JP7120889B2 - Thermoplastic resin composition and molded article thereof - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition and a molded article containing a modified polycarbonate copolymer derived from a specific bisphenol structural unit and a styrenic resin. More particularly, it relates to a resin composition and a molded article having good impact resistance, heat resistance, surface hardness and rigidity.

Polycarbonate resin is excellent in transparency, impact resistance, heat resistance, and dimensional stability. , and miscellaneous goods.

On the other hand, the polycarbonate resin has a pencil hardness of 2B measured according to JIS K5600-5-4, General Paint Test Method - Part 5: Mechanical Properties of Coating Film - Section 4: Scratch Hardness (Pencil Method). The surface is soft and easily damaged. In particular, mobile phones, liquid crystal televisions, speakers, portable game machines, laptop computers, and other electric/electronic/OA equipment housings, interior panels, door handles, steering wheels, car audio/car navigation frames, and shift knobs. Automobile exterior parts such as automobile interior parts, roof spoilers, window garnishes, furniture, and musical instruments are required to have a texture similar to high-grade lacquerware and a transparent color tone to create a sense of luxury. Scratches on the surface are fatal disfigurements.

As a method for improving the scratch resistance of polycarbonate resin, it is generally known to impart jet-blackness and scratch resistance by coating the surface of the resin. However, due to the wettability of the paint to the resin surface and the environmental conditions of the painting process, appearance defects such as pinholes, cracks, repelling, orange peel, and poor adhesion of the paint occur, resulting in a significant drop in the yield of the painting process. However, the problem is that the productivity is inferior.

As a method for improving the scratch resistance of polycarbonate resin without painting, a method of laminating an acrylic resin film or sheet on the surface of the resin is known. (For example, see Patent Document 1.) However, since acrylic resins have lower heat resistance than polycarbonate resins and are more likely to absorb water, there is a problem in that dimensional changes due to temperature and humidity are large, and warping occurs in the final product. Furthermore, there is a problem that the film thickness distribution of the acrylic resin film or sheet causes unevenness in appearance, impairing the high-class feeling of jet-black tone.

Therefore, it is known to use a copolymerized polycarbonate resin having a high surface hardness. (See, for example, Patent Document 2) However, although the copolymer polycarbonate resin has a high surface hardness, it has a problem of poor impact resistance. Further, a method for producing a polycarbonate or copolycarbonate having 2,2-bis(4-hydroxy-3-methylphenyl)propane as a structural unit is described. (See, for example, Patent Documents 3 to 7) The polycarbonate resin has an improved surface hardness, but has a problem of being inferior in heat resistance as compared with the polycarbonate resin. Further, a copolymer polycarbonate resin containing a 2,2-bis(4-hydroxy-3-methylphenyl)propane component and a 2,2-bis(4-hydroxyphenyl)propane component is mixed with a styrene resin and an impact modifier. The use of the resin composition obtained in this manner improves the surface hardness and impact resistance, but the problem is that the heat resistance is poor. (See, for example, Patent Document 8) Furthermore, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 2,2-bis(4-hydroxy-3-methylphenyl)propane, and 2,2-bis A method for producing a polycarbonate having (4-hydroxyphenyl)propane as a structural unit is described. (See, for example, Patent Document 9) Although the polycarbonate resin is excellent in surface hardness and heat resistance, there is no teaching of any knowledge regarding the effect on rigidity.

Therefore, at present, there are no polycarbonate resin compositions and molded articles excellent in impact resistance, heat resistance, surface hardness and rigidity.

JP 2007-160892 A Japanese Patent No. 5173803 JP-A-64-069625 JP-A-08-183852 JP-A-08-034846 Japanese Patent Application Laid-Open No. 2002-117580 Japanese Patent No. 3768903 Japanese Patent No. 5749635 WO2017/073508

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin composition and a molded product, particularly automotive interior and exterior parts, which are excellent in impact resistance, heat resistance, surface hardness and rigidity.

According to the present invention, the above problems are solved by the following configuration.
1. As main structural units, (A) (A-1) a structural unit (A-1) represented by the following formula (1), (A-2) a structural unit (A-2) represented by the following formula (2) ) and (A-3) composed of a structural unit (A-3) represented by the following formula (3), wherein the proportion of the structural unit (A-1) in all structural units is 5 to 15 mol%, and the structural unit ( 95 to 60 parts by weight of a polycarbonate copolymer (component A) having a proportion of A-2) of 20 to 60 mol% and a proportion of the structural unit (A-3) of 25 to 75 mol%, and (B) a styrene resin ( Component B) A polycarbonate resin composition comprising 5 to 40 parts by weight.

（式（１）中、Ｒ^１およびＲ^２は夫々独立して水素原子、芳香族基を含んでもよい炭素原子数１～９の炭化水素基またはハロゲン原子である。）

(In formula (1), R ¹ and R ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 9 carbon atoms which may contain an aromatic group, or a halogen atom.)

（式（２）中、Ｒ^３およびＲ^４は夫々独立して炭素原子数１～６のアルキル基またはハロゲン原子である。Ｘは、単結合、置換もしくは無置換のアルキレン基、置換もしくは無置換のアルキリデン基、硫黄原子または酸素原子である。）

(In formula (2), R ³ and R ⁴ are each independently an alkyl group having 1 to 6 carbon atoms or a halogen atom. X is a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted is an alkylidene group, a sulfur atom or an oxygen atom.)

（式（３）中、Ｗは、単結合、置換もしくは無置換のアルキレン基、置換もしくは無置換のアルキリデン基、硫黄原子または酸素原子を示す。）

(In formula (3), W represents a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkylidene group, a sulfur atom or an oxygen atom.)

2. R ¹ and R ² in formula (1) are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ³ and R ⁴ in formula (2) are each independently having 1 to 6 carbon atoms. 6 alkyl group, X is a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted alkylidene group having 1 to 10 carbon atoms, W in formula (3) is a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkylidene group having 1 to 10 carbon atoms.
3. 3. The polycarbonate resin composition as described in 1 or 2 above, wherein the polycarbonate copolymer has a glass transition temperature of 140 to 160°C.
4. 4. The polycarbonate resin composition as described in any one of 1 to 3 above, wherein the polycarbonate copolymer has a viscosity average molecular weight of 15,000 to 40,000.
5. 5. The polycarbonate resin composition according to any one of 1 to 4 above, wherein the structural unit (A-1) is a structural unit derived from 9,9-bis(4-hydroxy-3-methylphenyl)fluorene.
6. 6. The polycarbonate resin composition as described in any one of 1 to 5 above, wherein the structural unit (A-2) is a structural unit derived from 2,2-bis(4-hydroxy-3-methylphenyl)propane.
7. 7. The polycarbonate resin composition as described in any one of 1 to 6 above, wherein the structural unit (A-3) is a structural unit derived from 2,2-bis(4-hydroxyphenyl)propane.
8. 8. The polycarbonate according to any one of the preceding items 1 to 7, which contains 3 to 10 parts by weight of (C) an impact modifier (component C) excluding component B, relative to a total of 100 parts by weight of components A and B. Resin composition.
9. 9. The polycarbonate resin composition according to any one of the preceding items 1 to 8, wherein component C contains one or more rubber-modified resins selected from butadiene-based, acrylic-based and silicone-based resins or copolymers thereof.
10. A molded article obtained by molding the polycarbonate resin composition according to any one of 1 to 9 above.
11. Automobile interior and exterior parts using the molded product of the preceding item 10.

Since the resin composition of the present invention is excellent in impact resistance, heat resistance, surface hardness and rigidity, it is widely used in electrical and electronic applications, mechanical applications, OA applications, automobile interior and exterior parts, medical applications, and other various applications. Useful. Among others, the present invention provides molded articles that are extremely useful as interior parts for automobiles and exterior parts for automobiles, and the industrial effects of the present invention are extremely large.

The details of the present invention will be further described below.
<A component: Polycarbonate copolymer>
The polycarbonate copolymer of the present invention has, as main structural units, (A-1) a structural unit (A-1) represented by the following formula (1) and (A-2) a structural unit represented by the following formula (2). Structural units (A-2) and (A-3) are composed of structural units (A-3) represented by the following formula (3).

（式（１）中、Ｒ^１およびＲ^２は夫々独立して水素原子、芳香族基を含んでもよい炭素原子数１～９の炭化水素基またはハロゲン原子である。）

(In formula (1), R ¹ and R ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 9 carbon atoms which may contain an aromatic group, or a halogen atom.)

（式（２）中、Ｒ^３およびＲ^４は夫々独立して炭素原子数１～６のアルキル基またはハロゲン原子である。Ｘは、単結合、置換もしくは無置換のアルキレン基、置換もしくは無置換のアルキリデン基、硫黄原子または酸素原子である。）

(In formula (2), R ³ and R ⁴ are each independently an alkyl group having 1 to 6 carbon atoms or a halogen atom. X is a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted is an alkylidene group, a sulfur atom or an oxygen atom.)

（式（３）中、Ｗは、単結合、置換もしくは無置換のアルキレン基、置換もしくは無置換のアルキリデン基、硫黄原子または酸素原子を示す。）

(In formula (3), W represents a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkylidene group, a sulfur atom or an oxygen atom.)

Here, the term “main” means 70 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and most It indicates that the ratio is preferably 100 mol %.

In the structural unit (A-1) represented by the formula (1), R ¹ and R ² are preferably each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Dihydric phenols from which the structural unit (A-1) is derived include 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (BCF). be done. The most preferred dihydric phenol is 9,9-bis(4-hydroxy-3-methylphenyl)fluorene.

The ratio of the structural unit (A-1) to the total structural units in the polycarbonate copolymer of the present invention is 5 to 15 mol%, preferably 5 to 12 mol%, and 8 to 10 mol%. is more preferred. When the proportion of the structural unit (A-1) exceeds 15 mol %, the heat resistance is improved, but the impact resistance is poor. If the proportion of the structural unit (A-1) is less than 5 mol %, heat resistance, rigidity and surface hardness are poor.

In the structural unit (A-2) represented by the formula (2), R ³ and R ⁴ are preferably each independently an alkyl group having 1 to 6 carbon atoms, and X is a single bond, substituted or An unsubstituted alkylene group having 1 to 10 carbon atoms and a substituted or unsubstituted alkylidene group having 1 to 10 carbon atoms are preferred.

Examples of dihydric phenols from which the structural unit (A-2) is derived include 2,2-bis(4-hydroxy-3-methylphenyl)propane (hereinafter referred to as bisphenol C (BPC)), 2,2-bis( 4-hydroxy-3-isopropylphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane and the like. The most preferred dihydric phenol is bisphenol C.

The ratio of the structural unit (A-2) to the total structural units in the polycarbonate copolymer of the present invention is 20 to 60 mol%, preferably 30 to 50 mol%, and 40 to 50 mol%. is more preferred. If the proportion of the structural unit (A-2) exceeds 60 mol %, the impact resistance and heat resistance are degraded. If the proportion of the structural unit (A-2) is less than 20 mol %, the surface hardness and rigidity are poor.

In the structural unit (A-3) represented by the formula (3), W is a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted An alkylidene group is preferred.

Dihydric phenols from which the structural unit (A-3) is derived include 2,2-bis(4-hydroxyphenyl)propane (hereinafter referred to as bisphenol A (BPA)), 4,4′-dihydroxy-1,1 -biphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylthioether, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 1,1 -bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 4 ,4-bis(4-hydroxyphenyl)heptane, 2,2-bis(4-hydroxyphenyl)octane, 1,1-bis(4-hydroxyphenyl)decane and the like. The most preferred dihydric phenol is bisphenol A.

The ratio of the structural unit (A-3) to the total structural units in the polycarbonate copolymer of the present invention is 25 to 75 mol%, preferably 30 to 70 mol%, more preferably 35 to 65 mol%. When the proportion of the structural unit (A-3) exceeds 75 mol %, the surface hardness and rigidity are poor. If the proportion of the structural unit (A-3) is less than 25 mol %, the impact resistance and heat resistance are poor.

Further, the dihydric phenol from which the structural units other than the structural units (A-1), (A-2) and (A-3) are derived is preferably 2,6-dihydroxynaphthalene, hydroquinone, resorcinol, carbon number Resorcinol substituted with 1 to 3 alkyl groups, 3-(4-hydroxyphenyl)-1,1,3-trimethylindan-5-ol, 1-(4-hydroxyphenyl)-1,3,3-trimethyl indan-5-ol, 6,6'-dihydroxy-3,3,3',3'-tetramethylspiroindane, 1-methyl-1,3-bis(4-hydroxyphenyl)-3-isopropylcyclohexane, 1 -methyl-2-(4-hydroxyphenyl)-3-[1-(4-hydroxyphenyl)isopropyl]cyclohexane, 1,6-bis(4-hydroxyphenyl)-1,6-hexanedione, etc. . Other details of such polycarbonates are described in, for example, WO03/080728 pamphlet, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580. It is

The polycarbonate copolymer of the present invention is obtained by reacting a dihydric phenol with a carbonate precursor. Examples of the reaction method include an interfacial polycondensation method, a melt transesterification method, a solid-phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound. In the case of interfacial polycondensation, a monohydric phenol terminal terminator is usually used. Branched polycarbonates obtained by polymerizing trifunctional components may also be used, and copolymerized polycarbonates obtained by copolymerizing aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and vinyl monomers may also be used.

Reactions using, for example, phosgene as a carbonate precursor are usually carried out in the presence of an acid-binding agent and a solvent. Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and amine compounds such as pyridine. Examples of the solvent include halogenated hydrocarbons such as methylene chloride and chlorobenzene. A catalyst such as a tertiary amine or a quaternary ammonium salt may also be used to promote the reaction. At that time, the reaction temperature is usually 0 to 40° C., and the reaction time is several minutes to 5 hours.

The transesterification reaction using, for example, a carbonic acid diester as a carbonate precursor is carried out by stirring a predetermined proportion of the aromatic dihydroxy component with the carbonic acid diester under an inert gas atmosphere while heating to distill off the resulting alcohol or phenol. will be Although the reaction temperature varies depending on the boiling point of the alcohol or phenol to be produced, it is usually in the range of 120 to 300°C. The reaction is completed under reduced pressure from the initial stage while the alcohol or phenols produced are distilled off. In order to promote the reaction, a catalyst commonly used for transesterification can also be used. Examples of the carbonic acid diester used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like. Among these, diphenyl carbonate is particularly preferred.

Monofunctional phenols commonly used as terminal terminator can be used. Monofunctional phenols are commonly used as end-stoppers for molecular weight control, especially in the case of reactions using phosgene as the carbonate precursor, and the resulting polycarbonate resins are terminally based on monofunctional phenols. Since it is blocked by a group, it has excellent thermal stability compared to those that are not. Specific examples of the monofunctional phenols include phenol, m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, 1-phenylphenol, 2-phenylphenol, p-tert-butylphenol, Examples include p-cumylphenol, isooctylphenol, p-long-chain alkylphenol and the like.

The polycarbonate copolymer of the present invention can optionally be copolymerized with an aliphatic diol. For example isosorbide: 1,4:3,6-dianhydro-D-sorbitol, tricyclodecanedimethanol (TCDDM), 4,8-bis(hydroxymethyl)tricyclodecane, tetramethylcyclobutanediol (TMCBD), 2, 2,4,4-tetramethylcyclobutane-1,3-diol, mixed isomers, cis/trans-1,4-cyclohexanedimethanol (CHDM), cis/trans-1,4-bis(hydroxymethyl)cyclohexane, Cyclohex-1,4-ylenedimethanol, trans-1,4-cyclohexanedimethanol (tCHDM), trans-1,4-bis(hydroxymethyl)cyclohexane, cis-1,4-cyclohexanedimethanol (cCHDM), cis -1,4-bis(hydroxymethyl)cyclohexane, cis-1,2-cyclohexanedimethanol, 1,1'-bi(cyclohexyl)-4,4'-diol, spiroglycol, dicyclohexyl-4,4'-diol , 4,4′-dihydroxybicyclohexyl, and poly(ethylene glycol).

The polycarbonate copolymer of the present invention can be copolymerized with a fatty acid if necessary. For example, 1,10-dodecanedioic acid (DDDA), adipic acid, hexanedioic acid, isophthalic acid, 1,3-benzenedicarboxylic acid, terephthalic acid, 1,4-benzenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 3-hydroxybenzoic acid (mHBA), and 4-hydroxybenzoic acid (pHBA).

The polycarbonate copolymers of the present invention include polyester carbonates obtained by copolymerizing aromatic or aliphatic (including alicyclic) bifunctional carboxylic acids. Aliphatic bifunctional carboxylic acids are preferably α,ω-dicarboxylic acids. Aliphatic difunctional carboxylic acids include, for example, linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosanedioic acid, as well as cyclohexanedicarboxylic acid. Alicyclic dicarboxylic acids such as acids are preferred. These carboxylic acids may be copolymerized as long as the purpose is not impaired. The polycarbonate copolymer of the present invention can also be copolymerized with structural units containing polyorganosiloxane units, if necessary.

The polycarbonate copolymer of the present invention can be made into a branched polycarbonate by copolymerizing a structural unit containing a trifunctional or higher polyfunctional aromatic compound, if necessary. Polyfunctional aromatic compounds having a trifunctional or higher functionality used in branched polycarbonates include 4,6-dimethyl-2,4,6-tris(4-hydroxydiphenyl)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, and 4-{4-[1,1-bis( Preferable examples include trisphenols such as 4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol. Among them, 1,1,1-tris(4-hydroxyphenyl)ethane is preferred. Structural units derived from such polyfunctional aromatic compounds are preferably 0.03 to 1.5 mol%, more preferably 0.1 mol% in total 100 mol% with structural units from other divalent components. to 1.2 mol %, particularly preferably 0.2 to 1.0 mol %.

The branched structural unit is not only derived from a polyfunctional aromatic compound, but also derived without using a polyfunctional aromatic compound, such as a side reaction that occurs during a polymerization reaction by a melt transesterification method. may The ratio of such branched structures can be calculated by 1H-NMR measurement.

The polycarbonate copolymer of the present invention preferably has a viscosity average molecular weight (Mv) of 15,000 to 40,000, more preferably 16,000 to 30,000, and still more preferably 18,000 to 28,000. A polycarbonate copolymer having a viscosity-average molecular weight of less than 15,000 may not have practically sufficient impact resistance. On the other hand, a polycarbonate copolymer having a viscosity average molecular weight of more than 40,000 requires a high molding temperature or requires a special molding method, resulting in poor versatility. Injection speed dependence tends to increase, and the yield may decrease due to poor appearance and the like.

The viscosity-average molecular weight of the polycarbonate copolymer in the present invention is obtained by first calculating the specific viscosity (η _SP ) calculated by the following formula at 20° C. from a solution of 0.7 g of the polycarbonate copolymer dissolved in 100 ml of methylene chloride to determine the Ostwald viscosity. using a meter,
Specific viscosity (η _SP ) = (tt ₀ )/t ₀
[t ₀ is the number of seconds the methylene chloride falls, t is the number of seconds the sample solution falls]
The viscosity-average molecular weight Mv is calculated from the determined specific viscosity (η _SP ) by the following formula.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[η]=1.23×10 ⁻⁴ Mv ^0.83
c=0.7

The polycarbonate copolymer of the present invention preferably has a glass transition temperature of 140 to 160°C, more preferably 140 to 155°C, even more preferably 140 to 150°C. If the glass transition temperature is less than 140°C, the heat resistance may be poor, and if it exceeds 160°C, the impact resistance may be poor.

<B component: styrene resin>
The styrenic resin, which is the component B of the present invention, is one or more selected from resins composed of aromatic vinyl compound polymers or copolymers, or aromatic vinyl compounds and other vinyl monomers and rubbery polymers. It is preferable that the resin is a copolymer obtained by copolymerizing the above. The aromatic vinyl compound is preferably contained in an amount of 10% by weight or more in 100% by weight of the resin.

Examples of aromatic vinyl compounds include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert-butylstyrene, vinylnaphthalene, methoxystyrene, monobromostyrene, Dibromostyrene, fluorostyrene, tribromostyrene and the like can be mentioned, and styrene is particularly preferred.

Other vinyl monomers copolymerizable with aromatic vinyl compounds are preferably vinyl cyanide compounds and (meth)acrylic acid ester compounds. Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile, and acrylonitrile is particularly preferred.

Specific examples of (meth)acrylate compounds include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, Hexyl (meth)acrylate, Octyl (meth)acrylate, 2-Ethylhexyl (meth)acrylate, Cyclohexyl (meth)acrylate, Dodecyl (meth)acrylate, Octadecyl (meth)acrylate, Phenyl (meth)acrylate, Benzyl (meth)acrylate, etc. can be mentioned. The notation of (meth)acrylate indicates that both methacrylate and acrylate are included, and the notation of (meth)acrylic acid ester indicates that both methacrylic acid ester and acrylic acid ester are included. A particularly suitable (meth)acrylic ester compound is methyl methacrylate.

Other vinyl monomers copolymerizable with aromatic vinyl compounds other than vinyl cyanide compounds and (meth)acrylic acid ester compounds include epoxy group-containing methacrylic acid esters such as glycidyl methacrylate, maleimide, N-methylmaleimide, Maleimide monomers such as N-phenylmaleimide, α,β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic acid and itaconic acid, and their anhydrides.

Examples of the rubbery polymer include polybutadiene, polyisoprene, diene-based copolymers (e.g., random copolymers and block copolymers of styrene/butadiene, acrylonitrile/butadiene copolymers, and (meth)acrylic acid alkyl esters. and butadiene copolymers, etc.), copolymers of ethylene and α-olefins (e.g., ethylene/propylene random copolymers and block copolymers, ethylene/butene random copolymers and block copolymers, etc.) , copolymers of ethylene and unsaturated carboxylic acid esters (e.g., ethylene-methacrylate copolymers and ethylene-butyl acrylate copolymers), copolymers of ethylene and aliphatic vinyl (e.g., ethylene-vinyl acetate copolymers), ethylene and propylene and non-conjugated diene terpolymers (e.g. ethylene-propylene-hexadiene copolymers), acrylic rubbers (e.g. polybutyl acrylate, poly(2-ethylhexyl acrylate), and butyl acrylate and 2-ethylhexyl acrylate), and silicone rubber (e.g., polyorganosiloxane rubber, IPN type rubber consisting of a polyorganosiloxane rubber component and a polyalkyl (meth)acrylate rubber component; that is, two rubbers rubber having a structure in which the components are intertwined so that they cannot be separated, and IPN type rubber consisting of a polyorganosiloxane rubber component and a polyisobutylene rubber component, etc.). Among them, polybutadiene, polyisoprene, or diene-based copolymers are more preferable, and polybutadiene is particularly preferable. The content of these rubbery polymers is preferably 90% by weight or less, more preferably 80% by weight or less, based on 100% by weight of the styrenic resin.

Specific examples of styrene resins include styrene polymers such as polystyrene resins, HIPS resins, MS resins, ABS resins, AS resins, AES resins, ASA resins, MBS resins, MABS resins, MAS resins, and SMA resins. and styrenic thermoplastic elastomers (eg, (hydrogenated) styrene-butadiene-styrene copolymer, (hydrogenated) styrene-isoprene-styrene copolymer, etc.). The notation of (hydrogenated) means that both non-hydrogenated copolymers and hydrogenated copolymers are included. These are readily available. Among them, HIPS resins, ABS resins, AS resins, AES resins, ASA resins, MBS resins, MABS resins, MAS resins, and rubber-reinforced styrene resins such as styrene thermoplastic elastomers are more preferable.

Among these, HIPS resin, ABS resin, and AS resin are particularly preferred. ABS resin has excellent moldability for thin-walled molded products and also has good impact resistance. In particular, favorable properties are exhibited in combination with an aromatic polycarbonate resin. Here, MS resin is a copolymer resin mainly composed of methyl methacrylate and styrene, AES resin is a copolymer resin mainly composed of acrylonitrile, ethylene-propylene rubber and styrene, and ASA resin is mainly composed of acrylonitrile, styrene and acrylic rubber. MABS resin is a copolymer resin mainly composed of methyl methacrylate, acrylonitrile, butadiene and styrene, MAS resin is a copolymer resin mainly composed of methyl methacrylate, acrylic rubber and styrene, SMA resin is styrene and maleic anhydride A copolymer resin consisting primarily of acid (MA) is shown.

Styrenic resins can be used alone or in combination of two or more. For example, the ABS resin is generally a mixture of an AS polymer (a copolymer of acrylonitrile and styrene) and an ABS copolymer (a copolymer obtained by graft copolymerizing acrylonitrile and styrene to polybutadiene rubber). is also preferably used in the present invention.

Furthermore, the styrenic resin may have high stereoregularity such as syndiotactic polystyrene by using a catalyst such as a metallocene catalyst during its production. Furthermore, in some cases, polymers and copolymers with narrow molecular weight distributions, block copolymers, and polymers and copolymers with high stereoregularity obtained by methods such as anionic living polymerization and radical living polymerization, good too.

In the ABS resin used in the present invention, the proportion of the diene rubber component in 100% by weight of the ABS resin component (that is, in the total 100% by weight of the ABS polymer and the AS polymer) is preferably 5 to 80% by weight, and more preferably It is preferably 8 to 50% by weight, particularly preferably 10 to 30% by weight.

Examples of the vinyl cyanide compound used in the ABS resin include those mentioned above, and acrylonitrile is particularly preferred. As the aromatic vinyl compound, those mentioned above can also be used, but styrene and α-methylstyrene are particularly preferred. The ratio of the component grafted to the diene rubber component is preferably 95-20% by weight, more preferably 92-50% by weight, based on 100% by weight of the ABS resin component. Further, it is preferable that the vinyl cyanide compound is 5 to 50% by weight and the aromatic vinyl compound is 95 to 50% by weight based on 100% by weight of the total amount of the vinyl cyanide compound and the aromatic vinyl compound. Furthermore, it is also possible to use a mixture of methyl (meth) acrylate, ethyl acrylate, maleic anhydride, N-substituted maleimide, etc. for some of the components grafted to the above diene rubber component, and the content ratio of these in the ABS resin component is A content of 15% by weight or less is preferable. Furthermore, various conventionally known initiators, chain transfer agents, emulsifiers, etc., used in the reaction can be used as required.

The ABS resin preferably has a rubber particle size of 0.1 to 5.0 μm, more preferably 0.2 to 3.0 μm, and particularly preferably 0.3 to 1.5 μm. The rubber particle size distribution may be either a single distribution or one having two or more peaks, and the morphology of the rubber particles should also be such that the rubber particles form a single phase. Alternatively, it may have a salami structure by containing an occluded phase around rubber particles.

It is also well known that ABS resins contain copolymers of vinyl cyanide compounds and aromatic vinyl compounds that are not grafted onto diene rubber components. In the present invention, the ABS resin may contain a free polymer component generated during such polymerization as described above, and a vinyl compound polymer obtained by separately copolymerizing an aromatic vinyl compound and a vinyl cyanide compound. A blended combination may also be used. The reduced viscosity of the copolymer (AS copolymer) composed of the free vinyl cyanide compound and the aromatic vinyl compound is preferably 0.2 to 1 when the reduced viscosity (30° C.) obtained by the method described below is 0 dl/g, more preferably 0.3 to 0.7 dl/g.

The reduced viscosity was obtained by measuring 0.25 g of the AS copolymer precisely and dissolving it in 50 ml of dimethylformamide over 2 hours, using an Ubbelohde viscometer in an environment of 30°C. A viscometer with a solvent flowing time of 20 to 100 seconds is used. The reduced viscosity is obtained by the following equation from the number of seconds (t ₀ ) of the solvent flowing down and the number of seconds (t) of the solution flowing down.
Reduced viscosity (η _sp /C) = {(t/t ₀ )-1}/0.5
The proportion of free AS copolymer can be obtained by dissolving the ABS resin in a good solvent for the AS copolymer such as acetone and extracting the soluble matter. On the other hand, the insoluble matter (gel) becomes the net ABS copolymer.

The ratio of the vinyl cyanide compound and the aromatic vinyl compound grafted to the diene rubber component in the ABS copolymer (the ratio of the weight of the graft component to the weight of the diene rubber component), that is, the graft ratio (% by weight) is 20 ~200% is preferred, more preferably 20-80%.

Such ABS resin may be produced by any method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. ABS resins produced by bulk polymerization and suspension bulk polymerization are more preferred in terms of hydrolysis resistance. Also, the copolymerization may be carried out in one step or in multiple steps.

The AS resin in the present invention is a thermoplastic copolymer obtained by copolymerizing a vinyl cyanide compound and an aromatic vinyl compound. Examples of such a vinyl cyanide compound include those mentioned above, and acrylonitrile is particularly preferably used. Examples of the aromatic vinyl compound include those mentioned above, but styrene and α-methylstyrene are preferred. The ratio of each component in the AS resin is preferably 5 to 50% by weight, more preferably 15 to 35% by weight, and preferably 95% by weight of the vinyl cyanide compound, when the total is 100% by weight. ~50% by weight, more preferably 85-65% by weight. Further, these vinyl compounds may be copolymerized with other copolymerizable vinyl compounds. The content of these is preferably 15% by weight or less in the AS resin component. As for the initiator, chain transfer agent, etc. used in the reaction, various conventionally known ones can be used as required.

Such AS resin may be produced by any method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc., but bulk polymerization is preferred. The method of copolymerization may be either one-step copolymerization or multi-step copolymerization. The reduced viscosity of such AS resin is preferably 0.2 to 1.0 dl/g, more preferably 0.4 to 0.7 dl/g (the method for measuring the reduced viscosity is in accordance with the above method).

Such AS resin contains 15 to 35% by weight of acrylonitrile and 85 to 65% by weight of styrene in 100% by weight of the entire AS resin, is produced by bulk polymerization, and has a reduced viscosity of 0.4 to 0.7 dl. /g can be preferably used. In ABS resin, when an ABS copolymer and an AS copolymer are blended, the proportions of the aromatic vinyl compound and the vinyl cyanide compound in each copolymer may be the same or different. Preferably, they are substantially identical. Component B is preferably at least one styrenic resin selected from the group consisting of ABS resins and AS resins.

The amount of the styrene-based resin (component B) is 5 to 40 parts by weight, preferably 10 to 35 parts by weight, more preferably 15 to 30 parts by weight, based on the total 100 parts by weight of the components A and B. Most preferably 25-30 parts by weight. When the blending amount is more than the lower limit, excellent impact resistance is exhibited. Moreover, when the content is below the upper limit, excellent heat resistance and surface hardness can be obtained.

<Component C: Impact modifier other than component B>
The impact modifier (component C) used in the present invention is a rubber having a glass transition temperature of 10°C or lower, preferably -10°C or lower, more preferably -30°C or lower, other than the styrene resin (component B). A polymer composed of the rubber component and a copolymer obtained by bonding other polymer chains to the polymer composed of the rubber component are preferred. Furthermore, it is preferable that the rubber component is a polymer containing at least 35% by weight, more preferably 45% by weight in 100% by weight of the rubbery polymer. Practically, the upper limit of the content of the rubber component is preferably about 90% by weight.

The impact modifier is more preferably a copolymer formed by bonding other polymer chains. It is widely known that in the production of a rubber-like polymer in which other polymer chains are graft-bonded to a rubber component, a considerable amount of polymer or copolymer that is not grafted to the rubber component is produced. The C component of the present invention may contain such a free polymer or copolymer.

More specifically, as the impact modifier for component C, MB (methyl methacrylate-butadiene) copolymer, MA (methyl methacrylate-acrylic rubber) copolymer, methyl methacrylate-acrylic/butadiene rubber copolymer, methyl methacrylate - (acrylic/silicone IPN rubber) copolymers. Each of these copolymers is preferably a core-shell type graft copolymer in which polymer chains composed of the above-mentioned monomers are bonded to a polymer core composed of a rubber component. For example, rubber components mainly composed of butadiene rubber, acrylic rubber, or butadiene-acrylic composite rubber include Kaneace B series (e.g. B-56) manufactured by Kaneka Co., Ltd., Metabren C series manufactured by Mitsubishi Rayon Co., Ltd. C-223A, etc.), W series (e.g., W-450A, etc.), Kureha Chemical Industry Co., Ltd. Pararoid EXL series (e.g., EXL-2602, etc.), HIA series (e.g., HIA-15, etc.), BTA series (e.g., BTA) -III, etc.), KCA series, Rohm and Haas Paraloid EXL series, KM series (e.g. KM-336P, KM-357P, etc.), Ube Cycon Co., Ltd. UCL modifier resin series (UMG ABS Co., Ltd. ) and the UMG AXS resin series of )), and those mainly composed of acrylic-silicone composite rubber as a rubber component are commercially available from Mitsubishi Rayon Co., Ltd. under the trade names of METABLEN S-2001 and SRK-200. mentioned. In particular, a core-shell type graft copolymer composed of butadiene rubber as the rubber component is preferable in terms of impact improvement.

The rubber particle size of the impact modifier is preferably 0.1 to 5.0 μm, more preferably 0.2 to 3.0 μm, particularly preferably 0.2 to 1.5 μm. As for the distribution of the rubber particle size, it is possible to use either one having a single distribution or one having a plurality of peaks of two or more peaks. Alternatively, it may have a salami structure by containing an occluded phase around rubber particles.

In the rubbery polymer of the graft copolymer, the weight ratio of the grafted component to the rubber substrate (graft ratio (% by weight)) is preferably 10 to 100%, more preferably 15 to 70%, still more preferably 15-40%.

Further, examples of the impact modifier of the present invention include various thermoplastic elastomers composed of hard segments and soft segments. Examples of such thermoplastic elastomers include polyester elastomers, polyurethane elastomers, and olefinic elastomers.

In the present invention, the content of the impact modifier (component C) is preferably 3 to 10 parts by weight, more preferably 3 to 8 parts by weight, with respect to the total of 100 parts by weight of the components A and B. preferable. Below the upper limit, problems such as deterioration of heat resistance and surface hardness are less likely to occur, and above the lower limit, problems such as deterioration of impact resistance are less likely to occur.

<Other ingredients>
Additives can be added to the resin composition of the present invention depending on the purpose.
(i) Release agent It is preferable to mix a release agent with the resin composition of the present invention. Known release agents can be used in the present invention. For example, fatty acid esters, polyolefin waxes (polyethylene wax, 1-alkene polymer, etc., those modified with functional group-containing compounds such as acid modification can also be used), silicone compounds, fluorine compounds (typically polyfluoroalkyl ethers), fluorinated oils, etc.), paraffin wax, beeswax, and the like. Among these, fatty acid esters are preferred from the viewpoints of ease of availability, releasability and transparency. The content of the release agent is preferably 0.005 to 0.2 parts by weight, more preferably 0.007 to 0.1 parts by weight, and further It is preferably 0.01 to 0.06 parts by weight. If the content is less than the lower limit of the above range, the release property may not be sufficiently improved, and if the content exceeds the upper limit, appearance defects such as bleeding out may occur.

Fatty acid esters are preferred among the above release agents. Such fatty acid esters are esters of fatty alcohols and fatty carboxylic acids. Such fatty alcohols may be monohydric alcohols or polyhydric alcohols having a valence of 2 or more. The carbon number of the alcohol is preferably in the range of 3-32, more preferably in the range of 5-30. Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, ceryl alcohol, and triacontanol. Such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol-hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. Polyhydric alcohols are more preferred in the fatty acid ester of the present invention.

On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, more preferably 10 to 22 carbon atoms. Examples of the aliphatic carboxylic acid include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanic acid, icosanoic acid, and docosanoic acid (behenic acid), and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and cetoleic acid. can. Among the above, the aliphatic carboxylic acid preferably has 14 to 20 carbon atoms. Of these, saturated aliphatic carboxylic acids are preferred. Since such aliphatic carboxylic acids are usually produced from natural fats and oils such as animal fats (such as beef tallow and lard) and vegetable fats (such as palm oil), these aliphatic carboxylic acids usually have a number of carbon atoms is a mixture containing other carboxylic acid components with different Therefore, the production of the aliphatic carboxylic acid used in the present invention is also produced from such natural fats and oils, and is in the form of a mixture containing other carboxylic acid components. The acid value of the fatty acid ester is preferably 20 or less (can be substantially 0). However, in the case of a full ester (full ester), it is preferable to contain not a little free fatty acid in order to improve releasability. Further, the iodine value of the fatty acid ester is preferably 10 or less (can be substantially 0). These properties can be obtained by the method specified in JIS K 0070.

Fatty acid esters that can be used in the resin composition of the present invention may be either partial esters or full esters. Partial esters are more preferred in the present invention from the viewpoint of good releasability and durability. Among them, glycerin monoester is preferred. Glycerin monoesters are mainly composed of monoesters of glycerin and fatty acids, and suitable fatty acids include saturated fatty acids such as stearic acid, palmitic acid, behenic acid, arachidic acid, montanic acid, and lauric acid, oleic acid, and linoleic acid. , and unsaturated fatty acids such as sorbic acid, and particularly preferred are those based on glycerin monoesters of stearic acid, behenic acid and palmitic acid. Such fatty acids are synthesized from natural fatty acids and are mixed as described above. Glycerin monoester can be used in combination with other mold release agents, particularly fatty acid full esters, but even when used in combination, glycerin monoester is preferably the main component. That is, it is preferably 60% by weight or more in 100% by weight of the release agent.

Partial esters are often inferior to full esters in terms of thermal stability. To improve the thermal stability of such partial esters, the partial esters preferably have a sodium metal content of less than 20 ppm, more preferably less than 5 ppm, and even more preferably less than 1 ppm. A fatty acid partial ester having a sodium metal content of less than 1 ppm can be produced by producing a fatty acid partial ester by a conventional method and then purifying it by molecular distillation or the like.

Specifically, after removing gas and low-boiling substances with a spray nozzle degassing device, glycerol is distilled under the conditions of a distillation temperature of 120 to 150 ° C. and a degree of vacuum of 0.01 to 0.03 kPa using a falling film distillation device. After removing polyhydric alcohols such as alcohol, a centrifugal molecular distillation apparatus is used to distill a high-purity fatty acid partial ester under the conditions of a distillation temperature of 160 to 230 ° C. and a degree of vacuum of 0.01 to 0.2 Torr. and the like, and sodium metal can be removed as a distillation residue. By repeatedly subjecting the obtained distillate to molecular distillation, it is possible to further increase the purity and obtain a fatty acid partial ester with an even lower sodium metal content. In addition, it is also important to thoroughly clean the inside of the molecular distillation apparatus in advance by an appropriate method, and to prevent contamination of the sodium metal component from the external environment by, for example, increasing airtightness. Such fatty acid esters are available from specialized vendors (eg, Riken Vitamin Co., Ltd.).

(ii) Phosphorus-Based Stabilizer The resin composition of the present invention preferably further contains various phosphorus-based stabilizers mainly for the purpose of improving the thermal stability during molding. Phosphorous stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof. Further such phosphorus stabilizers include tertiary phosphines.

Specific examples of phosphite compounds include triphenylphosphite, tris(nonylphenyl)phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite, dioctylmonophenyl Phosphite, diisopropylmonophenylphosphite, monobutyldiphenylphosphite, monodecyldiphenylphosphite, monooctyldiphenylphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphite, tris( diethylphenyl)phosphite, tris(di-iso-propylphenyl)phosphite, tris(di-n-butylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2, 6-di-tert-butylphenyl)phosphite, distearylpentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl -4-methylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-ethylphenyl)pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, bis(nonylphenyl)penta Erythritol diphosphite, dicyclohexylpentaerythritol diphosphite and the like.

Furthermore, as other phosphite compounds, those having a cyclic structure which react with dihydric phenols can also be used. For example, 2,2′-methylenebis(4,6-di-tert-butylphenyl)(2,4-di-tert-butylphenyl)phosphite, 2,2′-methylenebis(4,6-di-tert- butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, 2,2′-methylenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite , 2,2′-ethylidenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite.

Phosphate compounds include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Diisopropyl phosphate and the like can be mentioned, and triphenyl phosphate and trimethyl phosphate are preferred.

Phosphonite compounds include tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylenedi Phosphonite, Tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylenediphosphonite, Tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite , tetrakis(2,6-di-tert-butylphenyl)-4,3′-biphenylenediphosphonite, tetrakis(2,6-di-tert-butylphenyl)-3,3′-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di -n-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite and the like, preferably tetrakis(di-tert-butylphenyl)-biphenylenediphosphonite, bis(di-tert-butylphenyl)-phenyl-phenylphosphonite, tetrakis(2, 4-di-tert-butylphenyl)-biphenylenediphosphonite, bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite are more preferred. Such a phosphonite compound can preferably be used in combination with a phosphite compound having an aryl group substituted with two or more alkyl groups.

Phosphonate compounds include dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate, and the like.

Tertiary phosphines include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, and tri-p-tolyl. Examples include phosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine.

The phosphorus-based stabilizers may be used singly or in combination of two or more. Among the phosphorus-based stabilizers, phosphite compounds or phosphonite compounds are preferred. In particular tris(2,4-di-tert-butylphenyl)phosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite and bis(2,4-di- tert-Butylphenyl)-phenyl-phenylphosphonite is preferred. A combination of these and a phosphate compound is also a preferred embodiment.

(iii) Hindered Phenolic Stabilizer The resin composition of the present invention may be blended with a hindered phenol stabilizer for the main purpose of improving the thermal stability during molding and heat aging resistance. can. Such hindered phenol stabilizers include, for example, α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl-β-(4′-hydroxy-3′,5′-di-tert-butylphenol ) 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′-dimethylene-bis(6-α-methyl-benzyl-p-cresol) 2,2′-ethylidene-bis(4,6-di-tert-butylphenol), 2,2′-butylidene-bis(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-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]- 1,1,-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, 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-butyl phenol), 2,2-thiodiethylenebis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy -3′,5′-di-tert-butylanilino)-1,3,5-triazine, N,N′-hexamethylenebis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butyl Phenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4 -hydroxyphenyl)isocyanurate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethyl benzyl)isocyanurate, 1,3,5-tris-2[3(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethylisocyanurate, and tetrakis[methylene-3-(3′,5 '-Di-tert-butyl-4-hydroxyphenyl)propionate]methane and the like are exemplified. All of these are readily available. The hindered phenol-based antioxidants may be used alone or in combination of two or more.

The content of the (ii) phosphorus-based stabilizer and (iii) the hindered phenol-based antioxidant is preferably 0.0001 to 1 part by weight with respect to the total 100 parts by weight of the A component and the B component, and more It is preferably 0.001 to 0.1 parts by weight, more preferably 0.005 to 0.1 parts by weight. If the amount of the stabilizer is less than the above range, it is difficult to obtain a good stabilizing effect. There is

Antioxidants other than the above-mentioned hindered phenol-based antioxidants can be appropriately used in the resin composition of the present invention. Such other antioxidants include, for example, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. The content of these other antioxidants is preferably 0.001 to 0.05 parts by weight per 100 parts by weight of the total of the A component and the B component.

The resin composition of the present invention also includes ultraviolet absorbers, light stabilizers, antistatic agents, heat ray absorbers, flame retardants, hydrolysis modifiers, inorganic fillers, antibacterial agents, photocatalytic antifouling agents, light It may contain a diffusing agent, a white pigment for high light reflection, and the like. These can be contained by appropriately selecting agents and blending amounts that do not interfere with the effects of the present invention.

(iv) Ultraviolet Absorber The resin composition of the present invention may contain an ultraviolet absorber. Specific examples of benzophenone-based UV absorbers of the present invention include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 2-hydroxy-4. -benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydrate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2, 2′,4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sodium sulfoxybenzophenone, bis Examples include (5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

Specific examples of benzotriazole-based UV absorbers include 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[ -(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole , 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 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-octoxyphenyl)benzotriazole, 2,2 '-methylenebis(4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis(1,3-benzoxazin-4-one), and 2-[2-hydroxy-3-(3, 4,5,6-Tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole, and 2-(2′-hydroxy-5-methacryloxyethylphenyl)-2H-benzotriazole and a vinyl system copolymerizable with said monomer 2-hydroxyphenyl- such as copolymers with monomers and copolymers of 2-(2'-hydroxy-5-acryloxyethylphenyl)-2H-benzotriazole and a vinyl monomer copolymerizable with the monomer A polymer having a 2H-benzotriazole skeleton is exemplified.

Specific examples of hydroxyphenyltriazine-based UV absorbers include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 2-(4 ,6-diphenyl-1,3,5-triazin-2-yl)-5-methyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-ethyloxy phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-propyloxyphenol, and 2-(4,6-diphenyl-1,3,5-triazine-2- yl)-5-butyloxyphenol and the like. Furthermore, 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hexyloxyphenol, etc., in which the phenyl group of the above-exemplified compounds is 2,4-dimethylphenyl A compound having a phenyl group is exemplified.

Specific examples of cyclic imino ester UV absorbers include 2,2′-p-phenylenebis(3,1-benzoxazin-4-one), 2,2′-(4,4′-diphenylene ) bis(3,1-benzoxazin-4-one) and 2,2′-(2,6-naphthalene)bis(3,1-benzoxazin-4-one).

Further, as the ultraviolet absorber, specifically in the cyanoacrylate type, for example, 1,3-bis-[(2′-cyano-3′,3′-diphenylacryloyl)oxy]-2,2-bis[(2- Examples include cyano-3,3-diphenylacryloyl)oxy]methyl)propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene.

Furthermore, the above-mentioned ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, so that the ultraviolet absorbing monomer and/or the photostable monomer having a hindered amine structure and the alkyl (meth)acrylate It may be a polymer-type ultraviolet absorber obtained by copolymerizing a monomer such as Preferred examples of the UV-absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic iminoester skeleton, and a cyanoacrylate skeleton in the ester substituent of the (meth)acrylic acid ester. be.

Among the above, benzotriazole and hydroxyphenyltriazine are preferred from the viewpoint of ultraviolet absorption ability, and cyclic iminoester and cyanoacrylate are preferred from the viewpoint of heat resistance and hue. The above UV absorbers may be used alone or in combination of two or more.

The content of the ultraviolet absorber is preferably 0.01 to 2 parts by weight, more preferably 0.03 to 2 parts by weight, and still more preferably 0.04 parts by weight with respect to the total 100 parts by weight of the components A and B. ~1 part by weight, most preferably 0.05-0.5 parts by weight.

(v) Flame Retardant The resin composition of the present invention may contain various compounds known as flame retardants for polycarbonate resins. Incorporation of compounds used as flame retardants not only improves flame retardancy, but also provides, based on the properties of each compound, improved antistatic properties, fluidity, stiffness, and thermal stability, for example.

Such flame retardants include (i) organic metal salt flame retardants (e.g., alkali (earth) metal salts of organic sulfonates, metal borate flame retardants, and metal stannate flame retardants), (ii) Organophosphorus flame retardants (e.g., monophosphate compounds, phosphate oligomeric compounds, phosphonate oligomeric compounds, phosphonitrile oligomeric compounds, phosphonic acid amide compounds, etc.), (iii) silicone flame retardants consisting of silicone compounds, and (iv) halogens flame retardants (eg, brominated epoxy resins, brominated polystyrene, brominated polycarbonates (including oligomers), brominated polyacrylates, chlorinated polyethylenes, etc.).

(vi) Anti-dripping agent The resin composition of the present invention may contain an anti-dripping agent. Better flame retardancy can be obtained by using such an anti-dripping agent together with the flame retardant. Examples of such anti-dripping agents include fluorine-containing polymers having fibril-forming ability. , etc.), partially fluorinated polymers as shown in U.S. Pat. No. 4,379,910, and polycarbonate resins produced from fluorinated diphenols. is).

Polytetrafluoroethylene (fibrillated PTFE) having fibril-forming ability has an extremely high molecular weight, and exhibits a tendency to become fibrous by binding PTFE to each other by an external action such as a shearing force. Its number average molecular weight ranges from 1.5 million to tens of millions. Such a lower limit is more preferably 3 million. Such number average molecular weight is calculated based on the melt viscosity of polytetrafluoroethylene at 380° C., as disclosed in JP-A-6-145520. That is, fibrillated PTFE has a melt viscosity of 107 to 1013 poise, preferably 108 to 1012 poise at 380° C. measured by the method described in the publication.

Such PTFE can be used not only in a solid form but also in an aqueous dispersion form. In addition, PTFE having such fibril-forming ability improves its dispersibility in resin, and it is also possible to use a PTFE mixture in which it is mixed with other resins in order to obtain better flame retardancy and mechanical properties. be. Further, as disclosed in JP-A-6-145520, those having such a fibrillated PTFE as a core and a low-molecular-weight polytetrafluoroethylene as a shell are also preferably used.

Examples of commercial products of fibrillated PTFE include Teflon (registered trademark) 6J manufactured by DuPont Fluorochemicals of Mitsui Co., Ltd., Polyflon MPA FA500 and F-201L manufactured by Daikin Chemical Industries, Ltd., and the like. Commercially available aqueous dispersions of fibrillated PTFE include Fluon AD-1 and AD-936 manufactured by Asahi ICI Fluoropolymers Co., Ltd.; Fluon D-1 and D-2 manufactured by Daikin Industries, Ltd.; Teflon (registered trademark) 30J manufactured by DuPont Fluorochemical Co., Ltd. can be mentioned as a representative.

Mixed forms of fibrillated PTFE include (1) a method of mixing an aqueous dispersion of fibrillated PTFE and an aqueous dispersion or solution of an organic polymer to co-precipitate to obtain a co-aggregated mixture (JP-A-60-258263; (2) A method of mixing an aqueous dispersion of fibrillated PTFE and dried organic polymer particles (described in JP-A-4-272957). (3) A method in which an aqueous dispersion of fibrillated PTFE and a solution of organic polymer particles are uniformly mixed, and the respective media are simultaneously removed from the mixture (JP-A-06-220210, JP-A-06-220210; 08-188653, etc.), (4) a method of polymerizing a monomer that forms an organic polymer in an aqueous dispersion of fibrillated PTFE (described in JP-A-9-95583, method), and (5) a method of uniformly mixing an aqueous PTFE dispersion and an organic polymer dispersion, further polymerizing a vinyl monomer in the mixed dispersion, and then obtaining a mixture (JP-A-11- 29679, etc.) can be used. Examples of commercial products of fibrillated PTFE in a mixed form include "METABLEN A3800" (trade name) manufactured by Mitsubishi Rayon Co., Ltd., and "BLENDEX B449" (trade name) manufactured by GE Specialty Chemicals.

In order to more effectively utilize the good mechanical properties and surface appearance of the resin composition of the present invention, the fibrillated PTFE is preferably dispersed as finely as possible. As a means of achieving such fine dispersion, the mixed form of fibrillated PTFE is advantageous. A method of directly supplying the aqueous dispersion form to the melt-kneader is also advantageous for fine dispersion. However, it should be noted that the hue of the aqueous dispersion is slightly deteriorated. The proportion of fibrillated PTFE in the mixed form is preferably 10-80% by weight, more preferably 15-75% by weight, based on 100% by weight of the mixture. When the proportion of fibrillated PTFE is within this range, good dispersibility of fibrillated PTFE can be achieved.

The content of the fibrillated PTFE is preferably 0.001 to 1 part by weight, more preferably 0.1 to 0.7 part by weight, per 100 parts by weight of the total of the A component and the B component.

(vii) Antistatic agent The resin composition of the present invention may be required to have antistatic performance, and in such cases, it preferably contains an antistatic agent. Examples of such antistatic agents include (1) phosphonium arylsulfonates represented by phosphonium dodecylbenzenesulfonate, organic phosphonium sulfonates such as phosphonium alkylsulfonate, and phosphonium tetrafluoroborate. Phosphonium borate salts are mentioned. The content of the phosphonium salt is appropriately 5 parts by weight or less, preferably 0.05 to 5 parts by weight, more preferably 1 to 3.5 parts by weight, based on the total of 100 parts by weight of component A and component B. parts, more preferably 1.5 to 3 parts by weight.

Examples of antistatic agents include (2) organic lithium sulfonate, organic sodium sulfonate, organic potassium sulfonate, organic cesium sulfonate, organic rubidium sulfonate, organic calcium sulfonate, organic magnesium sulfonate, and organic barium sulfonate. organic sulfonic acid alkali (earth) metal salts such as Such metal salts are also used as flame retardants, as described above. More specific examples of such metal salts include metal salts of dodecylbenzenesulfonic acid and metal salts of perfluoroalkanesulfonic acid. The content of the organic alkali (earth) metal sulfonate is appropriately 0.5 parts by weight or less, preferably 0.001 to 0.3, per 100 parts by weight in total of the components A and B. parts by weight, more preferably 0.005 to 0.2 parts by weight. Especially preferred are alkali metal salts such as potassium, cesium and rubidium.

Examples of antistatic agents include (3) organic sulfonate ammonium salts such as alkylsulfonate ammonium salts and arylsulfonate ammonium salts. The content of the ammonium salt is suitably 0.05 parts by weight or less based on the total of 100 parts by weight of the A component and the B component. The antistatic agent includes, for example, (4) a polymer containing a poly(oxyalkylene) glycol component such as polyetheresteramide as its constituent component. The content of the polymer is suitably 5 parts by weight or less per 100 parts by weight in total of the A component and the B component.

<Other additives>
In addition to the additives described above, the resin composition of the present invention may contain fluorescent dyes, fluorescent brighteners, inorganic phosphors (for example, phosphors having aluminate as a mother crystal), bluing agents, and liquid paraffin. A dispersing agent, a heat absorbing agent, a photochromic agent, and the like can be blended.

<Production of resin composition and molded article>
In producing the resin composition of the present invention, the production method is not particularly limited, and known production methods can be used. Generally, after premixing the polycarbonate copolymer and additives, the mixture is put into an extruder and melt-kneaded, and then the extruded thread is cooled and cut by a pelletizer to produce a pelletized molding material. Both a single-screw extruder and a twin-screw extruder can be used as the extruder, but the twin-screw extruder is preferable from the viewpoint of productivity and kneadability. A representative example of such a twin-screw extruder is ZSK (manufactured by Werner & Pfleiderer, trade name). Specific examples of similar types include TEX (manufactured by Japan Steel Works, Ltd., trade name), TEM (manufactured by Toshiba Machine Co., Ltd., trade name), and KTX (manufactured by Kobe Steel, Ltd., trade name). can be mentioned. As the extruder, it is preferable to use an extruder having a vent capable of degassing moisture in the raw material and volatile gas generated from the melt-kneaded resin. A vacuum pump is preferably installed from the vent for efficiently discharging generated moisture and volatile gas to the outside of the extruder. It is also possible to install a screen in front of the die portion of the extruder to remove foreign matters and the like mixed in the extruded raw material to remove the foreign matters from the resin composition. Such screens include wire meshes, screen changers, sintered metal plates (such as disk filters), and the like.

Furthermore, the additive can be supplied to the extruder independently, but it is preferable to premix it with the resin raw material as described above. Examples of such premixing means include Nauta mixers, V-blenders, Henschel mixers, mechanochemical devices, and extrusion mixers. A more suitable method is, for example, to prepare a master agent by mixing a portion of the raw materials and additives with a high-speed mixer such as a Henschel mixer, and then mix the master agent with the remaining resin raw material and a high-speed mixer such as a Nauta mixer. It is a method of mixing with a stirrer that is not

The resin extruded from the extruder is directly cut and pelletized, or is pelletized by forming strands and then cutting the strands with a pelletizer. It is preferable to clean the atmosphere around the extruder when it is necessary to reduce the influence of external dust and the like. Furthermore, in the production of such pellets, various methods that have already been proposed are used to narrow the shape distribution of pellets, further reduce miscuts, further reduce fine powder generated during transportation or transportation, and It is preferable to reduce air bubbles (vacuum air bubbles) generated inside the strands and pellets. In order to reduce miscutting, there are measures such as temperature control of threads during cutting with a pelletizer, blowing ion wind during cutting, optimization of the rake angle of the pelletizer, and appropriate formulation of mold release agent. a method of filtering a mixture of pellets and water to separate pellets, water, and miscut. An example of the measuring method is disclosed, for example, in Japanese Unexamined Patent Application Publication No. 2003-200421. These formulations enable high-cycle molding and a reduction in the proportion of defects such as silver.

The resin composition of the present invention can also be used to obtain desired molded articles by methods such as injection molding, injection compression molding, injection blow molding, extrusion molding, and blow molding.

Examples will be described below in detail, but the present invention is not limited to these as long as the gist of the present invention is not exceeded. The evaluation of physical properties in Examples and Comparative Examples was performed according to the following methods.

<Physical property evaluation>
(1) Viscosity-average molecular weight The specific viscosity (η _SP ) is obtained from a solution of 0.7 g of a polycarbonate copolymer dissolved in 100 ml of methylene chloride at 20°C using an Ostwald viscometer _. The viscosity average molecular weight (Mv) was calculated by.
Specific viscosity (η _SP ) = (tt ₀ )/t ₀
[t ₀ is the number of seconds the methylene chloride falls, t is the number of seconds the sample solution falls]
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[η]=1.23×10 ⁻⁴ Mv ^0.83
c=0.7

(2) Composition ratio 40 mg of polycarbonate copolymer was dissolved in 0.6 ml of heavy chloroform solution, and ¹ H-NMR was measured with a 400 MHz nuclear magnetic resonance apparatus manufactured by JEOL Ltd., and the characteristic spectral peak area of each structural unit was obtained. The composition ratio of the polycarbonate copolymer was calculated from the ratio.

(3) Glass transition temperature Using a thermal analysis system DSC-2910 manufactured by TA Instruments, under a nitrogen atmosphere (nitrogen flow rate: 40 ml / min) according to JIS K7121, heating rate: 20 ° C. / min. measured in

(4) Surface hardness (pencil hardness)
Using a mold having a cavity surface with an arithmetic average roughness (Ra) of 0.03 μm, using an injection molding machine SG260M-HP manufactured by Sumitomo Heavy Industries, Ltd., a cylinder temperature of 270 ° C. and a mold temperature of 70 ° C. Under the conditions, the width is 50 mm, the length is 90 mm, and the thickness is 3 mm (length 20 mm), 2 mm (length 45 mm), and 1 mm (length 25 mm) from the gate side with a holding time of 10 seconds and a cooling time of 20 seconds. A stepped plate was molded. The pencil hardness of the 2 mm thick portion of the three-stage plate was measured according to JIS K5600.

(5) Impact resistance (notched Charpy impact strength)
After drying the pellets at 110 ° C. for 5 hours, using a test piece molded at a cylinder temperature of 270 ° C. with an injection molding machine SG260M-HP manufactured by Sumitomo Heavy Industries, Ltd. Charpy notched test piece at 23 ° C. in accordance with ISO 179 Impact strength was measured. (Specimen shape: length 80 mm x width 10 mm x thickness 4 mm)

(6) Heat resistance After drying the pellets at 110 ° C for 5 hours, using a test piece molded at a cylinder temperature of 270 ° C with an injection molding machine SG260M-HP manufactured by Sumitomo Heavy Industries, Ltd., in accordance with ISO75-1 and ISO75-2 Then, the deflection temperature under load was measured. Load: 1.80 MPa. (Specimen shape: length 80 mm x width 10 mm x thickness 4 mm)

(7) Rigidity (flexural modulus)
After drying the pellets at 110° C. for 5 hours, the flexural modulus was measured according to ISO178 using a test piece molded at a cylinder temperature of 270° C. using an injection molding machine SG260M-HP manufactured by Sumitomo Heavy Industries, Ltd. (Specimen shape: length 80 mm x width 10 mm x thickness 4 mm)

(Examples 1 to 12, Comparative Examples 1 to 7)
To the powder obtained with the composition shown in Table 1, 0.05% by weight of tris(2,4-di-tert-butylphenyl)phosphite and 0.1% by weight of stearic acid monoglyceride were added. After uniformly mixing the A component, B component and C component with the composition described in 2 and 3, the powder is melted while degassing with a vented twin screw extruder [KTX-46 manufactured by Kobe Steel, Ltd.]. After kneading, a polycarbonate resin composition was obtained. Surface hardness, impact resistance, heat resistance and rigidity of the obtained resin composition were evaluated by the methods described above. Results are shown in Tables 2 and 3.

<Polycarbonate copolymer (component A)>
(PC-1)
A reactor equipped with a thermometer, stirrer and reflux condenser was charged with 4,555 parts of a 48% aqueous sodium hydroxide solution and 22,730 parts of ion-exchanged water, to which 9,9-bis(4-hydroxy-3 -methylphenyl) fluorene (manufactured by Honshu Chemical) 596 parts, bisphenol C (manufactured by Honshu Chemical) 1,213 parts, bisphenol A (manufactured by Nippon Steel Chemical) 2,159 parts, and hydrosulfite 7.94 parts (Wako Jun Pharmaceutical Co., Ltd.) was dissolved, 13,415 parts of methylene chloride was added, and 2,000 parts of phosgene was blown in at 15 to 25° C. over about 70 minutes while stirring. After the completion of the phosgene blowing, 650 parts of a 48% aqueous sodium hydroxide solution and 89.9 parts of p-tert-butylphenol are added, stirring is resumed, and after emulsification, 3.94 parts of triethylamine are added, and the mixture is further stirred at 28-35°C for 1 hour. to terminate the reaction.

After the completion of the reaction, the product was diluted with methylene chloride and washed with water, then hydrochloric acid was added to make it acidic and washed with water, and the water washing was repeated until the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, and the polycarbonate copolymer was obtained. of methylene chloride solution was obtained. Next, this solution is passed through a filter with an opening of 0.3 μm, and is added dropwise to hot water in a kneader with an isolated chamber having a foreign matter outlet at the bearing, and the polycarbonate copolymer is flaked while distilling off methylene chloride. Subsequently, the liquid-containing flakes were pulverized and dried to obtain a powder. Table 1 shows the measurement results of the composition ratio, viscosity-average molecular weight, and glass transition temperature of the obtained polycarbonate copolymer.

(PC-2)
By the same method as (PC-1) except that 1,618 parts of bisphenol C (manufactured by Honshu Chemical), 1,799 parts of bisphenol A (manufactured by Nippon Steel Chemical), and 87.6 parts of p-tert-butylphenol were used. A polycarbonate copolymer powder was obtained. Table 1 shows the measurement results of the composition ratio, viscosity-average molecular weight, and glass transition temperature of the obtained polycarbonate copolymer.

(PC-3)
Bisphenol C (manufactured by Honshu Chemical) 2,023 parts, bisphenol A (manufactured by Nippon Steel Chemical) 1,440 parts, p-tert-butylphenol 82.8 parts in the same manner as (PC-1) A polycarbonate copolymer powder was obtained. Table 1 shows the measurement results of the composition ratio, viscosity-average molecular weight, and glass transition temperature of the obtained polycarbonate copolymer.

(PC-4)
9,9-bis (4-hydroxy-3-methylphenyl) fluorene (manufactured by Honshu Chemical) 298 parts, bisphenol C (manufactured by Honshu Chemical) 1,820 parts, bisphenol A (manufactured by Nippon Steel Chemical) 1,799 parts, A polycarbonate copolymer powder was obtained in the same manner as in (PC-1) except that 71.0 parts of p-tert-butylphenol was used. Table 1 shows the measurement results of the composition ratio, viscosity-average molecular weight, and glass transition temperature of the obtained polycarbonate copolymer.

(PC-5)
9,9-bis (4-hydroxy-3-methylphenyl) fluorene (manufactured by Honshu Chemical) 894 parts, bisphenol C (manufactured by Honshu Chemical) 1,213 parts, bisphenol A (manufactured by Nippon Steel Chemical) 1,979 parts, A polycarbonate copolymer powder was obtained in the same manner as in (PC-1) except that 106.5 parts of p-tert-butylphenol was used. Table 1 shows the measurement results of the composition ratio, viscosity-average molecular weight, and glass transition temperature of the obtained polycarbonate copolymer.

(PC-6)
A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 4,555 parts of a 48% sodium hydroxide aqueous solution and 22,730 parts of ion-exchanged water, and 2,023 parts of bisphenol C (manufactured by Honshu Kagaku) was added. part, 1,799 parts of bisphenol A (manufactured by Nippon Steel Chemical), and 7.94 parts of hydrosulfite (manufactured by Wako Pure Chemical Industries) are dissolved, then 13,415 parts of methylene chloride are added, and the mixture is stirred to 15 to 25 parts. 2,000 parts of phosgene was blown into the flask over about 70 minutes. After the completion of the phosgene blowing, 650 parts of a 48% aqueous sodium hydroxide solution and 89.9 parts of p-tert-butylphenol are added, stirring is resumed, and after emulsification, 3.94 parts of triethylamine are added, and the mixture is further stirred at 28-35°C for 1 hour. to terminate the reaction.

After the completion of the reaction, the product was diluted with methylene chloride and washed with water, then hydrochloric acid was added to make it acidic and washed with water, and the water washing was repeated until the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, and the polycarbonate copolymer was obtained. of methylene chloride solution was obtained. Next, this solution is passed through a filter with an opening of 0.3 μm, and is added dropwise to hot water in a kneader with an isolated chamber having a foreign matter outlet at the bearing, and the polycarbonate copolymer is flaked while distilling off methylene chloride. Subsequently, the liquid-containing flakes were pulverized and dried to obtain powder (A).

A reactor equipped with a thermometer, stirrer and reflux condenser was charged with 4,936 parts of 48% aqueous sodium hydroxide solution and 21,550 parts of ion-exchanged water, to which 9,9-bis(4-hydroxy- After dissolving 1,696 parts of 3-methylphenyl)fluorene (manufactured by Honshu Chemical), 2,388 parts of bisphenol A (manufactured by Nippon Steel Chemical), and 8.17 parts of hydrosulfite (manufactured by Wako Pure Chemical), chloride 19,080 parts of methylene was added, and 2,000 parts of phosgene was blown in at 15 to 25° C. over about 70 minutes while stirring. After phosgene was blown in, 617 parts of a 48% sodium hydroxide aqueous solution and 85.3 parts of p-tert-butylphenol were added, and stirring was resumed. After emulsification, 3.94 parts of triethylamine was added, and the mixture was further stirred at 28 to 35°C for 1 hour. to terminate the reaction.

After the completion of the reaction, the product was diluted with methylene chloride and washed with water, then hydrochloric acid was added to make it acidic and washed with water, and the water washing was repeated until the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, and the polycarbonate copolymer was obtained. of methylene chloride solution was obtained. Next, this solution is passed through a filter with an opening of 0.3 μm, and is added dropwise to hot water in a kneader with an isolated chamber having a foreign matter outlet at the bearing, and the polycarbonate copolymer is flaked while distilling off methylene chloride. Subsequently, the liquid-containing flakes were pulverized and dried to obtain a powder (B).

70 parts by weight of powder (A) and 30 parts by weight of powder (B) were uniformly mixed to obtain a polycarbonate copolymer powder. Table 1 shows the measurement results of the composition ratio, viscosity-average molecular weight, and glass transition temperature of the obtained polycarbonate copolymer.

(PC-7)
9,9-bis (4-hydroxy-3-methylphenyl) fluorene (manufactured by Honshu Chemical) 179 parts, bisphenol C (manufactured by Honshu Chemical) 2,023 parts, bisphenol A (manufactured by Nippon Steel Chemical) 1,691 parts, A polycarbonate copolymer powder was obtained in the same manner as in (PC-1) except that 92.3 parts of p-tert-butylphenol was used. Table 1 shows the measurement results of the composition ratio, viscosity-average molecular weight, and glass transition temperature of the obtained polycarbonate copolymer.

(PC-8)
9,9-bis (4-hydroxy-3-methylphenyl) fluorene (manufactured by Honshu Chemical) 1,193 parts, bisphenol C (manufactured by Honshu Chemical) 1,618 parts, bisphenol A (manufactured by Nippon Steel Chemical) 1,439 Polycarbonate copolymer powder was obtained in the same manner as in (PC-1) except that 92.3 parts of p-tert-butylphenol was used. Table 1 shows the measurement results of the composition ratio, viscosity-average molecular weight, and glass transition temperature of the obtained polycarbonate copolymer.

(PC-9)
Without using bisphenol A, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (manufactured by Honshu Kagaku) 566 parts, bisphenol C (manufactured by Honshu Kagaku) 3,452 parts, p-tert-butylphenol 80. Polycarbonate copolymer powder was obtained in the same manner as in (PC-1) except that 1 part was used. Table 1 shows the measurement results of the composition ratio, viscosity-average molecular weight, and glass transition temperature of the obtained polycarbonate copolymer.

(PC-10)
Without using bisphenol C, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (manufactured by Honshu Chemical) 596 parts, bisphenol A (manufactured by Nippon Steel Chemical) 3,238 parts, p-tert-butylphenol A polycarbonate copolymer powder was obtained in the same manner as in (PC-1) except that the amount was 71.0 parts. Table 1 shows the measurement results of the composition ratio, viscosity-average molecular weight, and glass transition temperature of the obtained polycarbonate copolymer.

(PC-11)
Without using 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (manufactured by Honshu Chemical), bisphenol C (manufactured by Honshu Chemical) 2,023 parts, bisphenol A (manufactured by Nippon Steel Chemical) 1,799 Polycarbonate copolymer powder was obtained in the same manner as in (PC-1) except that 87.6 parts of p-tert-butylphenol was used. Table 1 shows the measurement results of the composition ratio, viscosity-average molecular weight, and glass transition temperature of the obtained polycarbonate copolymer.

<Styrene resin (B component)>
ABS: ABS resin [UT-61 (trade name) manufactured by Japan A&L Co., Ltd. (butadiene rubber component: about 14% by weight, weight average rubber particle diameter: 0.56 µm)]
AS: AS resin [Rytac-A BS-207 (trade name) manufactured by Japan A&L Co., Ltd. (weight average molecular weight 109,000)]
<Impact modifier (component C)>
C-1: Core-shell graft copolymer (Rohm and Haas Co.: Paraloid EXL-2602 (trade name))
C-2: Core-shell graft copolymer (manufactured by Mitsubishi Chemical Corporation: Metabrene S-2001 (trade name))
C-3: Core-shell graft copolymer (manufactured by Mitsubishi Chemical Corporation: Metabrene W-450A (trade name))

As is clear from the results in Tables 2 and 3, resin molded articles made from the resin composition of the present invention are excellent in impact resistance, heat resistance, surface hardness and rigidity. In Comparative Example 1, the content of the styrene-based resin is less than the claimed range, so the impact resistance is inferior to that in Examples. In Comparative Example 2, since the content of the styrene-based resin is larger than the claimed range, the surface hardness and heat resistance are inferior to those of Examples. Comparative Examples 3 and 7 are inferior in surface hardness, heat resistance and rigidity because the amount of component (A-1) in the polycarbonate copolymer is less than the claimed range. Comparative Example 4 is inferior in impact resistance because the amount of component (A-1) in the polycarbonate copolymer is larger than the claimed range. Comparative Example 5 does not contain the component (A-3) in the polycarbonate copolymer and the amount of the component (A-2) is larger than the scope of claims, so the impact resistance and heat resistance are inferior to those of Examples. . Comparative Example 6 does not contain component (A-2) in the polycarbonate copolymer and contains more component (A-3) than the scope of claims, and thus is inferior in surface hardness and rigidity to those of Examples.

The resin composition and molded article of the present invention can be used for mobile phones, liquid crystal televisions, speakers, portable game machines, housings and interior panels of electric/electronic/OA equipment typified by laptop computers, door handles, steering wheels, car audio equipment, etc. It can be used for automobile interior parts such as car navigation frames and shift knobs, automobile exterior parts such as roof spoilers and window garnishes, furniture, and musical instruments.

Claims (10)

(A) as main structural units, (A-1) a structural unit (A-1) represented by the following formula (1), (A-2) a structural unit (A-2) represented by the following formula (2) ) and (A-3) composed of a structural unit (A-3) represented by the following formula (3), wherein the proportion of the structural unit (A-1) in all structural units is 5 to 15 mol%, and the structural unit ( 95 to 60 parts by weight of a polycarbonate copolymer (component A) having a proportion of A-2) of 20 to 60 mol% and a proportion of the structural unit (A-3) of 25 to 75 mol% ; (B) a styrene resin ( Component B) 5 to 40 parts by weight and (C) 0 to 10 parts by weight of an impact modifier (Component C) other than Component B with respect to a total of 100 parts by weight of Components A and B. .

(In formula (1), R ¹ and R ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 9 carbon atoms which may contain an aromatic group, or a halogen atom.)

(In formula (2), R ³ and R ⁴ are each independently an alkyl group having 1 to 6 carbon atoms or a halogen atom. X is a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted is an alkylidene group, a sulfur atom or an oxygen atom.)

(In formula (3), W represents a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkylidene group, a sulfur atom or an oxygen atom.) R ¹ and R ² in formula (1) are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ³ and R ⁴ in formula (2) are each independently having 1 to 6 carbon atoms. 6 alkyl group, X is a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted alkylidene group having 1 to 10 carbon atoms, W in formula (3) is a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkylidene group having 1 to 10 carbon atoms. 3. The polycarbonate resin composition according to claim 1, wherein the polycarbonate copolymer has a glass transition temperature of 140 to 160.degree. 4. The polycarbonate resin composition according to any one of claims 1 to 3, wherein the polycarbonate copolymer has a viscosity average molecular weight of 15,000 to 40,000. 5. The polycarbonate resin composition according to any one of claims 1 to 4, wherein the structural unit (A-1) is a structural unit derived from 9,9-bis(4-hydroxy-3-methylphenyl)fluorene. 6. The polycarbonate resin composition according to any one of claims 1 to 5, wherein the structural unit (A-2) is a structural unit derived from 2,2-bis(4-hydroxy-3-methylphenyl)propane. 7. The polycarbonate resin composition according to any one of claims 1 to 6, wherein the structural unit (A-3) is a structural unit derived from 2,2-bis(4-hydroxyphenyl)propane. 8. The polycarbonate resin according to any one of claims 1 to 7 , wherein component C is a rubber-modified resin selected from the group consisting of butadiene-based, acrylic-based and silicone-based resins, or an impact modifier containing one or more of these copolymers. Composition. A molded article obtained by molding the polycarbonate resin composition according to any one of claims 1 to 8 . Automotive interior and exterior parts using the molded product of claim 9 .