weight of sodium pyrophosphate are charged into a reaction vessel, and after nitrogen substitution, the temperature is adjusted to 60 ° C., cumene hydroperoxide is 0.25% by weight, and sodium laurate is an emulsifier. The introduction of an initiator mixture of 1.5% by weight and 25% by weight of pure water was started to initiate the polymerization. The initiator mixture was continuously dropped over 6 hours, and at the same time, a mixture of 36.5% by weight of styrene, 13.5% by weight of acrylonitrile and 0.2% by weight of t-dodecyl mercaptan was added in a single amount over 4 hours. The body mixture was continuously added dropwise. After dropping of the monomer mixture, only the initiator mixture was continuously dropped for 2 hours to complete the polymerization. The polymerized latex was coagulated with 1.5% by weight sulfuric acid, then neutralized with sodium hydroxide, washed, centrifuged and dried to obtain a natural rubber-containing graft copolymer (II-10). The graft ratio was 38%, the internal graft ratio was 10%, and the weight average molecular weight of the methyl ethyl ketone-soluble component was 83,000.

  The blending ratio of natural rubber and synthetic rubber in the rubber-like polymer of each graft copolymer is shown in Table 1, and the composition of each graft copolymer is shown in Table 2.

Reference Example 3 Vinyl copolymer (III)
As the vinyl copolymer (III) used in the examples, vinyl copolymers (III-1) to (III-10) were prepared as follows.

Vinyl copolymer (III-1)
165 parts by weight of ion exchange with 0.05 parts by weight of a methyl methacrylate / acrylamide copolymer (described in Japanese Examined Patent Publication No. 45-24151) in a stainless steel autoclave having a capacity of 20 l and equipped with a baffle and a foudra-type stirring blade The solution dissolved in water was stirred at 400 rpm, and the inside of the system was replaced with nitrogen gas. Then 16 parts by weight acrylonitrile, 84 parts by weight styrene, 0.46 parts by weight t-dodecyl mercaptan, 0.39 parts by weight 2,2'-azobis (2,4-dimethylvaleronitrile), 0.05 A mixed solution of 2,2′-azobisisobutylnitrile in parts by weight was added with stirring in the reaction system, and a copolymerization reaction was started at 58 ° C. After 2 hours from the start of copolymerization, the temperature was raised to 100 ° C. over 50 minutes and held for 5 minutes, and then the slurry obtained by cooling was subjected to washing, dehydration and drying steps to obtain a vinyl copolymer (III-1 ) Was prepared. The intrinsic viscosity of the obtained vinyl copolymer (III-1) was 0.44 dl / g. The average vinyl cyanide content was 15% by weight, and the proportion of the copolymer having a composition higher by 2% by weight or more than the average vinyl cyanide content in the vinyl cyanide composition distribution was 30% by weight.

Vinyl copolymer (III-2)
A vinyl copolymer (III-2) was prepared in the same manner as the vinyl copolymer (III-1) except that 20 parts by weight of acrylonitrile and 80 parts by weight of styrene were used. The intrinsic viscosity of the obtained vinyl copolymer (III-2) was 0.42 dl / g. The average vinyl cyanide content was 19% by weight, and the proportion of the copolymer having a composition 2% by weight higher than the average vinyl cyanide content in the vinyl cyanide composition distribution was 35% by weight.

Vinyl copolymer (III-3)
A vinyl copolymer (III-3) was prepared in the same manner as the vinyl copolymer (III-1) except that 24 parts by weight of acrylonitrile and 76 parts by weight of styrene were used. The inherent viscosity of the obtained vinyl copolymer (III-3) was 0.42 dl / g. The average vinyl cyanide content was 23% by weight, and the proportion of the copolymer having a composition higher by 2% by weight or more than the average vinyl cyanide content in the vinyl cyanide composition distribution was 45% by weight.

Vinyl copolymer (III-4)
165 parts by weight of ion exchange with 0.05 parts by weight of a methyl methacrylate / acrylamide copolymer (described in Japanese Examined Patent Publication No. 45-24151) in a stainless steel autoclave having a capacity of 20 l and equipped with a baffle and a foudra-type stirring blade The solution dissolved in water was stirred at 400 rpm, and the inside of the system was replaced with nitrogen gas. Then 10 parts by weight acrylonitrile, 40 parts by weight styrene, 0.46 parts by weight t-dodecyl mercaptan, 0.39 parts by weight 2,2'-azobis (2,4-dimethylvaleronitrile), 0.05 A mixed solution of 2,2′-azobisisobutylnitrile in parts by weight was added with stirring in the reaction system, and a copolymerization reaction was started at 58 ° C. Polymerization proceeds while adding 10 parts by weight of acrylonitrile and 40 parts by weight of styrene over about 40 minutes 45 minutes after the start of copolymerization, and the temperature is raised to 100 ° C. over 50 minutes 2 hours after the start of copolymerization. The slurry obtained by holding for a minute and then cooling was subjected to washing, dehydration and drying steps to prepare a vinyl copolymer (III-4). The inherent viscosity of the obtained vinyl copolymer (III-4) was 0.43 dl / g. The average vinyl cyanide content was 19% by weight, and the proportion of the copolymer having a composition higher by 2% by weight or more than the average vinyl cyanide content in the vinyl cyanide composition distribution was 15% by weight.

Vinyl copolymer (III-5)
A vinyl copolymer (III-5) was prepared in the same manner as the vinyl copolymer (III-2) except that 0.82 parts by weight of t-dodecyl mercaptan was used. The inherent viscosity of the obtained vinyl copolymer (III-5) was 0.30 dl / g. The average vinyl cyanide content was 19% by weight, and the proportion of the copolymer having a composition higher by 2% by weight or more than the average vinyl cyanide content in the vinyl cyanide composition distribution was 28% by weight.

Vinyl copolymer (III-6)
A vinyl copolymer (III-6) was prepared in the same manner as the vinyl copolymer (III-2) except that t-dodecyl mercaptan was changed to 0.25 parts by weight. The inherent viscosity of the obtained vinyl copolymer (III-6) was 0.60 dl / g. The average vinyl cyanide content was 19% by weight, and the proportion of the copolymer having a composition higher by 2% by weight or more than the average vinyl cyanide content in the vinyl cyanide composition distribution was 30% by weight.

  As the vinyl copolymer (III) used in the comparative examples, vinyl copolymers (III-7) to (III-10) were prepared as follows.

Vinyl copolymer (III-7)
A vinyl copolymer (III-7) was prepared in the same manner as the vinyl copolymer (III-1) except that 28 parts by weight of acrylonitrile and 72 parts by weight of styrene were used. The inherent viscosity of the obtained vinyl copolymer (III-7) was 0.40 dl / g. The average vinyl cyanide content was 27% by weight, and the proportion of the copolymer having a composition 2% by weight higher than the average vinyl cyanide content in the vinyl cyanide composition distribution was 32% by weight.

Vinyl copolymer (III-8)
A vinyl copolymer (III-8) was prepared in the same manner as the vinyl copolymer (III-1) except that 12 parts by weight of acrylonitrile and 88 parts by weight of styrene were used. The inherent viscosity of the obtained vinyl copolymer (III-8) was 0.48 dl / g. The average vinyl cyanide content was 11% by weight, and the proportion of the copolymer having a composition higher by 2% by weight or more than the average vinyl cyanide content in the vinyl cyanide composition distribution was 44% by weight.

Vinyl copolymer (III-9)
Using a continuous bulk polymerization apparatus consisting of a preheater and a demonomer, 0.30 parts by weight of n-octyl mercaptan was added to a monomer mixture consisting of 80 parts by weight of styrene and 20 parts by weight of acrylonitrile, and the continuous bulk was formed at 135 kg / hour. Polymerized. In the polymerization reaction mixture, unreacted monomers were collected by evaporation under reduced pressure from a vent port using a single screw extruder type demonomer machine, and a vinyl copolymer (III-9) was prepared from one demonomer machine. The inherent viscosity of the obtained vinyl copolymer (III-9) was 0.41 dl / g. The average vinyl cyanide content was 19% by weight, and the proportion of the copolymer having a composition higher by 2% by weight or more than the average vinyl cyanide content in the vinyl cyanide composition distribution was 8% by weight.

Vinyl copolymer (III-10)
165 parts by weight of ion exchange with 0.05 parts by weight of a methyl methacrylate / acrylamide copolymer (described in Japanese Examined Patent Publication No. 45-24151) in a stainless steel autoclave having a capacity of 20 l and equipped with a baffle and a foudra-type stirring blade The solution dissolved in water was stirred at 400 rpm, and the inside of the system was replaced with nitrogen gas. 10 parts by weight acrylonitrile and 80 parts by weight styrene, 0.46 parts by weight t-dodecyl mercaptan, 0.39 parts by weight 2,2′-azobis (2,4-dimethylvaleronitrile), 0.05 parts by weight The 2,2′-azobisisobutylnitrile mixed solution was added with stirring in the reaction system, and the copolymerization reaction was started at 58 ° C. 2 hours after the start of the polymerization, 10 parts by weight of acrylonitrile is added to continue the polymerization, the temperature is raised to 100 ° C. over 50 minutes and held for 5 minutes, and then the slurry obtained by cooling is washed, dehydrated and dried. Then, a vinyl copolymer (III-10) was prepared. The inherent viscosity of the obtained vinyl copolymer (III-10) was 0.48 dl / g. The average vinyl cyanide content was 19% by weight, and the proportion of the copolymer having a composition higher by 2% by weight or more than the average vinyl cyanide content in the vinyl cyanide composition distribution was 55% by weight.

(Examples 1-17, Comparative Examples 1-12)
After blending the polycarbonate resin (I), the graft copolymer (II), and the vinyl copolymer (III) described in Reference Examples at the ratios shown in Tables 3 and 4, the mixture was stirred for 1 minute in a blender. The mixture was melt kneaded in a twin screw extruder ("PCM-30" manufactured by Ikekai Tekko Co., Ltd., temperature range: 240 to 250 ° C) with a screw diameter of 30 mm, and the molten resin discharged from the die nozzle was a water tank. And was cut by a cutter through a cutter to obtain resin pellets. The obtained resin pellets were evaluated by making test pieces with a molding machine (SE50DU injection molding machine manufactured by Sumitomo Heavy Industries, Ltd., molding temperature 250 ° C., mold temperature 60 ° C.) so as to be suitable for each physical property evaluation. .

  As shown in Tables 3 and 4, as a result of the evaluation, the following became clear.

  From the comparison of the results of Examples and Comparative Examples 1 to 6, in Comparative Example 1, the content of natural rubber was too much and the impact resistance was poor. In Comparative Example 2, the natural rubber used had a large weight average particle size, and the impact resistance was poor. In Comparative Example 3, the weight average particle size of the synthetic rubber was small, resulting in poor impact resistance. In Comparative Example 4, only natural rubber was used, resulting in poor impact resistance. In Comparative Example 5, since only the synthetic rubber was used, the impact resistance was lowered. In Comparative Example 6, the internal graft ratio of the rubber-like polymer (R) having a size of 1 μm or more was not more than a specified value, resulting in poor impact resistance.

  From the comparison of the results of Example and Comparative Example 7, the amount of aromatic vinyl monomer (d) used in vinyl copolymer (III) was less than the prescribed amount, and vinyl cyanide monomer (o ) Was greater than the specified amount, the fluidity decreased.

  From the comparison of the results of Example and Comparative Example 8, the amount of the aromatic vinyl monomer (d) used in the vinyl copolymer (III) was larger than the specified amount, and the vinyl cyanide monomer (O ) Was less than the specified amount, the impact strength decreased.

  From the comparison of the results of Example and Comparative Example 9, it was found that when a copolymer having a composition having a composition higher by 2% by weight or more than the average vinyl cyanide content of the vinyl copolymer was less than the specified amount, The impact strength decreased.

  From the comparison of the results of Example and Comparative Example 10, it was found that a copolymer having a composition having a composition higher by 2% by weight or more than the average vinyl cyanide content of the vinyl copolymer is more than the specified amount. Not only decreased fluidity but also impact strength.

  From the comparison of the results of Examples and Comparative Example 11, when the polycarbonate resin (I) is less than the specified amount and the graft copolymer (II) and the vinyl copolymer (III) are more than the specified amount, the impact strength and The deflection temperature under load decreased.

  From the comparison of the results of Example and Comparative Example 12, when the amount of the polycarbonate resin (I) is more than the specified amount and the amount of the graft copolymer (II) and the vinyl copolymer (III) is less than the specified amount, the weighted deflection is obtained. Although the temperature was high, the fluidity decreased.

  In the automotive field, the present invention includes automotive exterior parts such as rear spoilers, wheel caps, door mirrors and radiator grills, power window panels, center consoles, center clusters, lever controllers, console interior parts such as console boxes, rear spoilers, door mirrors, Automotive exterior parts such as roofs, fenders, and bumpers. In addition to the automobile field, it can be suitably used in fields such as OA equipment, home appliances, house building materials, suitcases and bags.

Claims (3)

Polycarbonate resin (I) 40 to 75 parts by weight, natural rubber 10 containing 5% by weight or more of natural rubber particles having a particle size of 1.0 μm or more, and having a weight average particle size of 0.3 to 1.2 μm In the presence of a rubbery polymer (a) consisting of 70% by weight and 30-90% by weight of a synthetic rubber having a weight average particle size in the range of 0.2-0.4 μm, at least an aromatic vinyl-based monomer A graft copolymer (II) obtained by graft copolymerizing a vinyl monomer mixture containing the body (I) and having an internal graft ratio of 20% or more of rubbery polymer particles having a particle diameter of 1.0 μm or more. A natural rubber-containing thermoplastic resin composition comprising 10 to 25 parts by weight, and 15 to 35 parts by weight of a vinyl copolymer (III) satisfying the following (A) and (B).
(A) Aromatic vinyl monomer (D) 74 to 85% by weight and vinyl cyanide monomer (e) 15 to 26% by weight are copolymerized.
(B) In the vinyl cyanide (III) composition distribution of vinyl cyanide, a copolymer having a composition 2 wt% or more higher than the average vinyl cyanide content is 10% in the vinyl copolymer (III). -50% by weight present.   The intrinsic viscosity of the vinyl copolymer (III) measured with a methyl ethyl ketone solvent, 30 ° C, an Ubbelohde viscometer is in the range of 0.35 to 0.50 dl / g, according to claim 1. Thermoplastic resin composition.   A molded product obtained by molding the thermoplastic resin composition according to claim 1.