JP4861086B2 - Aromatic polycarbonate resin composition - Google Patents

Description

  The present invention relates to an aromatic polycarbonate resin composition containing a fluidity improver, a surface improver, and an inorganic filler, and more specifically, mechanical strength, heat resistance, dimensional stability, fluidity, appearance, and coating film. It is related with the aromatic polycarbonate resin composition excellent in all the adhesiveness of, and the resin molded object formed by shape | molding this.

  Aromatic polycarbonate resins are widely used in many fields as resins having excellent heat resistance, impact resistance, transparency and the like. Among them, the polycarbonate resin composition reinforced with inorganic fillers such as glass fiber, carbon fiber, wollastonite, mica and talc shows various excellent performances such as dimensional stability, mechanical strength, and heat resistance. Widely used in industrial fields such as office automation equipment and electrical and electronic parts.

  A polycarbonate resin composition reinforced with an inorganic filler has such excellent dimensional stability and mechanical strength, but has low fluidity and makes it difficult to form a thin molded product. In addition, the inorganic filler may be raised on the surface of the molded product, not only deteriorating the appearance of the molded product, but also when coated, there is a problem that the coating film is easily peeled off. There have been significant restrictions on the use of electronic cameras such as digital cameras, portable terminal barrels, and housings, where appearance and paintability are important.

  As a method for improving appearance defects and coating film adhesion, which are disadvantages of such a polycarbonate resin composition, a resin composition in which a glass-based filler and a polycarbonate oligomer are blended with a polycarbonate resin has been proposed (see, for example, Patent Document 1). .

  In addition, fluidity and appearance of molded products are improved by blending a fluidity improver such as thermoplastic polyurethane, triphenyl phosphate, or polycaprolactone resin with a specific structure into a polycarbonate resin composition containing glass fibers. A method has been proposed (see, for example, Patent Documents 2 to 4).

  Furthermore, by blending an engineering plastics such as polycarbonate resin with a copolymer comprising an aromatic vinyl monomer unit and a (meth) acrylic acid ester monomer unit having an ester group having a phenyl group, A method for improving fluidity and chemical resistance without impairing the properties has been proposed (see, for example, Patent Document 5).

JP 60-4550 A JP-A-6-41415 Japanese Patent Laid-Open No. 7-3140 JP 63-6051 A WO2005 / 030819

  However, the method described in Patent Document 1 has a problem that mechanical strength and load deflection temperature are insufficient because a large amount of polycarbonate oligomer is blended in order to obtain fluidity suitable for thin-wall molding.

  In addition, in the methods described in Patent Documents 2 to 4, although the fluidity of the resin composition and the appearance of the resin molded body are improved, the mechanical strength is lowered, and furthermore, the thermal stability of the fluidity improver used is reduced. Since it is low, there has been a problem that the fluidity improver decomposes during molding and adhesion to the mold (mold deposit) occurs.

  In particular, this mold deposit has a higher molding temperature in recent years, especially due to the thinning of parts, in addition to the increase in frequency of continuous molding over a long period of time, like resin molding in the actual chemical industry. It has become an increasingly serious problem.

  Furthermore, in the method described in Patent Document 5, no examination has been made on the adhesiveness (paintability) of the coating film to the surface of the obtained resin molded body, and it still remains insufficient. According to experiments conducted by the present inventors, a polycarbonate resin, an aromatic vinyl monomer unit and a copolymer comprising a (meth) acrylic acid ester monomer unit having an ester group having a phenyl group described in Patent Document 5. In the resin molding which shape | molds the resin composition which consists only of a polymer and an inorganic filler, even if it applied the surface, the new subject that a coating film peeled easily was discovered.

  The object of the present invention is to have fluidity suitable for molding a thin-walled molded product without impairing the dimensional stability, mechanical strength, heat resistance, etc. of the polycarbonate resin composition containing an inorganic filler, And it is providing the aromatic polycarbonate resin composition used as the resin molding excellent in the external appearance and the adhesiveness of the coating film.

  In order to solve the above-mentioned problems, the present inventors have made intensive efforts. As a result, the aromatic polycarbonate resin contains a specific copolymer, an aromatic polycarbonate oligomer, and an inorganic filler. It has been found that by using an inorganic filler in combination, it has fluidity particularly suitable for molding a thin molded article. Furthermore, the present inventors have found that a resin molded body obtained by molding this resin composition is excellent in both appearance and coating film adhesion, and completed the present invention.

  That is, the gist of the present invention is that the aromatic polycarbonate resin (A) is 70 to 92% by weight, the aromatic vinyl monomer unit (b1) and the (meth) acrylic acid ester monomer unit (b2) in which the ester group has an aromatic ring. From 2 to 20% by weight of the copolymer (B) and an aromatic polycarbonate oligomer (C) having an average degree of polymerization of 2 to 15 of the structural unit represented by the following general formula [I] The present invention relates to an aromatic polycarbonate resin composition containing 10 to 100 parts by weight of an inorganic filler (D) with respect to 100 parts by weight of the resulting resin composition, and a resin molded body formed by molding the same.

（式中、Ｒは炭素数１〜１０の直鎖、分岐鎖または環状のアルキリデン基、アリール置換アルキリデン基、アリーレンジアルキリデン基、酸素原子、硫黄原子、カルボニル基、またはスルホニル基を示し、Ｒ_１ 〜Ｒ_４ は各々同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素数１〜４のアルキル基、またはアルケニル基を示す。）

Wherein R represents a linear, branched or cyclic alkylidene group having 1 to 10 carbon atoms, an aryl-substituted alkylidene group, an arylene alkylidene group, an oxygen atom, a sulfur atom, a carbonyl group, or a sulfonyl group, and R ₁ -R ₄ may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkenyl group.

  The aromatic polycarbonate resin composition of the present invention maintains excellent properties such as dimensional stability, mechanical strength, heat resistance, etc., and is excellent in fluidity. Is good, and has the characteristic of simultaneously producing the effect of excellent adhesion of the coating film. The resin composition of the present invention makes use of such properties, and in particular, is a resin member that is required to be thin and have high strength, specifically, for example, a main body housing such as a camera or a digital camera, a lens barrel housing, It can be suitably used as a part or housing for a mobile phone, a notebook computer, a video camera, a copy machine, a facsimile, or the like. In particular, it can be suitably used for digital cameras, portable terminal housings, lens barrels, and the like that are required to be light and thin.

  Hereinafter, the present invention will be described in more detail. In the present specification, the “group” of various compounds may have a substituent without departing from the gist of the present invention.

[1] Aromatic polycarbonate resin (A)
The aromatic polycarbonate resin (A) used in the present invention (hereinafter sometimes referred to as component A) is not particularly limited, and any conventionally known aromatic polycarbonate resin can be used. Specifically, for example, a linear or branched thermoplastic aromatic polycarbonate polymer or copolymer obtained by reacting an aromatic dihydroxy compound and a carbonate precursor, or a small amount of a polyhydroxy compound or the like together therewith. It is a coalescence.

  The production method of the aromatic polycarbonate resin (A) used in the present invention is not limited, and any conventionally known method can be used. Specific examples include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer.

  Examples of the aromatic dihydroxy compound used as a raw material for the aromatic polycarbonate resin include 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A) and 2,2-bis (3,5-dibromo-4-hydroxy). Phenyl) propane (= tetrabromobisphenol A), bis (4-hydroxyphenyl) methane, 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-bromo-4-hydroxy) Phenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) 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-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxyphenyl) -1,1,1 -Trichloropropane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexachloropropane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3 Bis (hydroxyaryl) alkanes exemplified by 3,3-hexafluoropropane and the like;

  Exemplified by 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, etc. Bis (hydroxyaryl) cycloalkanes; cardostructure-containing bisphenols exemplified by 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene and the like ;

  Dihydroxy diaryl ethers exemplified by 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether and the like; 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy-3, Dihydroxydiaryl sulfides exemplified by 3′-dimethyldiphenyl sulfide and the like;

  Dihydroxydiaryl sulfoxides exemplified by 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide, etc .; 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxy- Dihydroxydiaryl sulfones exemplified by 3,3′-dimethyldiphenylsulfone; hydroquinone, resorcin, 4,4′-dihydroxydiphenyl and the like.

  Among these, bis (4-hydroxyphenyl) alkanes are preferable, and 2,2-bis (4-hydroxyphenyl) propane [= bisphenol A] is particularly preferable from the viewpoint of impact resistance. These aromatic dihydroxy compounds may be used alone or in combination of two or more.

  Carbonate precursors to be reacted with aromatic dihydroxy compounds include carbonyl halides, carbonate esters, haloformates, and the like. 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. These carbonate precursors may also be used alone or in combination of two or more.

  The aromatic polycarbonate resin (A) used in the present invention may be a branched aromatic polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound. Specific examples of the trifunctional or higher polyfunctional aromatic compound include phloroglucin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2. , 4,6-tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3,1,3,5-tri (4-hydroxyphenyl) Polyhydroxy compounds exemplified by benzene, 1,1,1-tri (4-hydroxyphenyl) ethane and the like; 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chloroisatin 5,7-dichloroisatin, 5-bromoisatin and the like.

  Of these, 1,1,1-tri (4-hydroxyphenyl) ethane is preferred. The polyfunctional aromatic compound can be used by substituting a part of the aromatic dihydroxy compound, and the amount used can be appropriately selected and determined, but is 0.01% relative to the aromatic dihydroxy compound. It is preferable that it is 10 mol%, and it is especially preferable that it is 0.1-2 mol%.

  Next, a method for producing an aromatic polycarbonate resin will be described. First, the interfacial polymerization method will be described. In this production method, the reaction is usually carried out in the presence of an organic solvent inert to the reaction and an aqueous alkaline solution while maintaining the pH at 9 or higher. First, an aromatic dihydroxy compound and, if necessary, a molecular weight adjusting agent (terminal terminator) and an antioxidant for preventing the aromatic dihydroxy compound are reacted with phosgene.

  Next, an aromatic polycarbonate is obtained by adding a polymerization catalyst such as a tertiary amine or a quaternary ammonium salt and performing interfacial polymerization. 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, several minutes (for example, 10 minutes) to several hours (for example, 6 hours).

  Here, examples of the organic solvent inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, 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 compounds having a monovalent phenolic hydroxyl group. 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 50 to 0.5 mol, more preferably 30 to 1 mol, per 100 mol of the aromatic dihydroxy compound.

  Polymerization catalysts include tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine and pyridine: quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium chloride Etc.

  Next, the melt transesterification method will be described. This production method is based on, for example, a transesterification reaction between a carbonic acid diester and an aromatic dihydroxy compound. Examples of the carbonic acid diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate and di-tert-butyl carbonate, and substituted diphenyl carbonates such as diphenyl carbonate and ditolyl carbonate. Among them, diphenyl carbonate or substituted diphenyl carbonate is preferable as the carbonic acid diester, and diphenyl carbonate is particularly preferable.

  Generally, in the melt transesterification method, an aromatic polycarbonate having a desired molecular weight and terminal hydroxyl group amount is obtained by adjusting the mixing ratio of the carbonic acid diester and the aromatic dihydroxy compound or adjusting the degree of vacuum during the reaction. Can do. As a more aggressive method, an adjustment method in which a terminal terminator is added separately during the reaction is also well known.

  Examples of the terminal terminator include monohydric phenols, monovalent carboxylic acids, and carbonic acid diesters. The amount of terminal hydroxyl groups has a great influence on the thermal stability, hydrolysis stability, color tone and the like of the product aromatic polycarbonate, and therefore may be selected and determined as appropriate depending on the application. In order to give practical physical properties, it is usually 1000 ppm or less, and preferably 700 ppm or less.

  When the aromatic polycarbonate resin used in the present invention is produced by a transesterification method, the amount of terminal hydroxyl groups is preferably 100 ppm or more. By setting the terminal hydroxyl group amount to 100 ppm or more, a decrease in molecular weight can be suppressed, and the color tone can be improved. Such an aromatic polycarbonate resin may be produced using an equimolar amount or more of a carbonic acid diester with respect to 1 mol of the aromatic dihydroxy compound, and among these, 1.01 to 1.3 mol is preferably used.

  In the melt transesterification method, a transesterification catalyst is usually used. As the transesterification catalyst, any conventionally known catalyst can be used, and is not particularly limited, but among them, an alkali metal compound and / or an alkaline earth metal compound is preferable. In addition, a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound may be used in combination.

  As conditions for the melt transesterification reaction, the reaction temperature is usually 100 to 320 ° C., the pressure is finally 2 mmHg or less, and the polycondensation reaction is performed while removing by-products such as aromatic hydroxy compounds. The method of performing is mentioned. This reaction may be carried out batchwise or continuously. Among these, it is preferable to carry out in a continuous manner in consideration of the stability of the resin composition of the present invention.

  The catalyst deactivator used in the melt transesterification method is not particularly limited as long as it is a compound that neutralizes the catalyst. Specifically, for example, a sulfur-containing acidic compound or a derivative thereof is preferably used. Usually, the amount of the catalyst deactivator used is preferably 0.5 to 10 equivalents, more preferably 1 to 5 equivalents, with respect to the alkali metal contained in the transesterification catalyst. Further, the concentration of the catalyst deactivator in the finally obtained aromatic polycarbonate resin is preferably 1 to 100 ppm, and more preferably 1 to 20 ppm.

  The molecular weight of the aromatic polycarbonate resin (A) used in the present invention is preferably 10000 to 25000 in terms of viscosity average molecular weight [Mv] converted from the solution viscosity. By setting the viscosity average molecular weight of the aromatic polycarbonate resin (A) to 10,000 or more, the mechanical strength tends to be further improved, and it is more preferable when used for applications requiring high mechanical strength. On the other hand, when the viscosity average molecular weight is 25000 or less, the fluidity is improved and the molding process becomes easy.

  Among them, the viscosity average molecular weight is preferably 11000 to 23000, and particularly preferably 12000 to 22000. In the present invention, two or more types of aromatic polycarbonate resins having different viscosity average molecular weights may be used. If the aromatic polycarbonate resin mixture has such a viscosity average molecular weight, of course, the viscosity average molecular weight is within the above preferred range. An aromatic polycarbonate resin that is outside may be mixed and used.

Here, the viscosity average molecular weight [Mv] is obtained by using methylene chloride as a solvent and obtaining an intrinsic viscosity [η] (unit: dl / g) at a temperature of 20 ° C. using an Ubbelohde viscometer. , Η = 1.23 × 10 ⁻⁴ M ^0.83 . The intrinsic viscosity [η] is a value calculated from the following equation by measuring the specific viscosity [η _sp ] at each solution concentration [C] (g / dl).

  Further, as the aromatic polycarbonate resin (A) used in the present invention, not only virgin raw materials but also aromatic polycarbonate resins regenerated from used products, so-called material recycled aromatic polycarbonate resins may be used. Used products include optical recording media such as optical disks, light guide plates, vehicle window glass, vehicle headlamp lenses, windshields, and other vehicle transparent members, water bottle containers, glasses lenses, soundproof walls, glass windows, waves, etc. A building member such as a plate is preferred. Also, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used. The regenerated aromatic polycarbonate resin is preferably 80% by weight or less of (A), more preferably 50% by weight or less.

[2] Copolymer (B)
In the present invention, for the purpose of improving fluidity, a copolymer comprising an aromatic vinyl monomer unit (b1) and a (meth) acrylic acid ester monomer unit (b2) in which the ester group has an aromatic ring ( B) (hereinafter simply referred to as “copolymer (B)” or B component). The content of each monomer unit constituting the copolymer (B) used in the present invention is arbitrary, but usually 0.5 to 99.5% by weight of the aromatic vinyl monomer unit (b1), and an ester group The (meth) acrylic acid ester monomer unit (b2) in which is a (substituted) aromatic ring is 0.5 to 99.5% by weight. Further, it may contain 0 to 40% by weight of other monomer units (b3) as necessary.

  Specific examples of the aromatic vinyl monomer unit (b1) include styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene, p-methoxystyrene, o-methoxystyrene, 2, Examples include 4-dimethylstyrene, chlorostyrene, promostyrene, and vinyl toluene. These may be used alone or in combination of two or more at any ratio. Among these, styrene, α-methylstyrene, and pt-butylstyrene are preferable.

  The content of the aromatic vinyl monomer unit (b1) in the copolymer (B) is 0.5 to 99.5% by weight. The content is preferably 10 to 98% by weight, more preferably 20 to 96% by weight, further 50 to 93% by weight, and particularly preferably 75 to 90% by weight. When the aromatic vinyl monomer unit (b1) exceeds 99.5% by weight, the compatibility may be insufficient, delamination may occur, and the appearance and mechanical strength may be impaired. Conversely, less than 0.5% by weight However, fluidity and chemical resistance tend to decrease.

  As the (meth) acrylic acid ester monomer unit (b2) (hereinafter sometimes simply referred to as “b2”) in which the ester group is an aromatic ring or an aromatic ring having a substituent, the aromatic ring is a phenyl group. Specifically, for example, phenyl (meth) acrylate, 4-t-butylphenyl (meth) acrylate, bromophenyl (meth) acrylate, dibromophenyl (meth) acrylate, monochlorophenyl (meth) acrylate, etc. Is mentioned. These may be used alone or in combination of two or more at any ratio. Of these, phenyl (meth) acrylate is preferred.

  The present invention is also characterized by containing a specific amount of the content of (b2) in the copolymer (B). The content of (b2) in the copolymer (B) is usually 0.5 to 99.5% by weight. If the amount of (b2) is too small, the compatibility with the aromatic polycarbonate resin is insufficient. For example, even if a coating film is provided on the surface of the resin molded article, it may cause deterioration of the appearance and mechanical strength. is there. On the other hand, if the amount is too large, the fluidity of the resin component in the present invention tends to decrease.

  This is because the amount of (b2) is too large, the compatibility between the aromatic polycarbonate resin (A) and the copolymer (B) proceeds excessively, and the copolymer (B) becomes compatible at the molecular level. This is probably because the properties of the aromatic polycarbonate resin (A) having a lower fluidity are expressed and the fluidity improving effect is lowered.

  Therefore, the content of (b2) is preferably 2 to 90% by weight, more preferably 4 to 80% by weight, more preferably 7 to 50% by weight, and particularly preferably 10 to 25% by weight.

  The copolymer (B) used in the present invention can be copolymerized with an aromatic vinyl monomer or a (meth) acrylic acid ester monomer having a phenyl group or a substituted phenyl group, as long as the characteristics are not impaired. The other monomer unit (b3) may be contained in an amount of 0 to 40% by weight.

  Examples of the other monomer unit (b3) include α, β-unsaturated monomers. Specific examples include (meth) acrylates having a reactive functional group such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and lauryl (meth) acrylate, vinyl benzoate, and vinyl acetate. . These may be used alone or in combination of two or more at any ratio. In the copolymer (B), if there are too many other monomer units (b3), the fluidity and chemical resistance tend to be lowered, so the content in the copolymer (B) Usually, it is preferably 30% by weight or less, more preferably 20% by weight or less, further 10% by weight or less, and particularly preferably 5% by weight or less.

  Although the weight average molecular weight (Mw) of the copolymer (b) used for this invention is arbitrary, it is 5000-150,000 normally. If the weight average molecular weight is too small, appearance defects such as mold deposits, fish eyes, and silver are likely to occur. On the other hand, if the weight average molecular weight is too large, the effect of improving fluidity is reduced. Therefore, the weight average molecular weight is preferably 10,000 to 140000, more preferably 15,000 to 130,000, more preferably 30000 to 120,000, and particularly preferably 40000 to 100,000.

  The production method of the copolymer (B) is arbitrary, and may be produced using any conventionally known polymerization method. Specific examples include an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, and a bulk polymerization method. When the emulsion polymerization method is used, the residual salt may cause thermal decomposition of the aromatic polycarbonate resin. Therefore, whether the residual salt is recovered by salting out coagulation using a carboxylate emulsifier or the like. It is preferable to use a nonionic anionic emulsifier such as phosphate ester and salt out and coagulate with a calcium acetate salt. As the copolymer (B) used in the present invention, for example, those described in International Application Publication No. WO2005 / 030819 can be used.

[3] Aromatic polycarbonate oligomer (C)
In the present invention, the aromatic polycarbonate oligomer (C) (hereinafter sometimes referred to as C component) has the following general formula [I] as a structural unit (monomer unit), and the average polymerization degree of this monomer unit is 2 ~ 15 oligomers.

（式中、Ｒは炭素数１〜１０の直鎖、分岐鎖または環状のアルキリデン基、アリール置換アルキリデン基、アリーレンジアルキリデン基、酸素原子、硫黄原子、カルボニル基、またはスルホニル基を示し、Ｒ_１ 〜Ｒ_４ は各々同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素数１〜４のアルキル基、またはアルケニル基を示す。）

Wherein R represents a linear, branched or cyclic alkylidene group having 1 to 10 carbon atoms, an aryl-substituted alkylidene group, an arylene alkylidene group, an oxygen atom, a sulfur atom, a carbonyl group, or a sulfonyl group, and R ₁ -R ₄ may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkenyl group.

  The method for producing the aromatic polycarbonate oligomer (C) used in the present invention is not particularly limited, but usually, using the same dihydric phenols and carbonate precursor as those used for producing the aromatic polycarbonate resin described above, It can be produced in the same manner as in the production method of the aromatic polycarbonate resin (A) except that a larger amount of the molecular weight modifier or the terminal terminator is used than that used in the production of a normal aromatic polycarbonate resin.

  Examples of the molecular weight regulator or the terminal terminator include a compound having a monovalent phenolic hydroxyl group and a compound having an aromatic carboxylic acid group. Specific examples include phenol, pt-butylphenol, aliphatic carboxylic acid chloride, aliphatic carboxylic acid, aromatic carboxylic acid, and hydroxybenzoic acid. These may be used alone or in combination of two or more at any ratio.

  The average degree of polymerization of the aromatic polycarbonate oligomer (C) used in the present invention is 2 to 15. In addition, the aromatic polycarbonate oligomer used in the present invention may be one kind or a mixture of two or more kinds within the average polymerization degree range. When the average degree of polymerization is less than 2, it becomes easy to bleed out from the resin molded body during molding of the resin composition of the present invention. Conversely, when the average degree of polymerization exceeds 15, the aromatic polycarbonate is formed on the surface of the resin molded body. Since it is difficult for the oligomers to collect, the inorganic filler (D) is exposed on the surface of the molded article, and satisfactory coating adhesion cannot be obtained. Therefore, the average degree of polymerization of the aromatic polycarbonate oligomer is preferably 4-12.

[4] Inorganic filler (D)
The inorganic filler (D) (hereinafter sometimes referred to as D component) in the present invention is a solid inorganic compound. The solid form (appearance) is not particularly limited, and may be any of a spherical shape, a plate shape, a needle shape, a fiber shape, an amorphous shape, and the like.

  The spherical shape includes not only a spherical shape but also an elliptical cross section or a substantially oval shape to some extent. Preferably, the aspect ratio (the longest diameter of the spherical body / the minimum diameter of the spherical body) ) Is in the range of 0.5 to 2 and is preferably close to 1. The plate-like form is one having an aspect ratio (the length of the longest side of the plate-like surface of the plate-like powder / the thickness of the plate-like body) in the range of 2 to 100.

  What has an acicular shape means that the length is less than 500 μm and the aspect ratio (particle length / particle diameter) is in the range of 2-20. The fibrous form has a length of 500 μm or more. The appearance of the inorganic filler can be easily determined by, for example, an electron micrograph. Among these, as the inorganic filler (D) used in the present invention, it is preferable to use a plate-like or fibrous inorganic filler in order to improve the dimensional stability and rigidity of the finally obtained resin composition.

  Among the inorganic fillers (D) used in the present invention, as the plate-like filler (d1), specifically, for example, magnesium silicate such as talc, kaolinite, clay, mica, graphite, sericite, montmorillonite, plate-like Examples thereof include calcium carbonate, plate-like alumina, plate-like boehmite, and glass flakes. Examples of the fibrous filler (d2) include glass fiber, carbon fiber, metal fiber, mineral fiber, and ceramic whisker. Examples of the acicular filler (d3) include calcium silicate such as wollastonite, moss heidi, zonotlite, calcium titanate, aluminum borate, acicular calcium carbonate, acicular titanium oxide, tetrapot type zinc oxide, acicular boehmite and the like. Can be mentioned.

The average particle diameter of the plate-like filler (d1) may be appropriately selected and determined according to the physical properties to be imparted to the resin molded body of the present invention, and specifically, for example, 0.1 to 300 μm. . If the average particle size is too small, the reinforcing effect tends to be insufficient, while if it is too large, the appearance of the resin molded product and the impact resistance may be lowered. Therefore, the average particle diameter of the plate filler (d1) is preferably 0.3 to 100 μm, particularly preferably 0.5 to 50 μm. Here the average particle diameter refers to the D ₅₀ as measured in the liquid phase precipitation method using X-ray transmission. An apparatus that can perform such measurement includes a Sedigraph particle size analyzer (manufactured by Micromeritics Instruments, model: model 5100).

  The average fiber length and average fiber diameter of the fibrous filler (d2) may be appropriately selected and determined according to the physical properties to be imparted to the resin molded body of the present invention. Specifically, for example, the average fiber length is 500 μm to 6 mm, and the average fiber diameter is 1 to 20 μm. If the average fiber length is too long, an appearance defect may occur due to jumping out of the fiber during coating on the surface of the resin molded body. On the other hand, even if it is too short, the aspect ratio becomes small, so that sufficient strength cannot be obtained. Further, if the average fiber diameter is too thin, the reinforcing effect is insufficient, and conversely, if the fiber is too thick, the appearance of the resin molded body is lowered. Therefore, the fiber diameter is preferably 2 to 17 μm, particularly 3 to 15 μm. preferable. In addition, the fiber diameter of a fibrous filler can be easily measured with an electron micrograph.

  The acicular filler (d3) preferably has an average fiber length of 1 μm or more and less than 500 μm, more preferably 10 to 300 μm, and particularly preferably 20 to 200 μm. Moreover, it is preferable that the average fiber diameter is 1-10 micrometers. Moreover, you may use what processed the acicular filler into various forms, such as cross shape and plate shape.

  The inorganic filler (D) used in the present invention is preferably treated with a sizing agent or a surface treatment agent in order to improve interfacial adhesion with the aromatic polycarbonate resin (A) or the copolymer (B). . Specific examples of such sizing agents and surface treatment agents include functional compounds such as epoxy compounds, acrylic compounds, isocyanate compounds, silane compounds, and titanate compounds. These compounds may be used after being subjected to surface treatment or convergence treatment of the inorganic filler (D) in advance, or may be added simultaneously during material preparation, for example, mixing and kneading. Although the usage-amount of a surface treating agent should just select and determine suitably, it is preferable that it is 0-10 weight% normally with respect to an inorganic filler (D), and 0.05-5 weight% especially.

  The aromatic polycarbonate resin composition of the present invention comprises the above-described aromatic polycarbonate resin (A) 70 to 92% by weight, (meth) acrylic acid ester having an aromatic vinyl monomer unit (b2) and an ester group having a phenyl group. An inorganic filler (100 parts by weight of a resin composition comprising 2 to 20% by weight of a copolymer (B) composed of a monomer unit (b2) and 2 to 10% by weight of an aromatic polycarbonate oligomer (C). It is a resin composition containing 10 to 100 parts by weight of D).

  In 100 parts by weight of the resin composition composed of the A component to the C component, if the content of the A component is less than 70% by weight, the mechanical strength and the load deflection temperature of the resin composition are lowered. Fluidity decreases. If the B component is less than 2% by weight, the fluidity is inferior, whereas if it exceeds 20% by weight, the impact resistance and load deflection temperature are lowered. On the other hand, if the C component is less than 2% by weight, the paintability is lowered. Conversely, if it exceeds 10% by weight, the mechanical strength and the load deflection temperature are lowered.

  In the polycarbonate resin resin composition of this invention, D component is contained 10-100 weight part with respect to 100 weight part of resin compositions which consist of A component-C component mentioned above. If the D component is less than 10 parts by weight, the dimensional stability and rigidity will be insufficient. Conversely, if it exceeds 100 parts by weight, the paintability, appearance and fluidity will decrease.

  Among them, the component D is preferably composed of a plate-like filler (d1), a fibrous filler (d2), and a needle-like filler (d3). Particularly, the plate-like filler (d1) and the fibrous filler ( It is preferable to consist of d2). When the inorganic fillers having different shapes are used, the weight ratio of each is preferably 1.5 ≦ d1 / (d2 + d3) ≦ 10, and in particular, the plate-like filler (d1) and the fibrous filler. The weight ratio (d1 / d2) of (d2) is preferably 1.5 ≦ d1 / d2 ≦ 10. When d1 / d2 is 1.5 or more, the dimensional stability tends to be improved, and when it is 10 or less, the mechanical strength can be improved.

  In the polycarbonate resin composition of the present invention, if necessary, other resins (E) and various resin additives (in addition to the above-mentioned components A to D), as long as the object of the present invention is not impaired. F) may be included.

  Specific examples of other resins (E) include polyolefin resins such as polyethylene resins and polypropylene resins, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, polyphenylene ether resins, polyphenylene sulfide resins, and polysulfone resins. , Polymethacrylate resin, phenol resin, epoxy resin and the like.

  As the resin additive (F), any conventionally known antioxidant, heat stabilizer, impact resistance improver, weather resistance improver, release agent, antistatic agent, dye / pigment, antifogging agent, lubricant -An antiblocking agent, a plasticizer, a dispersing agent, a fungicide, etc. are mentioned. These may be used alone or in combination of two or more at any ratio.

  The polycarbonate resin composition of the present invention can be produced by a known method for producing a thermoplastic resin composition. Specifically, the above-described components A to D, and additive components to be included as necessary are mixed in advance using various mixers such as a tumbler and a Henschel mixer, and then mixed with a Banbury mixer, A resin composition can be produced by melt kneading using a kneading machine, brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader or the like.

  Also, the resin composition can be produced without mixing each component in advance, or by mixing only a part of the components and supplying them to an extruder using a feeder and melt-kneading them. Furthermore, when the D component is an inorganic filler that is easily destroyed by melt-kneading, a method is also available in which a component other than the D component is collectively introduced into the upstream portion, and the D component is added after the middle stream and melt-kneaded with the resin component. It is preferable from the viewpoint of the mechanical strength of the composition.

  The polycarbonate resin composition of the present invention is used as a resin material for production (molding) of various products (molded products). The molding method is not particularly limited, and any conventionally known thermoplastic resin molding method can be used. Specifically, for example, a general injection molding method, an ultra-high speed injection molding method, an injection compression molding method, a two-color molding method, a hollow molding method such as gas assist, a molding method using a heat insulating mold, a rapid heating mold Molding method, foam molding (including supercritical fluid), insert molding, in-mold coating (IMC) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding Law.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In the following examples and comparative examples, the blending amount represents parts by weight.

  Each raw material used in Examples and Comparative Examples is as follows.

<A component>
A-1 Polycarbonate Iupilon S-3000F Mv21000 manufactured by Mitsubishi Gas Chemical Company, Inc.

A-2 Polycarbonate Iupilon H-4000F Mv16000 made by Mitsubishi Gas Chemical Company

A-3 Polycarbonate Iupilon H-7000F Mv14000 manufactured by Mitsubishi Gas Chemical Company, Inc.

<B component>
B-1 TP-003 made by Mitsubishi Rayon Co., Ltd. Styrene / phenyl methacrylate (85/15 wt%) copolymer Mw50000

B-2 Polycaprolactone Placcel H1P manufactured by Daicel Chemical Industries, Ltd. Number average molecular weight 10,000.

<C component>
C Polycarbonate oligomer made by Mitsubishi Gas Chemical Company Iupilon AL-071 (7-mer oligomer)

<D component>
D-1-a Glass flake REFG301 made by Nippon Sheet Glass Co., Ltd. Average major axis 150μm, thickness 5μm

D-1-b Phosphorous graphite manufactured by Nishimura Graphite Co., Ltd. PB90 Average particle size 14μm

D-2 Glass fiber manufactured by Nippon Electric Glass Co., Ltd. ECS03T571 Average diameter 13μm, length 2mm

D-3 Kawai Lime Industry Co., Ltd. Needle Boehmite BMI Average particle size 4-6 μm, aspect ratio 30-50

<E component>
E mold release agent manufactured by KOKUNIS JAPAN Co., Ltd. pentaerythritol tetrastearate VPG861

(Examples 1-8, Comparative Examples 1-5)
[Pellet making]
After uniformly mixing the resin composition blended in the components and proportions shown in Table 1 with a tumbler mixer, the resin composition was used at a cylinder temperature of 260 ° C. using a twin screw extruder (30 mmφ) having two feed ports. The plate-like filler and the fibrous filler were fed into the kneader from the main hopper and melted and kneaded to produce pellets.

[Mechanical properties evaluation]
Using the obtained pellets, an ISO multipurpose test piece was prepared under the conditions of a cylinder temperature of 280 ° C. and a mold temperature of 110 ° C. using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., Cycap M-2, mold clamping force 75T). Manufactured, flexural modulus (measured by a three-point bending test by the ISO 178 bending test method), and Charpy impact strength (measured in a non-notched manner by ISO 179. Note that the case where the test machine capacity was not broken at 50 J was designated as NB. ) Was measured. The results are shown in Tables 1 and 2.

[Fluidity evaluation]
Using the same pellet molding machine as the above-mentioned mechanical property evaluation test piece production, the obtained pellets were converted into a bar flow mold having a width of 20 mm and a thickness of 0.5 mm under the conditions of a cylinder temperature of 300 ° C and a mold temperature of 100 ° C Was used to measure the flow length. The results are shown in Tables 1 and 2.

[Evaluation of molding shrinkage and peeling properties]
The obtained pellets were molded into an 80 mm × 40 mm × 3 mm plate using the above-described injection molding machine under conditions of a cylinder temperature of 300 ° C. and a mold temperature of 100 ° C. The mold shrinkage after the plate was conditioned at 23 ° C. and 50% RH for 48 hours was measured. The measurement was performed in the flow direction (parallel) and the vertical direction of the resin from the gate. In addition, a cellophane tape was applied to the surface of the plate after humidity control, and the surface state after peeling was observed. If the peeling was not observed on the surface of the resin molded body, OK was indicated, and if no peeling was observed, NG was indicated. It was written in 1 and 2.

Claims (4)

A copolymer comprising 70 to 92% by weight of an aromatic polycarbonate resin (A), an aromatic vinyl monomer unit (b1), and a (meth) acrylic acid ester monomer unit (b2) having an aromatic ring in the ester group 100 parts by weight of a resin composition comprising (B) 2 to 20% by weight and 2 to 10% by weight of an aromatic polycarbonate oligomer (C) having an average degree of polymerization of 2 to 15 of the structural unit represented by the following general formula [I] An aromatic polycarbonate resin composition containing 10 to 100 parts by weight of an inorganic filler (D).

(Wherein R represents a linear, branched or cyclic alkylidene group having 1 to 10 carbon atoms, an aryl-substituted alkylidene group, an arylene alkylidene group, an oxygen atom, a sulfur atom, a carbonyl group, or a sulfonyl group; _{1 to} R ₄ may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkenyl group.   The inorganic filler (D) includes two or more selected from the group consisting of a plate-like inorganic filler (d1), a fibrous inorganic filler (d2), and an acicular inorganic filler (d3). The aromatic polycarbonate resin composition according to claim 1.   The weight ratio of the plate-like inorganic filler (d1), the fibrous inorganic filler (d2), and the needle-like inorganic filler (d3) is 1.5 ≦ d1 / (d2 + d3) ≦ 10, The aromatic polycarbonate resin composition according to claim 2. The resin molding formed by shape | molding the aromatic polycarbonate resin composition in any one of Claims 1 thru | or 3.