JP5301799B2 - Slidable resin composition and molded product formed therefrom - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a slidable polycarbonate resin composition that exhibits excellent sliding properties without detriment to impact strengths, heat resistance and dimensional stability which are properties inherent in the polycarbonate resin without using a fluorine-containing sliding agent, and to provide a molded article formed of the same. <P>SOLUTION: The flame-retardant aromatic polycarbonate resin composition comprises 100 pts.wt. of (A) an aromatic polycarbonate resin, 3.0-7.0 pts.wt. of (B) an acrylic-modified polyorganosiloxane (component B), 4.0-9.0 pts.wt. of (C) an organic phosphorous compound-based flame retardant (component C) and 0.01-1 pt.wt. of (D) a fluorine-containing drip inhibitor (component D), where the acrylic-modified polyorganosiloxane (component B) is one obtained by graft-copolymerizing (B2) a mixture (component B2) composed of 70-100 wt.% of (meth)acrylic ester (component B2-1) and 0-30 wt.% of other copolymerizable monomers (component B2-2) onto (B1) polyorganosiloxane (component B1) represented by general formula (1) in a weight ratio of the component B2/component B1 of 5/95 to 95/5. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a polycarbonate resin composition having excellent sliding characteristics and a molded product formed therefrom. More specifically, a flame-retardant polycarbonate resin composition excellent in sliding characteristics and surface appearance and molding formed therefrom without impairing the original properties of the polycarbonate resin such as impact resistance, heat resistance, dimensional stability and flame retardancy Related to goods.

  Aromatic polycarbonate resin has many excellent material properties, so various products are made using processing methods that are simple and highly productive, such as injection molding, and are used in a wide range of industrial fields. Yes. In particular, in the OA equipment and electrical / electronic equipment fields, aromatic polycarbonate resins with excellent dimensional accuracy, mechanical strength, and heat resistance are used for sliding members such as gears in order to reduce size and weight and reduce the number of parts. Is increasing. However, when the polycarbonate resin is used alone, the slidability is unsatisfactory, and improvement of the slidability is required.

  For example, it has been reported that a resin such as polytetrafluoroethylene, polyolefin, polyamide, or polyester is added to a polycarbonate resin as a sliding property improving material (see Patent Documents 1 and 2). However, when polytetrafluoroethylene resin is blended with polycarbonate resin, there arises a problem that molding processability and impact strength are lowered. In addition, halogen compounds such as polytetrafluoroethylene resin generate hydrofluoric acid when molded products containing them are incinerated as waste, and are currently refrained from being used like organic halogen flame retardants. ing. Due to the increasing demand for environmentally friendly materials, there is a demand for sliding materials that do not use fluorine-based sliding agents such as polytetrafluoroethylene resin.

  In addition, sliding agents such as polyolefin, polyamide, and polyester can not only obtain sliding characteristics equivalent to fluorine-based sliding agents, but polycarbonate resins such as mechanical strength, heat resistance, and flame resistance are inherently possessed. The characteristics are damaged.

  On the other hand, it has also been proposed to add silicone oil, which is a chemically and physically stable lubricant, to polycarbonate resin (see Patent Document 3). However, since the silicone oil on the surface of the molded product oozes out and is consumed for a short time, although it exhibits excellent slidability in the initial stage, the long-term slidability is insufficient and the surface is sticky. There were also problems such as, and it was not satisfactory. In addition, in order to obtain sufficient slidability, it is necessary to add a large amount of silicone oil. As a result, gloss unevenness due to phase separation of silicone oil is likely to occur on the surface of the molded product, which is practically satisfactory. It wasn't going.

Japanese Unexamined Patent Publication No. 63-213555 Japanese Patent Laid-Open No. 4-136065 Japanese Patent Publication No. 36-7641

  Under such circumstances, the present invention has excellent sliding characteristics and surface appearance without using a fluorine-based sliding agent, and has the impact properties, heat resistance, and dimensional stability that are inherent characteristics of polycarbonate resin. Another object of the present invention is to provide a slidable polycarbonate resin composition that does not impair flame retardancy and a molded article formed thereby.

  As a result of intensive studies to achieve the above-mentioned object, the present inventor has obtained (meth) acrylic acid ester and other copolymerizable monomers, preferably only (meth) acrylic acid ester, on the aromatic polycarbonate resin. A resin composition comprising a specific amount of grafted polyorganosiloxane, organophosphorus compound flame retardant, and fluorine-containing anti-dripping agent is excellent in impact strength, heat resistance, slidability, and surface appearance. The present invention has been found. That is, the present invention relates to (B) acrylic-modified polyorganosiloxane (component B) 3.0 to 7.0 parts by weight, (C) an organophosphorus compound-based flame retardant (100) relative to 100 parts by weight of the aromatic polycarbonate resin (A). C component) 4.0 to 9.0 parts by weight, and (D) fluorine-containing anti-dripping agent (D component) 0.01 to 1 part by weight. The acrylic-modified polyorganosiloxane (component B) is ( B1) Polyorganosiloxane (B1 component) represented by the following general formula (1) is added to (B2) (meth) acrylic acid ester (B2-1 component) 70% to 100% by weight and other copolymerizable units. Graft copolymerization of a mixture (B2 component) consisting of 0% to 30% by weight (B2-2 component) in a ratio of 5/95 to 95/5 expressed as a weight ratio of B2 component / B1 component. Acrylic modified polyolga There is provided a flame retardant aromatic polycarbonate resin composition which is a siloxane.

［式中、Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立に炭素数１〜２０の炭化水素基、又は炭素数１〜２０のハロゲン化炭化水素基を表し、Ｙはビニル基、アリル基、およびγ−（メタ）アクリロキシプロピル基からなる群より選択されるラジカル反応性基、又は−ＳＨ基を持つ有機基を表す。Ｘ^１及びＸ^２は、それぞれ独立に水素原子、炭素数１〜４のアルキル基又は−ＳｉＲ^４Ｒ^５Ｒ^６（Ｒ^４、Ｒ^５は独立に炭素数１〜２０の炭化水素基、又は炭素数１〜２０のハロゲン化炭化水素基を表し、Ｒ^６は炭素数１〜２０の炭化水素基、炭素数１〜２０のハロゲン化炭化水素基、又はビニル基、アリル基、およびγ−（メタ）アクリロキシプロピル基からなる群より選択されるラジカル反応性基又は−ＳＨ基を持つ有機基を表す。）で示される基を表し、ｍは１０，０００以下の正の整数、ｎは１〜５００の整数であり、シロキサン鎖には分岐があってもよい。］

[Wherein R ¹ , R ² and R ³ each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms, Y represents a vinyl group, an allyl group, And a radical reactive group selected from the group consisting of γ- (meth) acryloxypropyl groups, or an organic group having an —SH group. X ¹ and X ² are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or —SiR ⁴ R ⁵ R ⁶ (R ⁴ and R ⁵ are independently a hydrocarbon group having 1 to 20 carbon atoms, or carbon Represents a halogenated hydrocarbon group having 1 to 20 carbon atoms, and R ⁶ represents a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or a vinyl group, an allyl group, and γ- (meta ) Represents a radical-reactive group selected from the group consisting of acryloxypropyl groups or an organic group having an —SH group.), M is a positive integer of 10,000 or less, and n is 1 to 1 It is an integer of 500, and the siloxane chain may be branched. ]

Details of the present invention will be described below.
(Component A: aromatic polycarbonate resin)
The aromatic polycarbonate resin used as the component A in the present invention is obtained by reacting a dihydric phenol and a carbonate precursor. Examples of the reaction method include an interfacial polymerization 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.

  Representative examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl). ) Propane (commonly called bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl)- 1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) Pentane, 4,4 ′-(p-phenylenediisopropylidene) diphenol, 4,4 ′-(m-phenylenediisopropyl Pyridene) diphenol, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ester, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) Examples include fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. A preferred dihydric phenol is bis (4-hydroxyphenyl) alkane, and bisphenol A is particularly preferred from the viewpoint of impact resistance, and is widely used.

In the present invention, in addition to bisphenol A-based polycarbonate, which is a general-purpose polycarbonate, it is possible to use a special polycarbonate produced using other dihydric phenols as the A component.
For example, as part or all of the dihydric phenol component, 4,4 ′-(m-phenylenediisopropylidene) diphenol (hereinafter sometimes abbreviated as “BPM”), 1,1-bis (4-hydroxy) Phenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as “Bis-TMC”), 9,9-bis (4-hydroxyphenyl) Polycarbonate (homopolymer or copolymer) using fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as “BCF”) has dimensions due to water absorption. It is suitable for applications where the demands for change and shape stability are particularly severe. These dihydric phenols other than BPA are preferably used in an amount of 5 mol% or more, particularly 10 mol% or more of the entire dihydric phenol component constituting the polycarbonate.

In particular, when high rigidity and better hydrolysis resistance are required, it is particularly preferable that the component A constituting the resin composition is a copolymerized polycarbonate of the following (1) to (3). is there.
(1) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and BCF Of 20 to 80 mol% (more preferably 25 to 60 mol%, more preferably 35 to 55 mol%).
(2) BPA is 10 to 95 mol% (more preferably 50 to 90 mol%, more preferably 60 to 85 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and BCF Is 5 to 90 mol% (more preferably 10 to 50 mol%, more preferably 15 to 40 mol%).
(3) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and Bis -Copolymer polycarbonate in which TMC is 20 to 80 mol% (more preferably 25 to 60 mol%, still more preferably 35 to 55 mol%).

  These special polycarbonates may be used alone or in combination of two or more. Moreover, these can also be mixed and used for the bisphenol A type polycarbonate generally used.

  The production method and characteristics of these special polycarbonates are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580. ing.

Of the various polycarbonates described above, those having a water absorption and Tg (glass transition temperature) adjusted within the following ranges by adjusting the copolymer composition, etc. have good hydrolysis resistance of the polymer itself, and Since it is remarkably excellent in low warpage after molding, it is particularly suitable in a field where form stability is required.
(I) polycarbonate having a water absorption of 0.05 to 0.15%, preferably 0.06 to 0.13% and Tg of 120 to 180 ° C, or (ii) Tg of 160 to 250 ° C, Polycarbonate which is preferably 170 to 230 ° C. and has a water absorption of 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27%.

  Here, the water absorption of the polycarbonate is a value obtained by measuring the moisture content after being immersed in water at 23 ° C. for 24 hours in accordance with ISO 62-1980 using a disc-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm. is there. Moreover, Tg (glass transition temperature) is a value calculated | required by the differential scanning calorimeter (DSC) measurement based on JISK7121.

  As the carbonate precursor, carbonyl halide, carbonic acid diester, haloformate or the like is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.

  In producing the aromatic polycarbonate resin by the interfacial polymerization method using the dihydric phenol and the carbonate precursor, a catalyst, a terminal terminator, and an antioxidant for preventing the dihydric phenol from being oxidized as necessary. Etc. may be used. The aromatic polycarbonate resin of the present invention is a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, a polyester copolymerized with an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. Carbonate resins, copolymerized polycarbonate resins copolymerized with bifunctional alcohols (including alicyclics), and polyester carbonate resins copolymerized with such bifunctional carboxylic acids and difunctional alcohols are included. Moreover, the mixture which mixed 2 or more types of the obtained aromatic polycarbonate resin may be sufficient.

  Since the branched polycarbonate resin can synergistically improve the drip prevention ability of the flame retardant aromatic polycarbonate resin composition of the present invention, its use is preferable. Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin include phloroglucin, phloroglucid, or 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, 4- {4- [ Trisphenol such as 1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol, tetra (4-hydride) Loxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acids Among them, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable. 1-Tris (4-hydroxyphenyl) ethane is preferred.

The ratio of the polyfunctional compound in the branched polycarbonate resin is 0.001 to 1 mol%, preferably 0.005 to 0.9 mol%, more preferably 0.01 to 0.8 mol in the total amount of the aromatic polycarbonate resin. The mol%, particularly preferably 0.05 to 0.4 mol%. In particular, in the case of the melt transesterification method, a branched structure may occur as a side reaction. The amount of the branched structure is also preferably in the above-mentioned range in the total amount of the aromatic polycarbonate resin. Such a branched structure amount can be calculated by ¹ H-NMR measurement.

The aliphatic bifunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Examples of the aliphatic difunctional carboxylic acid include sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, icosanedioic acid and other straight-chain saturated aliphatic dicarboxylic acids, and cyclohexanedicarboxylic acid. Preferred are alicyclic dicarboxylic acids such as As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecane dimethanol.
Further, a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units can also be used.

The reaction forms such as interfacial polymerization, melt transesterification, solid phase transesterification of carbonate prepolymer, and ring-opening polymerization of cyclic carbonate compounds, which are methods for producing the polycarbonate resin of the present invention, are various documents and patent publications. This is a well-known method.
The details of the reaction formats other than those described above are also well known in books and patent publications.

In producing the flame retardant aromatic polycarbonate resin composition of the present invention, the viscosity average molecular weight (M) of the aromatic polycarbonate resin is not particularly limited, but is preferably 1 × 10 ^{4 to} 5 × 10 ⁴ , more preferably ^{1.4 × 10 4 ~3 × 10 4} , more preferably from ^{1.4 × 10 4 ~2.4 × 10 4} .

Aromatic polycarbonate resins having a viscosity average molecular weight of less than 1 × 10 ⁴ may not provide practically expected impact resistance or the like, and may not provide sufficient drip-preventing ability, so that flame retardancy is not obtained. Inferior. On the other hand, a resin composition obtained from an aromatic polycarbonate resin having a viscosity average molecular weight exceeding 5 × 10 ⁴ is inferior in versatility in that it is inferior in fluidity during injection molding. In addition, the characteristics of the present invention may not be fully utilized due to an increase in the molding temperature.

The aromatic polycarbonate resin may be obtained by mixing those having a viscosity average molecular weight outside the above range. In particular, an aromatic polycarbonate resin having a viscosity average molecular weight exceeding the above range (5 × 10 ⁴ ) can further improve the drip prevention ability synergistically by improving the entropy elasticity of the resin. This improvement effect is even better than the branched polycarbonate. As a more suitable aspect, the A component is an aromatic polycarbonate resin (A-3-1 component) having a viscosity average molecular weight of 7 × 10 ^{4 to} 3 × 10 ⁵ , and a viscosity average molecular weight of 1 × 10 ^{4 to} 3 × 10 ⁴ . An aromatic polycarbonate resin (A3 component) consisting of an aromatic polycarbonate resin (A-3-2 component) and having a viscosity average molecular weight of 1.6 × 10 ^{4 to} 3.5 × 10 ⁴ (hereinafter, “high molecular weight component”) It is also possible to use "containing aromatic polycarbonate resin".

In such a high molecular weight component-containing aromatic polycarbonate resin (A3 component), the molecular weight of the A-3-1 component is preferably 7 × 10 ⁴ to 2 × 10 ⁵ , more preferably 8 × 10 ⁴ to 2 × 10 ⁵ , It is preferably 1 × 10 ⁵ to 2 × 10 ⁵ , particularly preferably 1 × 10 ^{5 to} 1.6 × 10 ⁵ . The molecular weight of the A-3-2 component is preferably 1 × 10 ^{4 to} 1.5 × 10 ⁴ , more preferably 1.1 × 10 ^{4 to} 2.4 × 10 ⁴ , and still more preferably 1.2 × 10 ^4. to 2.4 × 10 ^4, particularly preferably ^{1.2 × 10 4 ~2.3 × 10 4} .

  The high molecular weight component-containing aromatic polycarbonate resin (A3 component) can be obtained by mixing the A-3-1 component and the A-3-2 component at various ratios and adjusting them so as to satisfy a predetermined molecular weight range. . Preferably, in A100 component 100 weight%, A-3-1 component is 2 to 40 weight%, More preferably, A3-1 component is 3 to 30 weight%, More preferably, A- The 3-1 component is 4 to 20% by weight, and the A-3-1 component is particularly preferably 5 to 20% by weight.

  In addition, as a method for preparing the A-3 component, (1) a method in which the A-3-1 component and the A-3-2 component are independently polymerized and mixed, and (2) JP-A-5-306336. The method of producing an aromatic polycarbonate resin showing a plurality of polymer peaks in a molecular weight distribution chart by GPC method, represented by the method shown in Japanese Patent Publication No. Gazette, in the same system, the aromatic polycarbonate resin of the present invention A- A method of producing so as to satisfy the conditions of one component, and (3) an aromatic polycarbonate resin obtained by such a production method (production method of (2)), a separately produced A-3-1 component and / or Examples thereof include a method of mixing the A-3-2 component.

The viscosity average molecular weight referred to in the present invention is first determined by using an Ostwald viscometer from a solution in which 0.7 g of aromatic polycarbonate is dissolved in 100 ml of methylene chloride at 20 ° C. with a specific viscosity (η _SP ) calculated by the following formula. ,
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
The viscosity average molecular weight M 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 M ^0.83
c = 0.7

Moreover, the calculation method of the said viscosity average molecular weight is applied also to the viscosity average molecular weight measurement of the resin composition of this invention and the molded article shape | molded from this resin composition. That is, in the present invention, these viscosity average molecular weights are obtained by inserting the specific viscosity (η _sp ) obtained at 20 ° C. from a solution obtained by dissolving 0.7 g of a molded product in 100 ml of methylene chloride into the above formula.

(B component: acrylic modified polyorganosiloxane formed by graft copolymerization of (meth) acrylic acid ester and other copolymerizable monomers)
Component B in the present invention is a graft copolymer of (meth) acrylic acid ester and other copolymerizable monomer, preferably (meth) acrylic acid ester, onto polyorganosiloxane represented by the following general formula (1). An acrylic-modified polyorganosiloxane obtained by polymerization.

［式中、Ｒ^１，Ｒ^２，及びＲ^３はそれぞれ独立にメチル基、エチル基、プロピル基、ブチル基等のアルキル基、フェニル基、トリル基、キシリル基、ナフチル基等のアリール基で例示される炭素数１〜２０の炭化水素基、又はこれらの基の炭素原子に結合した水素原子の少なくとも一つをハロゲン原子で置換した基を表す。Ｙはビニル基、アリル基、およびγ−メタクリロキシプロピル基からなる群より選択されるラジカル反応性基、又はγ−メルカプトプロピル基で例示される−ＳＨ基を持つ有機基を表す。Ｘ^１及びＸ^２は独立に水素原子、メチル基、エチル基、プロピル基、ブチル基等の炭素数１〜４のアルキル基、又は−ＳｉＲ^４Ｒ^５Ｒ^６（Ｒ^４、及びＲ^５は独立にＲ^１〜Ｒ^３で例示された炭素数１〜２０の炭化水素基、炭素数１〜２０のハロゲン化炭化水素基を表し、Ｒ^６は炭素数１〜２０の炭化水素基、炭素数１〜２０のハロゲン化炭化水素基、又はＹで例示されたラジカル反応性基もしくは−ＳＨ基を持つ有機基を表す。）で示されるトリオルガノシリル基を表す。ｍは１０，０００以下の正の整数を表し、ｎは１〜５００の整数を表す。なお、１分子中で、Ｒ^１〜Ｒ^６、Ｙの各々は同一でも異なっていてもよい。］

[Wherein R ¹ , R ² and R ³ are each independently an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, or an aryl group such as a phenyl group, a tolyl group, a xylyl group or a naphthyl group. Represents a group obtained by substituting at least one of the hydrogen atoms bonded to the carbon atom of these groups with a halogen atom. Y represents a radical reactive group selected from the group consisting of a vinyl group, an allyl group, and a γ-methacryloxypropyl group, or an organic group having an —SH group exemplified by a γ-mercaptopropyl group. X ¹ and X ² are independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, or —SiR ⁴ R ⁵ R ⁶ (R ⁴ and R ⁵ are independently Represents a hydrocarbon group having 1 to 20 carbon atoms and a halogenated hydrocarbon group having 1 to 20 carbon atoms exemplified by R ^{1 to} R ³ , and R ⁶ is a hydrocarbon group having 1 to 20 carbon atoms and 1 carbon atom. Represents a halogenated hydrocarbon group of -20, or an organic group having a radical-reactive group or -SH group exemplified as Y). m represents a positive integer of 10,000 or less, and n represents an integer of 1 to 500. In each molecule, each of R ^{1 to} R ⁶ and Y may be the same or different. ]

  Such an acrylic-modified polyorganosiloxane can be produced by a known method. For example, it can be produced by using a linear or cyclic low molecular weight polyorganosiloxane or alkoxysilane having the above group and combining hydrolysis, polymerization, and equilibration means. Hydrolysis, polymerization, and equilibration can be performed in a state dispersed in water by a known technique.

  Moreover, (meth) acrylic acid ester (B2-1 component) is acrylic acid or methacrylic acid alkyl ester, hydroxyalkyl ester, alkoxyalkyl ester, etc., specifically, methyl acrylate, ethyl acrylate, acrylic Isopropyl acid, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, n-octyl acrylate, 2-hydroxyethyl acrylate, 2-methoxy acrylate Acrylic esters such as ethyl, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate Le, methacrylic acid n-lauryl, 2-hydroxyethyl methacrylate can be exemplified methacrylic acid esters such as methacrylic acid-2-ethoxyethyl. These can be used alone or in combination of two or more, and methyl methacrylate and 2-hydroxyethyl methacrylate are particularly preferred.

  Further, as other monomers (B2-2 component) copolymerizable with (meth) acrylic acid ester, styrene compounds such as styrene, vinyltoluene and α-methylstyrene, acrylonitrile and methacrylonitrile are used. Unsaturated nitriles, halogenated olefins such as vinyl chloride and vinylidene chloride, vinyl esters such as vinyl acetate and vinyl propionate, unsaturated amides such as acrylamide, methacrylamide and N-methylolacrylamide, acrylic acid, methacrylic acid, anhydrous In addition to monomers having one double bond such as unsaturated carboxylic acid such as maleic acid, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, allyl methacrylate, triallyl cyanurate ,bird It can be mentioned polyunsaturated monomers such as Lil isocyanurate as a representative example. Two or more of these can be used.

  The content of these other copolymerizable monomers is 30% by weight or less, preferably 28% by weight or less, more preferably 26% by weight or less, where the total amount with the (meth) acrylic acid ester is 100% by weight. It is.

  Graft copolymerization can be performed by a known technique. For example, graft copolymerization can be performed by emulsifying and dispersing polyorganosiloxane and (meth) acrylic acid ester or a mixture of this and other monomers in water and polymerizing in the presence of a radical polymerization initiator. The emulsifier and radical polymerization initiator used in this method may be those known for emulsion polymerization. After completion of the polymerization, a graft copolymer can be obtained by salting out, filtering, washing with water and drying. In this emulsion graft copolymerization, if the polyorganosiloxane is produced in a state of being dispersed in water as described above, the resulting polyorganosiloxane emulsion can be used as it is as a raw material for graft copolymerization.

  The acrylic modified polyorganosiloxane of the present invention is a mixture of (meth) acrylic acid ester and other copolymerizable monomer (B2 component) with respect to polyorganosiloxane (B1 component), and the weight of B2 component / B1 component. Expressed by graft copolymerization at a ratio of 5/95 to 95/5, preferably 10/90 to 80/20, more preferably 15/85 to 70/30, particularly preferably 20/80 to 60/40. is there. In this weight ratio, if the (meth) acrylic acid ester and the other copolymerizable monomer are less than 5, the compatibility with the polycarbonate is insufficient and the mechanical strength and the appearance of the molded product are difficult. If it exceeds, slidability is insufficient.

  A polyorganosiloxane obtained by graft copolymerization of such (meth) acrylic acid ester and other copolymerizable monomers is sold, for example, under the trade name “Charine” by Nissin Chemical Co., Ltd. It can also be easily obtained from the market.

  The content of the acrylic modified polyorganosiloxane (component B) obtained by graft copolymerization of (meth) acrylic acid ester and other copolymerizable monomers is 3.0 with respect to 100 parts by weight of the polycarbonate resin (component A). To 7.0 parts by weight, preferably 3.2 to 6.8 parts by weight, and more preferably 3.4 to 6.6 parts by weight. If the proportion of the acrylic-modified polyorganosiloxane (component B) is less than 3.0 parts by weight, the effect of improving the slidability is unsatisfactory, and if it exceeds 7.0 parts by weight, the appearance deteriorates due to excessive surface migration, Moreover, there is a possibility that the mechanical characteristics may be lowered, which is not preferable.

(C component: organophosphorus compound flame retardant)
Examples of the organic phosphorus compound-based flame retardant used as the component C of the present invention include red phosphorus and organic phosphate ester-based flame retardants. Among them, an organic phosphate ester flame retardant is preferable, and one or more phosphate esters represented by the following formula (2) are particularly preferable.

（式中のＸは、ハイドロキノン、レゾルシノール、ビス（４−ヒドロキシジフェニル）メタン、ビスフェノールＡ、ジヒドロキシジフェニル、ジヒドロキシナフタレン、ビス（４−ヒドロキシフェニル）スルホン、ビス（４−ヒドロキシフェニル）ケトン、およびビス（４−ヒドロキシフェニル）サルファイドからなる群より選ばれるジヒドロキシ化合物より誘導される二価フェノール残基であり、ｊ、ｋ、ｌ及びｍはそれぞれ独立して０または１であり、ｎは０〜５の整数であり（ただし、重合度ｎの異なるリン酸エステルの混合物の場合はｎはその平均値を表す。）、Ｒ^１、Ｒ^２、Ｒ^３、およびＲ^４はそれぞれ独立してハロゲン原子で置換されてもよいフェノール、クレゾール、キシレノール、イソプロピルフェノール、ブチルフェノール、およびｐ−クミルフェノールからなる群より選ばれるアリール基より誘導される一価のフェノール残基である。）

(X in the formula is hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, and bis ( 4-hydroxyphenyl) a dihydric phenol residue derived from a dihydroxy compound selected from the group consisting of sulfides, j, k, l and m are each independently 0 or 1, and n is 0-5 It is an integer (however, in the case of a mixture of phosphate esters having different polymerization degrees n, n represents the average value), and R ¹ , R ² , R ³ , and R ⁴ are each independently substituted with a halogen atom. Phenol, cresol, xylenol, isopropylphenol, butylphenol And a monovalent phenol residue derived from an aryl group selected from the group consisting of diol and p-cumylphenol.)

Among these, preferably, X in the above formula includes a divalent phenol residue derived from a dihydroxy compound selected from the group consisting of hydroquinone, resorcinol, and bisphenol A, and j, k, l and m are Each is 1, n is an integer of 0 to 3 (however, in the case of a mixture of phosphate esters having different polymerization degrees n, n represents an average value thereof), R ¹ , R ² , R ³ , and R ⁴ is a monovalent phenol residue derived from an aryl group selected from the group consisting of phenol, cresol, and xylenol each independently substituted with one or more halogen atoms. Furthermore, particularly preferably, X is a divalent phenol residue derived from resorcinol, j, k, l and m are each 1, n is 0 or 1, and R ¹ , R ² , R ³ and R ⁴ are each independently a monovalent phenol residue derived from phenol or xylenol. Among these organic phosphates, triphenyl phosphate is preferable as a phosphate compound, and resorcinol bis (dixylenyl phosphate) and bisphenol A bis (diphenyl phosphate) are preferable as phosphate oligomers because of excellent hydrolysis resistance. More preferred are resorcinol bis (dixylenyl phosphate) and bisphenol A bis (diphenyl phosphate) from the viewpoint of heat resistance.

  The content of the organophosphorus compound-based flame retardant (C component) of the present invention is 4.0 to 9.0 parts by weight, preferably 4.8 to 8.4 parts by weight with respect to 100 parts by weight of the A component. More preferably, it is 5.2 to 8.0 parts by weight. Such a suitable composition ratio provides an aromatic polycarbonate resin composition having good flame retardancy. If the organophosphorus compound-based flame retardant is too less than the above range, it is difficult to obtain a flame retardant effect, and if it is more than the above range, the limit PV value due to a decrease in physical properties and a decrease in heat resistance. May cause a decrease in

(D component: fluorine-containing anti-drip agent)
Examples of the fluorine-containing anti-drip agent used as the component D of the present invention include polytetrafluoroethylene having fibril forming ability.
Polytetrafluoroethylene (PTFE) having the ability to form fibrils has a very high molecular weight, and exhibits a tendency to bind PTFE to each other by an external action such as shearing force to form a fiber. The molecular weight is 1 million to 10 million, more preferably 2 million to 9 million in the number average molecular weight determined from the standard specific gravity. Such PTFE can be used in solid form or in the form of an aqueous dispersion. In addition, PTFE having such fibril-forming ability can improve the dispersibility in the resin, and it is also possible to use a PTFE mixture in a mixed form with other resins in order to obtain better flame retardancy and mechanical properties. is there. Examples of commercially available PTFE having such fibril forming ability include Teflon (registered trademark) 6J from Mitsui DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500 and F-201L from Daikin Chemical Industries, Ltd. Commercially available aqueous dispersions of PTFE include: Fullon AD-1, AD-936 manufactured by Asahi IC Fluoropolymers Co., Ltd. Fullon D-1, D-2 manufactured by Daikin Industries, Ltd., Mitsui DuPont Fluoro A typical example is Teflon (registered trademark) 30J manufactured by Chemical Corporation.

As a mixed form of PTFE, (1) a method in which an aqueous dispersion of PTFE and an aqueous dispersion or solution of an organic polymer are mixed and co-precipitated to obtain a co-aggregated mixture (Japanese Patent Application Laid-Open No. 60-258263; (Method described in JP-A-63-154744), (2) A method of mixing an aqueous dispersion of PTFE and dried organic polymer particles (method described in JP-A-4-272957), (3) A method in which an aqueous dispersion of PTFE and an organic polymer particle solution are uniformly mixed, and each medium is simultaneously removed from the mixture (described in JP-A-06-220210, JP-A-08-188653, etc.) And (4) a method of polymerizing monomers forming an organic polymer in an aqueous dispersion of PTFE (a method described in JP-A-9-95583), and (5) A method in which an aqueous dispersion of TFE and an organic polymer dispersion are uniformly mixed, and then a vinyl monomer is further polymerized in the mixed dispersion, and then a mixture is obtained (described in JP-A-11-29679, etc.). Those obtained by (Method) can be used. Examples of commercially available PTFE in a mixed form include “Metablene A3000” (trade name) manufactured by Mitsubishi Rayon Co., Ltd. and “BLENDEX B449” (trade name) manufactured by GE Specialty Chemicals.

  As a ratio of PTFE in the mixed form, 1 to 60% by weight of PTFE is preferable in 100% by weight of the PTFE mixture, and more preferably 5 to 55% by weight. When the ratio of PTFE is within such a range, good dispersibility of PTFE can be achieved.

  The content of the fluorine-containing anti-dripping agent (D component) of the present invention is 0.01 to 1 part by weight, preferably 0.03 to 0.8 part by weight, more preferably 0, per 100 parts by weight of the component A. 0.05 to 0.6 parts by weight. If the D component is less than 0.01 parts by weight, it is difficult to obtain a flame retardant effect.

(Other additives)
In the polycarbonate resin composition of the present invention, various additives, reinforcing agents, and the like that are usually blended in a polycarbonate resin can be blended.

(Phosphorus stabilizer)
The aromatic polycarbonate resin composition of the present invention preferably further contains a phosphorus stabilizer. Such phosphorus stabilizers improve thermal stability during production or molding, and improve mechanical properties, hue, and molding stability. Further, since there is a considerable amount of oxidative degradation in ultraviolet degradation, it has an auxiliary effect in suppressing such degradation. Examples of such phosphorus stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof.

  Specifically, as the phosphite compound, for example, triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl Phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, tris ( Diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylpheny) ) Phosphite, tris (2,6-di-tert-butylphenyl) phosphite, distearyl pentaerythritol 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 Phyto, bis (nonylphenyl) pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite, and the like.

  Further, as other phosphite compounds, those which react with dihydric phenols and have a cyclic structure can 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.

  Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Examples thereof include diisopropyl phosphate, and triphenyl phosphate and trimethyl phosphate are preferable.

  Examples of the phosphonite compound 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′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, 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, and tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, bis (Di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl)- More preferred is phenyl-phenylphosphonite. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted.

  Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

  The phosphorus stabilizers can be used alone or in combination of two or more. Among the phosphorus stabilizers, phosphite compounds or phosphonite compounds are preferable. 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.

(Hindered phenol stabilizer)
The aromatic polycarbonate resin composition of the present invention can further contain a hindered phenol-based stabilizer, and such inclusion is particularly effective in preventing dry heat deterioration. In addition, since the ultraviolet ray deterioration is accompanied by oxidative deterioration, it is effective in suppressing such deterioration. Examples of such hindered phenol stabilizers include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylfel). ) 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-butylphenol), 2,2-thio Ethylenebis- [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-butylphenyl) butane, 1,3,3 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-dimethylbenzyl) isocyanurate 1,3,5-tris 2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate and tetrakis [methylene-3- (3 ′, 5′-di- tert-butyl-4-hydroxyphenyl) propionate] methane and the like. All of these are readily available. The said hindered phenolic antioxidant can be used individually or in combination of 2 or more types.

  At least one stabilizer selected from phosphorus stabilizers and hindered phenol stabilizers is 0.001 to 1 part by weight, preferably 0.003 to 100 parts by weight of the aromatic polycarbonate resin (component A). 0.5 parts by weight, more preferably 0.005 to 0.1 parts by weight. When the amount of the stabilizer is less than the above range, it is difficult to obtain a good stabilizing effect. When the amount exceeds the above range, the physical properties of the composition may be deteriorated and the flame retardancy may be deteriorated.

(Reinforcing filler)
Various kinds of known fillers can be blended in the aromatic polycarbonate resin composition of the present invention as a reinforcing filler. Such fillers include, for example, talc, wollastonite, mica, clay, montmorillonite, smectite, kaolin, calcium carbonate, glass fiber, glass beads, glass balloon, glass milled fiber, glass flake, carbon fiber, carbon flake. , Carbon beads, carbon milled fibers, metal flakes, metal fibers, metal coated glass fibers, metal coated carbon fibers, metal coated glass flakes, silica, ceramic particles, ceramic fibers, ceramic balloons, graphite, aramid fibers, and various whiskers (titanium) Acid potassium whisker, aluminum borate whisker, basic magnesium sulfate, etc.). These reinforcing fillers may be used alone or in combination of two or more. The filler is preferably in the range of 1 to 50 parts by weight per 100 parts by weight of component A.

(White pigment for light reflection)
The aromatic polycarbonate resin of the present invention provides a resin composition having better characteristics even by blending a white pigment. As the white pigment, a titanium dioxide (particularly titanium dioxide treated with an organic surface treatment agent such as silicone) pigment is particularly preferred, and the proportion thereof is 1 to 30 parts by weight, more preferably 2 to 20 parts by weight per 100 parts by weight of component A. Is preferred.

(Radical generator)
The aromatic polycarbonate resin composition of the present invention can contain a radical generator. Preferred radical generators include 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, organic peroxides such as dicumyl peroxide, 2,3-dimethyl-2,3- Diphenylbutane (Dicumyl) and the like can be mentioned, and these are commercially available under the trade names such as Perhexin 25B, Parkmill D, and NOFMER BC manufactured by NOF Corporation. In particular, those that generate as little radicals as possible at the time of melt kneading and that generate stable radicals to some extent at the time of combustion are preferred, so 2,3-dimethyl-2,3-diphenylbutane (dicumyl) is more preferred as a radical generator. be able to. When flame retardancy is required, the flame retardancy can be further improved by such a radical generator. The ratio is 0.001-0.3 weight part with respect to 100 weight part of A component, More preferably, 0.01-0.1 weight part is preferable.

(Light stabilizer)
The polycarbonate resin composition of the present invention includes bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis. (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1 , 2,3,4-butanetetracarboxylate, poly {[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2, 2,6,6-tetramethylpiperidyl) imino] hexamethylene [(2,2,6,6-tetramethylpiperidyl) imino]}, and polymethylpropyl 3-oxy- [4- (2,2,6, - it may also include tetramethyl) piperidinyl] hindered amine light stabilizer represented by a siloxane.
The above light stabilizers may be used alone or in a mixture of two or more. The amount of the light stabilizer used is preferably 0.0005 to 3 parts by weight, more preferably 0.01 to 2 parts by weight, and 0.02 to 1 part by weight based on 100 parts by weight of the aromatic polycarbonate resin (component A). Further preferred.

(Other resins and elastomers)
In the aromatic polycarbonate resin composition of the present invention, other resins and elastomers can be used in a small proportion within a range in which the object of the present invention is not impaired.
Examples of such other resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polyethylene, and polypropylene. And other resins such as polyolefin resin, polystyrene resin, acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), polymethacrylate resin, phenol resin, and epoxy resin.

  As the elastomer, for example, isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, MBS (methyl methacrylate / sterene / butadiene) which is a core-shell type elastomer. Examples thereof include rubber and MAS (methyl methacrylate / acrylonitrile / styrene) rubber.

In addition, in the aromatic polycarbonate resin composition of the present invention, additives known per se can be blended in a small proportion for imparting various functions to the molded article and improving the characteristics. These additives are used in usual amounts as long as the object of the present invention is not impaired.
Examples of such additives include colorants (for example, pigments and dyes such as carbon black and titanium oxide), inorganic phosphors (for example, phosphors having aluminate as a base crystal), antistatic agents, flow modifiers, crystals. Nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (eg fine particle titanium oxide, fine particle zinc oxide), impact modifiers typified by graft rubber, infrared absorbers (heat ray absorbers), and photochromic agents Can be mentioned.

(Manufacture of polycarbonate resin composition)
Arbitrary methods are employ | adopted in order to manufacture the aromatic polycarbonate resin composition of this invention. For example, components A to D, and optionally other components are mixed thoroughly using premixing means such as a V-type blender, Henschel mixer, mechanochemical apparatus, and extrusion mixer, respectively. Examples thereof include granulation with a briquetting machine and the like, followed by melt kneading with a melt kneader typified by a vent type biaxial ruder, and pelletization with a device such as a pelletizer.
As a method for supplying each component to the melt kneader, (i) a method in which components A to D and other components are independently supplied to the melt kneader, and (ii) components A to D and other components An example is a method in which a part is premixed and then supplied to the melt kneader independently of the remaining components.

  As the extruder, one having a vent capable of degassing moisture in the raw material and volatile gas generated from the melt-kneaded resin can be preferably used. From the vent, a vacuum pump is preferably installed for efficiently discharging generated moisture and volatile gas to the outside of the extruder. It is also possible to remove a foreign substance from the resin composition by installing a screen for removing the foreign substance mixed in the extrusion raw material in the zone in front of the extruder die. Examples of such a screen include a wire mesh, a screen changer, a sintered metal plate (such as a disk filter), and the like. Examples of the melt kneader include a banbury mixer, a kneading roll, a single screw extruder, a multi-screw extruder having three or more axes, in addition to a twin screw extruder.

  The resin extruded as described above is directly cut into pellets, or after forming strands, the strands are cut with a pelletizer to be pelletized. When it is necessary to reduce the influence of external dust during pelletization, it is preferable to clean the atmosphere around the extruder. Although the shape of the obtained pellet can take general shapes, such as a cylinder, a prism, and a spherical shape, it is more preferably a cylinder. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and still more preferably 2 to 3.3 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and still more preferably 2.5 to 3.5 mm.

(Molding)
A molded article comprising the aromatic polycarbonate resin composition of the present invention can be usually obtained by injection molding the pellet. In such injection molding, not only ordinary molding methods but also injection compression molding, injection press molding, gas assist injection molding, foam molding (including a method of injecting a supercritical fluid), insert molding, in-mold coating molding, heat insulation Examples thereof include mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding. In addition, either a cold runner method or a hot runner method can be selected for molding.

  Moreover, according to this invention, a polycarbonate resin composition can be extrusion-molded and it can also be made into shapes, such as various profile extrusion molded articles, a sheet | seat, and a film. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can also be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. Further, the polycarbonate resin composition of the present invention can be formed into a molded product by rotational molding or blow molding.

(surface treatment)
Further, the molded article of the present invention can be subjected to various surface treatments. As the surface treatment, various surface treatments such as a hard coat, a water / oil repellent coat, a hydrophilic coat, an antistatic coat, an ultraviolet absorption coat, an infrared absorption coat, and metalizing (evaporation) can be performed. Examples of the surface treatment method include liquid deposition, vapor deposition, thermal spraying, and plating. As the vapor deposition method, either a physical vapor deposition method or a chemical vapor deposition method can be used. Examples of physical vapor deposition include vacuum vapor deposition, sputtering, and ion plating. Examples of the chemical vapor deposition (CVD) method include a thermal CVD method, a plasma CVD method, and a photo CVD method.

  The aromatic polycarbonate resin composition of the present invention has excellent sliding characteristics without using a fluorine-based sliding agent, and has impact strength, heat resistance, dimensional stability, and flame retardancy, which are inherent characteristics of polycarbonate resin. Therefore, it is useful for internal mechanism parts such as electric / electronic equipment and office equipment, which are particularly demanding for the environment, and its industrial usefulness is extremely large.

  The form of the present invention considered to be the best by the present inventor is a collection of the preferable ranges of the above requirements. For example, typical examples are described in the following examples. Of course, the present invention is not limited to these forms.

  The present invention will be further described below with reference to examples, but the present invention is not limited thereto. The following items were evaluated.

[Examples 1 to 5 and Comparative Examples 1 to 8]
The resin composition described in Table 1 was prepared as follows. Each component of the ratio of Table 1 was measured, it mixed uniformly using the tumbler, and this mixture was thrown into the extruder and preparation of the resin composition was performed. As the extruder, a vent type twin screw extruder (Kobe Steel Works KTX-30) having a diameter of 30 mmφ was used. Strands were extruded under conditions of cylinder temperature and die temperature of 280 ° C. and vent suction of 3000 Pa, cooled in a water bath, then cut into strands with a pelletizer, and pelletized. The obtained pellets were dried with a hot air circulation dryer at 120 ° C. for 6 hours, and a test piece was molded with an injection molding machine [Toshiba Machine Co., Ltd. IS150EN-5Y] at a cylinder temperature of 280 ° C. and a mold temperature of 70 ° C. Then, evaluation was performed by the following method.

(Evaluation method)
(1) Coefficient of dynamic friction A reciprocating friction and wear tester AFT-15M manufactured by Orientec Co., Ltd. was used as an evaluation device. A pin-shaped test piece (material: steel) having a spherical surface at the tip, in which a hemisphere having a diameter of 5 mmφ and a cylinder having a diameter of 5 mmφ and a length of 30 mmφ were combined at a circular cross section, was mounted on the fixed-side test piece holder. On the other hand, a flat test piece having a length of 150 mm, a width of 150 mm, and a thickness of 2 mm was prepared from the resin compositions of Examples and Comparative Examples (a gate is a fin gate having a width of 40 mm and a thickness of 1 mm from one end of the side) by injection molding. The part was cut into a length of 50 mm and a width of 100 mm, and the cut specimen was fixed on a pedestal that reciprocated. Load load in the state where the cylindrical axis direction of the pin-shaped test piece and the plane normal direction of the flat-plate test piece are parallel to the flat surface portion of the cutting test piece of the flat plate-shaped test piece. It contacted in the state which applied the load of 9.8N. In such a contact state, a capacitance connected to the pin-shaped test piece side by reciprocating 1,000 times a distance of 25 mm each way on a straight line in a plane at a rate of 2 seconds per reciprocation in an atmosphere of 23 ° C. and relative humidity 50% RH. The frictional force after 1000 operations was measured with a 49N load cell, and the dynamic friction coefficient was calculated from the relationship with the load.

(2) Limit PV value Cylindrical test pieces with an outer diameter of 25 mm and an inner diameter of 20 mm are molded, and a thrust friction wear test (cylindrical test piece is used with a friction tester [Flictron friction wear tester manufactured by Orientec Co., Ltd.] Under constant load, the end surface of the mating material was contacted and rotated). As the counterpart material, carbon steel for machine structure (S-45C) is used in a non-lubricated state, and the pressure load is 0 to 500 kg every 3 minutes under the condition of a sliding speed of 20 cm / sec (rotation speed: 167 rpm). The limit PV value was measured while changing in stages. The limit PV value here refers to a value obtained by multiplying the limit pressure load (P) and the sliding speed (V) at which the sliding surface of the material deforms (melts) due to frictional heat generation and breaks.

(3) Impact resistance According to ISO 179, the Charpy impact strength with a notch was measured.

(4) Heat resistance According to ISO 75-1 and 75-2, the deflection temperature under load was measured. The measurement load was 1.80 MPa.

(5) Flame retardancy Evaluation was performed by a vertical combustion test based on the UL standard 94 using a test piece having a thickness of 1.5 mm prepared according to the UL standard.

(6) Appearance A square plate having a width of 50 mm, a length of 80 mm, and a thickness of 2 mm was visually measured. ○ indicates that the surface appearance is good, x indicates that gloss unevenness is caused by phase separation on the surface of the molded product, or the acrylic modified polyorganosiloxane component is peeled off from the molded product surface during injection molding .

The raw materials used in Table 1 are as follows.
(A component)
PC-1: Aromatic polycarbonate resin
[L-1225WP manufactured by Teijin Chemicals Ltd., viscosity average molecular weight 22,400]
PC-2: Aromatic polycarbonate resin
[L-1225WX manufactured by Teijin Chemicals Ltd., viscosity average molecular weight 19,700]
(B component)
R-170: Acrylic modified polyorganosiloxane
[Nishin Chemical Industry Co., Ltd. Charine R-170, polydimethylsiloxane content 70 wt%]
(Other than B component)
PTFE: Polytetrafluoroethylene resin
[Lebron L-5, manufactured by Daikin Industries, Ltd., average particle size of about 7 μm]
(C component)
PX-200: Phosphate ester mainly composed of resornol bis [di (2,6-dimethylphenyl) phosphate]
[PX-200 manufactured by Daihachi Chemical Industry Co., Ltd.]
(D component)
FA500: polytetrafluoroethylene having fibril-forming ability
[Polyflon MP FA500 manufactured by Daikin Industries, Ltd.]
(Other ingredients)
IRX: Phosphite compound
[Irgafos 168 manufactured by Ciba Specialty Chemicals]

  From the comparison between Examples and Comparative Examples in Table 1, it can be seen that the aromatic polycarbonate resin composition of the present invention is excellent in sliding properties, impact resistance, heat resistance and flame retardancy.

Claims (5)

(B) Acrylic-modified polyorganosiloxane (component B) 3.0 to 7.0 parts by weight with respect to 100 parts by weight of aromatic polycarbonate resin (A), (C) Organophosphorus compound-based flame retardant (component C) 4 0.0 to 9.0 parts by weight, and (D) a fluorine-containing anti-dripping agent (component D) 0.01 to 1 part by weight, and the acrylic-modified polyorganosiloxane (component B) is (B1) The polyorganosiloxane represented by the formula (1) (component B1), (B2) (meth) acrylic acid ester (component B2-1) 70% by weight to 100% by weight and other copolymerizable monomers (B2) -2 component) Acrylic modified polyorgano prepared by graft copolymerization of a mixture (B2 component) consisting of 0 wt% to 30 wt% in a ratio of B2 component / B1 component at a ratio of 5/95 to 95/5 siloxane der Ri And flame retardant aromatic polycarbonate resin composition characterized by containing no silicone oil.

[Wherein R ¹ , R ² and R ³ each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms, Y represents a vinyl group, an allyl group, And a radical reactive group selected from the group consisting of γ- (meth) acryloxypropyl groups, or an organic group having an —SH group. X ¹ and X ² are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or —SiR ⁴ R ⁵ R ⁶ (R ⁴ and R ⁵ are independently a hydrocarbon group having 1 to 20 carbon atoms, or carbon Represents a halogenated hydrocarbon group having 1 to 20 carbon atoms, and R ⁶ represents a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or a vinyl group, an allyl group, and γ- (meta ) Represents a radical-reactive group selected from the group consisting of acryloxypropyl groups or an organic group having an —SH group.), M is a positive integer of 10,000 or less, and n is 1 to 1 It is an integer of 500, and the siloxane chain may be branched. ]   The flame retardant aromatic polycarbonate resin composition according to claim 1, wherein the B2-1 component is methyl methacrylate and / or 2-hydroxyethyl methacrylate.   The flame-retardant aromatic polycarbonate resin composition according to claim 1 or 2, wherein the weight ratio of B2 component / B1 component is 20/80 to 60/40. The flame retardant aromatic polycarbonate resin composition according to any one of claims 1 to 3, wherein the organic phosphorus compound-based flame retardant is a phosphoric acid ester represented by the following formula (2).

(X in the formula is hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, and bis ( 4-hydroxyphenyl) a dihydric phenol residue derived from a dihydroxy compound selected from the group consisting of sulfides, j, k, l and m are each independently 0 or 1, and n is 0-5 It is an integer (however, in the case of a mixture of phosphate esters having different polymerization degrees n, n represents the average value), and R ¹ , R ² , R ³ , and R ⁴ are each independently substituted with a halogen atom. Phenol, cresol, xylenol, isopropylphenol, butylphenol And a monovalent phenol residue derived from an aryl group selected from the group consisting of diol and p-cumylphenol.)   The molded article formed from the flame-retardant aromatic polycarbonate resin composition in any one of the said Claims 1-4.