JP2012241089A - High-cycle moldable thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which has a specific heat conductivity without impairing the characteristics of resin and is improved in molding cycle properties.SOLUTION: The thermoplastic resin composition includes: (A) a thermoplastic resin (component A); (B) graphite subjected to thermal expansion treatment (component B); and, if needed, (C) a reinforcement filler (component C). The composition has a heat conductivity within the range of 0.3-0.8 W/m.K.

Description

  The present invention relates to a thermoplastic resin composition having a specific thermal conductivity and improved molding cycle performance without impairing the properties of the resin.

  Thermoplastic resins are widely used in all industries because of their ease of production and molding. In particular, polycarbonate-based resin compositions generally have excellent heat resistance and impact resistance, and are widely used in electronic devices, machines, automobiles, and the like. In recent years, household appliances and information devices have been significantly reduced in weight, size and cost, and their outer shell parts have become extremely thin. For this reason, the characteristics required for the resin material become higher, and at the same time, the requirements for cost are becoming stricter. A number of cost reduction methods have been studied. One of the methods is shortening the molding cycle, especially reducing the man-hours by reducing the resin cooling time in the mold and reducing the mold. Therefore, there is a demand for a resin material having thermal conductivity that can shorten the cooling time without impairing conventional resin characteristics such as fluidity and impact characteristics.

  In general, resin materials have low thermal conductivity. Conventionally, in order to impart thermal conductivity, aluminum oxide, boron nitride, aluminum nitride, silicon nitride, magnesium oxide, zinc oxide, silicon carbide, quartz, aluminum hydroxide, etc. These are filled with fillers such as metal oxides, metal nitrides, metal carbides and metal hydroxides. However, these fillers do not necessarily have a sufficient thermal conductivity-imparting effect, and the amount of filler filling increases, so that the physical properties, particularly impact properties, are significantly reduced and the original properties of the resin are impaired. There is a problem.

  On the other hand, a thermally conductive polymer material in which a carbon material with high thermal conductivity is filled in a polymer material has been proposed. For example, a method of adding graphitized carbon fiber to a polymer material (see Patent Documents 1 to 3) and a method of adding pitch-based carbon fiber are known. It is industrially inexpensive and cannot be obtained in large quantities, and is not practical from the viewpoint of cost reduction.

A method of adding graphite to a thermoplastic resin is known. However, scaly graphite and granular graphite have low thermal conductivity imparting efficiency, and it becomes difficult to maintain the conventional characteristics by increasing the filling amount.
As a method for enhancing the thermal conductivity imparting effect of graphite, a method of adding graphite and an acidic group-containing organic compound subjected to thermal expansion treatment to a thermoplastic resin (see Patent Document 4) is disclosed. Is greatly damaged and there is room for improvement.

  Furthermore, although a method of blending a phosphorus compound and thermally expandable graphite into a resin (see Patent Documents 5 to 7)) is known, the thermally expandable graphite expands when a thermal load is applied during combustion. At times and in the molded product, the graphite layers are not sufficiently expanded, and the thermal conductivity is not satisfactory as compared with graphite subjected to thermal expansion treatment.

JP 2002-088250 A JP 2002-339171 A JP 2003-112915 A JP 2007-016093 A JP 2000-063619 A JP-A-9-296119 JP 2010-090214 A

  An object of the present invention is to provide a thermoplastic resin composition having a specific thermal conductivity and improved molding cycle performance without impairing the properties of the resin.

  As a result of intensive investigations in view of the above-mentioned problems of the prior art, the present inventor blended graphite that has undergone thermal expansion treatment with a thermoplastic resin, and imparted a specific thermal conductivity such as impact characteristics of the resin. It has been found that the molding cycle performance can be remarkably improved without impairing the characteristics.

  That is, the object of the present invention consists of (A) a thermoplastic resin (A component) and (B) graphite subjected to a thermal expansion treatment (B component), and optionally (C) a reinforcing filler (C component), And it is achieved by the thermoplastic resin composition characterized by having a thermal conductivity in the range of 0.3 to 0.8 W / m · K.

(Component A: thermoplastic resin)
(A-1 component: aromatic polycarbonate resin)
The aromatic polycarbonate resin used as the A component thermoplastic resin 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 resin, copolymer polycarbonate resin copolymerized with bifunctional alcohol (including alicyclic), and polyester carbonate resin copolymerized with such bifunctional carboxylic acid and bifunctional alcohol are included. Moreover, the mixture which mixed 2 or more types of the obtained aromatic polycarbonate resin may be sufficient.

  The branched polycarbonate resin can impart anti-drip performance and the like to the glass reinforced resin composition of the present invention. 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 structural unit derived from the polyfunctional aromatic compound in the branched polycarbonate is preferably a total of 100 mol% of the structural unit derived from the dihydric phenol and the structural unit derived from the polyfunctional aromatic compound. It is 0.01-1 mol%, More preferably, it is 0.05-0.9 mol%, Most preferably, it is 0.05-0.8 mol%.

In particular, in the case of the melt transesterification method, a branched structural unit may be generated as a side reaction, and the amount of the branched structural unit is preferably 100% by mole in total with the structural unit derived from dihydric phenol. 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, particularly preferably 0.01 to 0.8 mol% is preferable. The ratio of the branched structure 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.

  Reaction formats such as interfacial polymerization, melt transesterification, carbonate prepolymer solid phase transesterification, and ring-opening polymerization of cyclic carbonate compounds, which are methods for producing the polycarbonate-based resin of the present invention, are various documents and patent publications. This is a well-known method.

In producing the thermoplastic resin composition of the present invention, the viscosity average molecular weight (M) of the polycarbonate-based 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} .

With a polycarbonate resin having a viscosity average molecular weight of less than 1 × 10 ⁴ , good mechanical properties cannot be obtained. 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 said polycarbonate-type resin may be obtained by mixing that whose viscosity average molecular weight is outside the said range. In particular, a polycarbonate resin having a viscosity average molecular weight exceeding the above range (5 × 10 ⁴ ) improves the entropy elasticity of the resin. As a result, good moldability is exhibited in gas assist molding and foam molding which may be used when molding a reinforced resin material into a structural member. Such improvement in moldability is even better than that of the branched polycarbonate. As a more suitable aspect, the A component has a viscosity average molecular weight of 7 × 10 ^{4 to} 3 × 10 ^{5 and} a polycarbonate resin (A-1-1-1 component), and the viscosity average molecular weight of 1 × 10 ^{4 to} 3 × 10 ^4. Polycarbonate resin (A-1-1 component) having a viscosity average molecular weight of 1.6 × 10 ^{4 to} 3.5 × 10 ⁴ Hereinafter, it may be referred to as “a high molecular weight component-containing polycarbonate resin”.

In such a high molecular weight component-containing polycarbonate resin (A-1-1 component), the molecular weight of the A-1-1-1 component is preferably 7 × 10 ⁴ to 2 × 10 ⁵ , more preferably 8 × 10 ⁴ to 2. × 10 ⁵ , more preferably 1 × 10 ⁵ to 2 × 10 ⁵ , and particularly preferably 1 × 10 ^{5 to} 1.6 × 10 ⁵ . The molecular weight of the A-1-1-2 component is preferably 1 × 10 ^{4 to} 2.5 × 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 to} 2.3 × 10 ⁴ .

  The high molecular weight component-containing polycarbonate resin (A-1-1 component) is a mixture of the A-1-1-1 component and the A-1-1-2 component in various proportions so as to satisfy a predetermined molecular weight range. It can be obtained by adjusting. Preferably, in 100% by weight of the A-1-1 component, the A-1-1-1 component is 2 to 40% by weight, and more preferably, the A-1-1-1 component is 3 to 30% by weight. More preferably, the A-1-1-1 component is 4 to 20% by weight, and particularly preferably the A-1-1-1 component is 5 to 20% by weight.

  Moreover, as a preparation method of A-1-1 component, (1) The method of superposing | polymerizing each A-1-1-1 component and A-1-1-2 component independently, and mixing these, (2 ) A method for producing an aromatic polycarbonate resin showing a plurality of polymer peaks in a molecular weight distribution chart by GPC method represented by the method disclosed in Japanese Patent Application Laid-Open No. 5-306336 in the same system. And (3) an aromatic polycarbonate resin obtained by the production method (production method (2)) and A separately produced A. Examples thereof include a method of mixing the 1-1-1 component and / or the A-1-1-2 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 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

The viscosity average molecular weight of the polycarbonate resin in the thermoplastic reinforced resin composition of the present invention is calculated as follows. That is, the composition is mixed with 20 to 30 times its weight of methylene chloride to dissolve the soluble component in the composition. Such soluble matter is collected by Celite filtration. Thereafter, the solvent in the obtained solution is removed. The solid after removal of the solvent is sufficiently dried to obtain a solid component that dissolves in methylene chloride. A specific viscosity at 20 ° C. is determined from a solution obtained by dissolving 0.7 g of the solid in 100 ml of methylene chloride in the same manner as described above, and the viscosity average molecular weight M is calculated from the specific viscosity in the same manner as described above.
The content of the component A-1 in the component A is preferably 50% by weight or more, more preferably 55% by weight or more, and further preferably 60% by weight or more.

(A-2 component: liquid crystal polyester resin)
The A-2 component liquid crystal polyester resin used in the present invention is a thermotropic liquid crystal polyester resin, and has a property that polymer molecular chains are aligned in a certain direction in a molten state. The arrangement state may be any of nematic, smectic, cholesteric, and discotic, and may exhibit two or more forms. Furthermore, the structure of the liquid crystal polyester resin may be any structure such as a main chain type, a side chain type, and a rigid main chain bent side chain type, but a main chain type liquid crystal polyester resin is preferred.

  The form of the arrangement state, that is, the property of the anisotropic molten phase can be confirmed by a conventional polarization inspection method using an orthogonal polarizer. More specifically, the anisotropic molten phase can be confirmed by using a Leitz polarizing microscope and observing a molten sample placed on a Leitz hot stage at a magnification of 40 times in a nitrogen atmosphere. When inspected between crossed polarizers, the polymer of the present invention transmits polarized light and exhibits optical anisotropy even in a molten stationary state.

  Further, the heat resistance of the liquid crystal polyester resin may be in any range, but it is appropriate that the liquid crystal polyester resin melts at a portion close to the processing temperature of the polycarbonate resin to form a liquid crystal phase. In this respect, it is more preferable that the deflection temperature under load of the liquid crystalline polyester is 150 to 280 ° C, preferably 180 to 250 ° C. Such liquid crystal polyesters belong to the so-called heat resistant category II. In the case of such heat resistance, excellent moldability is achieved as compared with type I having higher heat resistance, and good flame retardancy is achieved as compared with type III having lower heat resistance.

  The liquid crystal polyester resin used in the present invention contains a polyester unit and a polyesteramide unit, preferably an aromatic polyester resin and an aromatic polyesteramide resin, and the aromatic polyester unit and the aromatic polyesteramide unit are in the same molecular chain. A liquid crystal polyester resin partially contained in is also a preferred example.

Particularly preferred are wholly aromatic polyester resins and wholly aromatic polyester amides having unit constituents derived from one or more compounds selected from the group consisting of aromatic hydroxycarboxylic acids, aromatic hydroxyamines and aromatic diamines. Resin. More specifically,
1) a liquid crystal polyester resin synthesized mainly from one or more of aromatic hydroxycarboxylic acids and derivatives thereof,
2) Mainly a) one or more aromatic hydroxycarboxylic acids and derivatives thereof, b) one or more aromatic dicarboxylic acids, alicyclic dicarboxylic acids and derivatives thereof, and c) aromatic diols , A liquid crystal polyester resin synthesized from at least one or more of alicyclic diol, aliphatic diol and derivatives thereof,
3) Mainly a) one or more aromatic hydroxycarboxylic acids and derivatives thereof, b) one or more aromatic hydroxyamines, aromatic diamines and derivatives thereof, and c) aromatic dicarboxylic acids, A liquid crystal polyesteramide resin synthesized from one or more of alicyclic dicarboxylic acids and derivatives thereof,
4) Mainly a) one or more aromatic hydroxycarboxylic acids and derivatives thereof, b) one or more aromatic hydroxyamines, aromatic diamines and derivatives thereof, c) aromatic dicarboxylic acids and fats A liquid crystalline polyester amide resin synthesized from one or more of a cyclic dicarboxylic acid and a derivative thereof; and d) at least one or more of an aromatic diol, an alicyclic diol, an aliphatic diol and a derivative thereof. 1) Liquid crystalline polyester resins synthesized mainly from one or more of aromatic hydroxycarboxylic acids and derivatives thereof are preferred.
Furthermore, you may use a molecular weight modifier together with said structural component as needed.

  Preferred examples of specific compounds used for the synthesis of the liquid crystalline polyester resin of the present invention include 2,6-naphthalenedicarboxylic acid, 2,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 6-hydroxy-2-naphthoic acid and the like. Na-phthalene compounds, biphenyl compounds such as 4,4′-diphenyldicarboxylic acid and 4,4′-dihydroxybiphenyl, para-position substitution such as p-hydroxybenzoic acid, terephthalic acid, hydroquinone, p-aminophenol and p-phenylenediamine Benzene compounds and their nuclear substituted benzene compounds (substituents are selected from chlorine, bromine, methyl, phenyl, 1-phenylethyl), meta-substituted benzene compounds such as isophthalic acid and resorcin, and the following general formula (1 ), (2) or (3)Among these, p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid are particularly preferable, and a liquid crystal polyester resin obtained by mixing both is preferable. As for the ratio of both, the range of 90-50 mol% is preferable for the former, The range of 80-65 mol% is more preferable, The range of 10-50 mol% is preferable for the latter, The range of 20-35 mol% is more preferable.

（但し、Ｘは炭素数１〜４のアルキレン基およびアルキリデン基、−Ｏ−、−ＳＯ−、−ＳＯ_２−、−Ｓ−、並びに−ＣＯ−よりなる群より選ばれる基であり、Ｙは−（ＣＨ_２）_ｎ−（ｎ＝１〜４）、および−Ｏ（ＣＨ_２）_ｎＯ−（ｎ＝１〜４）よりなる群より選ばれる基である。）

(However, X is a group selected from the group consisting of an alkylene group having 1 to 4 carbon atoms and an alkylidene group, —O—, —SO—, —SO ₂ —, —S—, and —CO—, and Y is It is a group selected from the group consisting of — (CH ₂ ) _n — (n = 1 to 4) and —O (CH ₂ ) _n O— (n = 1 to 4).

  The liquid crystal polyester resin used in the present invention may contain a polyalkylene terephthalate-derived unit that does not partially exhibit an anisotropic molten phase in the same molecular chain in addition to the above-described constituent components. In this case, the alkyl group has 2 to 4 carbon atoms.

The basic production method of the liquid crystal polyester resin used in the present invention is not particularly limited, and can be produced according to a known polycondensation method of a liquid crystal polyester resin. The liquid crystalline polyester resin also has a logarithmic viscosity of at least about 2.0 dl / g, such as about 2.0-10.0 dl / g when dissolved in pentafluorophenol at 60% at a concentration of 0.1% by weight ( IV values) are generally indicated.
The content of the liquid crystal polymer is preferably 1 to 40 parts by weight, more preferably 4 to 30 parts by weight, and still more preferably 5 to 20 parts by weight per 100 parts by weight of the component A-1.

(A-3 component: styrene resin)
In the present invention, a styrene resin (component A-3) can be used as the thermoplastic resin. Since this styrenic resin has good moldability, moderate heat resistance and flame retardancy, it is a preferred thermoplastic resin in order to maintain a balance between these properties.
Such a styrenic resin is a copolymer or copolymer of an aromatic vinyl compound, and, if necessary, at least one selected from other vinyl monomers and rubbery polymers copolymerizable therewith. It is a polymer obtained by polymerization.

  As the aromatic vinyl compound, styrene is particularly preferable. Preferable examples of the other vinyl monomer copolymerizable with the aromatic vinyl compound include a vinyl cyanide compound and a (meth) acrylic acid ester compound. A particularly preferred vinyl cyanide compound is acrylonitrile, and a particularly preferred (meth) acrylic acid ester compound is methyl methacrylate.

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

  Examples of the rubbery polymer copolymerizable with the aromatic vinyl compound include polybutadiene, polyisoprene, and diene copolymers (eg, styrene / butadiene random copolymers and block copolymers, acrylonitrile / butadiene copolymers). , And (meth) acrylic acid alkyl ester and butadiene copolymers), ethylene and α-olefin copolymers (eg, ethylene / propylene random copolymers and block copolymers, ethylene / butene random copolymers). Polymers and block copolymers), copolymers of ethylene and unsaturated carboxylic acid esters (for example, ethylene / methacrylate copolymers and ethylene / butyl acrylate copolymers), copolymers of ethylene and aliphatic vinyl. Polymer (for example, ethylene / vinyl acetate copolymer) ), Ethylene, propylene and non-conjugated diene terpolymers (eg, ethylene / propylene / hexadiene copolymer), acrylic rubbers (eg, polybutyl acrylate, poly (2-ethylhexyl acrylate), and butyl acrylate 2 A copolymer with ethylhexyl acrylate, etc.), and a silicone rubber (for example, polyorganosiloxane rubber, IPN type rubber comprising a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component; that is, two rubber components And rubbers having a structure in which they are entangled with each other so that they cannot be separated, and an IPN type rubber composed of a polyorganosiloxane rubber component and a polyisobutylene rubber component.

  Specific examples of the styrene resin include styrene resins such as polystyrene resin, HIPS resin, MS resin, ABS resin, AS resin, AES resin, ASA resin, MBS resin, MABS resin, MAS resin, and SMA resin. And (hydrogenated) styrene-butadiene-styrene copolymer resin, (hydrogenated) styrene-isoprene-styrene copolymer resin, and the like. In addition, the notation of (hydrogenated) means that both non-hydrogenated resin and hydrogenated resin are included. Here, the MS resin is a copolymer resin mainly composed of methyl methacrylate and styrene, the AES resin is a copolymer resin mainly composed of acrylonitrile, ethylene-propylene rubber, and styrene, and the ASA resin is mainly composed of acrylonitrile, styrene, and acrylic rubber. MABS resin is a copolymer resin mainly composed of methyl methacrylate, acrylonitrile, butadiene and styrene, MAS resin is a copolymer resin mainly composed of methyl methacrylate, acrylic rubber and styrene, and SMA resin is styrene and A copolymer resin mainly composed of maleic anhydride (MA) is shown.

  Such a styrenic resin may have a high stereoregularity such as syndiotactic polystyrene by using a catalyst such as a metallocene catalyst during the production thereof. Further, in some cases, polymers and copolymers having a narrow molecular weight distribution, block copolymers, and polymers and copolymers having high stereoregularity obtained by methods such as anion living polymerization and radical living polymerization are used. It is also possible.

  Among these, acrylonitrile / styrene copolymer resin (AS resin) and acrylonitrile / butadiene / styrene copolymer resin (ABS resin) are preferable. It is also possible to use a mixture of two or more styrenic polymers.

  The AS resin used in the present invention is a thermoplastic copolymer obtained by copolymerizing a vinyl cyanide compound and an aromatic vinyl compound. As such a vinyl cyanide compound, acrylonitrile can be particularly preferably used. As the aromatic vinyl compound, styrene and α-methylstyrene can be preferably used. The proportion of each component in the AS resin is 5 to 50% by weight, preferably 15 to 35% by weight of vinyl cyanide compound, 95 to 50% by weight of aromatic vinyl compound, when the total is 100% by weight. Preferably it is 85 to 65% by weight. Further, these vinyl compounds may be used in combination with other copolymerizable vinyl compounds described above, and the content ratio thereof is preferably 15% by weight or less in the AS resin component. Moreover, conventionally well-known various things can be used for the initiator, chain transfer agent, etc. which are used by reaction as needed.

Such an AS resin may be produced by any of bulk polymerization, suspension polymerization, and emulsion polymerization, but is preferably bulk polymerization. The copolymerization method may be either one-stage copolymerization or multistage copolymerization. The AS resin has a reduced viscosity of 0.2 to 1.0 dl / g, preferably 0.3 to 0.5 dl / g. The reduced viscosity is a value obtained by precisely weighing 0.25 g of AS resin and measuring a solution obtained by dissolving in 50 ml of dimethylformamide over 2 hours in an environment of 30 ° C. using an Ubbelohde viscometer. A viscometer having a solvent flow time of 20 to 100 seconds is used. The reduced viscosity is determined from the following formula from the solvent flow down seconds (t ₀ ) and the solution flow down seconds (t).
Reduced viscosity (η _sp / C) = {(t / t ₀ ) −1} /0.5
When the reduced viscosity is less than 0.2 dl / g, the impact is lowered, and when it exceeds 1.0 dl / g, the fluidity is deteriorated.

  The ABS resin used in the present invention is a mixture of a thermoplastic graft copolymer obtained by graft polymerization of a vinyl cyanide compound and an aromatic vinyl compound to a diene rubber component, and a copolymer of a vinyl cyanide compound and an aromatic vinyl compound. It is. As the diene rubber component forming this ABS resin, for example, rubber having a glass transition temperature of −30 ° C. or lower such as polybutadiene, polyisoprene and styrene-butadiene copolymer is used, and the proportion thereof is 100% by weight of the ABS resin component. The content is preferably 5 to 80% by weight, more preferably 8 to 50% by weight, and particularly preferably 10 to 30% by weight. As the vinyl cyanide compound grafted on the diene rubber component, acrylonitrile is particularly preferably used. As the aromatic vinyl compound grafted on the diene rubber component, styrene and α-methylstyrene are particularly preferably used. The ratio of the component grafted to the diene rubber component is preferably 95 to 20% by weight, particularly preferably 50 to 90% by weight, based on 100% by weight of the ABS resin component. Furthermore, it is preferable that the vinyl cyanide compound is 5 to 50% by weight and the aromatic vinyl compound is 95 to 50% by weight with respect to 100% by weight of the total amount of the vinyl cyanide compound and the aromatic vinyl compound. Further, methyl (meth) acrylate, ethyl acrylate, maleic anhydride, N-substituted maleimide and the like can be mixed and used for a part of the components grafted to the diene rubber component, and the content ratio thereof is in the ABS resin component. What is 15 weight% or less is preferable. Furthermore, conventionally known various initiators, chain transfer agents, emulsifiers and the like can be used as necessary.

  In the ABS resin of the present invention, the rubber particle diameter is preferably 0.1 to 5.0 μm, more preferably 0.15 to 1.5 μm, and particularly preferably 0.2 to 0.8 μm. As the distribution of the rubber particle diameter, either a single distribution or a rubber particle having two or more peaks can be used, and the rubber particles form a single phase in the morphology. Alternatively, it may have a salami structure by containing an occluded phase around the rubber particles.

  In addition, it is well known that the ABS resin contains a vinyl cyanide compound and an aromatic vinyl compound that are not grafted to the diene rubber component, and the ABS resin of the present invention is free of the occurrence of such polymerization. The polymer component may be contained. The reduced viscosity of the copolymer comprising such free vinyl cyanide compound and aromatic vinyl compound is preferably 0.2 to 1.0 dl / g, more preferably reduced viscosity (30 ° C.) determined by the method described above. 0.3 to 0.7 dl / g.

  The ratio of the grafted vinyl cyanide compound and aromatic vinyl compound is preferably 20 to 200%, more preferably 20 to 70% in terms of graft ratio (% by weight) with respect to the diene rubber component. is there.

  Such an ABS resin may be produced by any of bulk polymerization, suspension polymerization, and emulsion polymerization, but is preferably bulk polymerization. Further, as such bulk polymerization method, typically, continuous bulk polymerization method (so-called Toray method) described in Chemical Engineering Vol. 48, No. 6, page 415 (1984), and Chemical Engineering Vol. 53, No. 6, page 423 ( 1989), a continuous bulk polymerization method (so-called Mitsui Toatsu method) is exemplified. Any ABS resin is preferably used as the ABS resin of the present invention. Further, the copolymerization may be carried out in one step or in multiple steps. Moreover, what blended the vinyl compound polymer obtained by copolymerizing an aromatic vinyl compound and a vinyl cyanide component separately to the ABS resin obtained by this manufacturing method can also be used preferably.

As the AS resin and the ABS resin, those having a reduced amount of alkali (earth) metal are more preferable from the viewpoint of good thermal stability and hydrolysis resistance. The amount of alkali (earth) metal in the styrenic resin is preferably less than 100 ppm, more preferably less than 80 ppm, still more preferably less than 50 ppm, and particularly preferably less than 10 ppm. Also from this point, AS resin and ABS resin by a bulk polymerization method are preferably used. Furthermore, in relation to such good thermal stability and hydrolysis resistance, when an emulsifier is used in the AS resin and ABS resin, the emulsifier is preferably a sulfonate salt, more preferably an alkyl sulfonic acid. It is salt. When a coagulant is used, the coagulant is preferably sulfuric acid or an alkaline earth metal salt of sulfuric acid.
The blending amount of the styrenic resin is preferably 1 to 100 parts by weight, more preferably 5 to 80 parts by weight, even more preferably 10 to 70 parts by weight per 100 parts by weight of the component A-1.

(Other thermoplastic resins)
As thermoplastic resins other than the components A-1, A-2 and A-3, aromatic polyester resins (polyethylene terephthalate resin (PET resin), polybutylene terephthalate resin (PBT resin)), polyphenylene sulfide resin (PPS resin) , Cyclohexanedimethanol copolymerized polyethylene terephthalate resin (so-called PET-G resin), polyethylene naphthalate resin, and polybutylene naphthalate resin), polymethyl methacrylate resin (PMMA resin), cyclic polyolefin resin, polylactic acid resin, polycaprolactone Examples include resins and polyolefin resins (polyethylene resin, ethylene- (α-olefin) copolymer resin, polypropylene resin, propylene- (α-olefin) copolymer resin, and the like). Examples of the rubbery polymer include various core-shell type graft copolymers and thermoplastic elastomers. The content of the other thermoplastic resin and rubber polymer is preferably 100 parts by weight or less, more preferably 80 parts by weight or less, based on 100 parts by weight of the component A-1.

(B component: graphite subjected to thermal expansion treatment)
The graphite subjected to the thermal expansion treatment used as the B component in the present invention is an irregular arrangement obtained by heat-treating natural graphite, petroleum coke, petroleum pitch, amorphous carbon, etc. naturally produced as minerals at 2000 ° C. or higher. Artificial graphite with artificially oriented micro graphite crystals is immersed in concentrated sulfuric acid, concentrated nitric acid, etc., and further treated by adding an oxidizing agent such as hydrogen peroxide or hydrochloric acid to produce a graphite intercalation compound. And then rapidly washed at 800 to 1000 ° C. and expanded in the C-axis direction of the raw material graphite. When graphite that is not subjected to thermal expansion treatment is used, dispersibility in the resin is poor, and thermal conductivity and flame retardancy are significantly reduced. The graphite subjected to the thermal expansion treatment is particularly preferably natural graphite.

  The graphite subjected to the thermal expansion treatment is desirably graphite prepared by pulverizing after the thermal expansion treatment. Further, the expanded graphite subjected to the thermal expansion treatment has a shape expanded in a bowl shape, and generally has a specific volume of 100 cc / g or more, and is pulverized using various known pulverizers as it is. However, it is more preferable that the expanded graphite expanded in a bowl shape is pressed and compressed into a sheet shape using a roll, a press or the like, and is pulverized by various known pulverizers.

  The graphite subjected to this thermal expansion treatment is classified and used as necessary, and further, washed and dried as necessary to reduce the remaining acid component. The average particle diameter is preferably 0.1 to 1000 μm, and more preferably 25 to 1000 μm. If the average particle size is less than 0.1 μm, the extrusion stability during production of the resin composition is poor and the productivity is lowered, which is not preferable. When the average particle diameter exceeds 1000 μm, the appearance of the surface of the molded product is deteriorated, which is not preferable.

  The surface of the graphite subjected to the thermal expansion treatment in the present invention is subjected to surface treatment such as epoxy treatment, urethane treatment, silane in order to increase the affinity with the aromatic polycarbonate resin as long as the characteristics of the composition of the present invention are not impaired. Coupling treatment, oxidation treatment, etc. may be performed. Furthermore, the apparent bulk specific gravity of the graphite subjected to the thermal expansion treatment of the present invention is preferably 0.01 to 0.50 g / cc, more preferably 0.05 to 0.30 g / cc, and 0.10 to 0.25 g / cc. More preferred is cc. When the apparent bulk specific gravity exceeds 0.50 g / cc, the expansion ratio of the expanded graphite is low, which is not preferable because of poor heat conductivity and flame retardancy. An apparent bulk specific gravity of less than 0.01 g / cc is not preferable because the extrusion stability during production of the resin composition is poor and the productivity is lowered.

  The content of the B component is preferably 1 to 8 parts by weight, more preferably 2 to 7 parts by weight, and further preferably 2 to 6 parts by weight with respect to 100 parts by weight of the total of the A component and the C component. If the B component content is less than 1 part by weight, sufficient thermal conductivity cannot be obtained to reduce the cooling time, and if it exceeds 8 parts by weight, the thermal conductivity is improved but the cooling time shortening effect has reached its peak. In addition, physical properties such as impact characteristics and fluidity are significantly deteriorated, which is not preferable.

(C component: reinforcing filler)
The reinforcing filler which is the component C of the present invention can be blended in order to obtain a thermoplastic tree seed composition having better rigidity, dimensional accuracy, and heat resistance. Examples of reinforcing fillers include known fibrous fillers and plate-like fillers.

(Fibrous filler)
Examples of the fibrous filler used in the composition of the present invention include known fibrous fillers. As such fibrous filler, glass fiber having a round cross section, the average value of the major axis of the fiber cross section is 10 to 50 μm, and the average value of the ratio of major axis to minor axis (major axis / minor axis) is 1.5 to 8 A certain flat cross-section glass fiber, glass milled fiber, wollastonite, basalt fiber and the like are preferably exemplified. As such a fibrous filler, a filler whose surface is coated with a metal oxide such as titanium oxide, zinc oxide, cerium oxide, and silicon oxide can also be used. The fibrous filler may be surface-treated with various surface treatment agents in advance. Such surface treatment agents include silane coupling agents (including alkylalkoxysilanes and polyorganohydrogensiloxanes), higher fatty acid esters, acid compounds (for example, phosphorous acid, phosphoric acid, carboxylic acid, and carboxylic acid anhydrides). Etc.) and various surface treatment agents such as wax. Furthermore, it may be granulated with a sizing agent such as various resins, higher fatty acid esters, and waxes. Among these fibrous fillers, the above-mentioned flat cross-section glass fibers are most preferably used.

  The flat cross-section glass fiber of the present invention has an average value of the major axis of the fiber cross section of 10 to 50 μm, preferably 15 to 40 μm, more preferably 20 to 35 μm, and an average value of the ratio of major axis to minor axis (major axis / minor axis). Is 1.5 to 8, preferably 2 to 6, more preferably 2.5 to 5. When using flat cross-section glass fibers with an average ratio of major axis to minor axis within this range, anisotropy is greatly improved compared to using non-circular cross-section fibers of less than 1.5, and flame retardancy is also achieved. Can be greatly improved. This improvement in flame retardancy is achieved by aligning the long side surface of the flat cross-section glass fiber parallel to the surface of the molded product on the surface of the molded product. It is considered that the blocking effect works more effectively than the circular cross-section fiber. In addition to the flat shape, the flat cross-sectional shape includes an elliptical shape, an eyebrow shape, a trefoil shape, or a similar non-circular cross-sectional shape. Of these, a flat shape is preferable from the viewpoint of improving mechanical strength and low anisotropy. The ratio of the average fiber length to the average fiber diameter (aspect ratio) of the flat cross-section glass fiber is preferably 2 to 120, more preferably 2.5 to 70, still more preferably 3 to 50, and the fiber length and the average fiber. When the diameter ratio is less than 2, the effect of improving the mechanical strength is small, and when the ratio of the fiber length to the average fiber diameter exceeds 120, the anisotropy increases and the appearance of the molded product may deteriorate. The average fiber diameter of such flat cross-section glass fibers refers to the number average fiber diameter when the flat cross-sectional shape is converted to a true circle of the same area. The average fiber length refers to the number average fiber length in the glass fiber reinforced polycarbonate resin composition of the present invention. The number-average fiber length is a value calculated by an image analyzer from an image obtained by observing the residue of the filler collected by processing such as high-temperature ashing of a molded product, dissolution with a solvent, and decomposition with a chemical, using an optical microscope. It is. Further, when calculating such a value, the fiber diameter is used as a guide and the length is less than that.

Various glass compositions represented by A glass, C glass, E glass, etc. are applied to the glass composition of said flat cross-section glass fiber, and it is not specifically limited. Such a glass filler may contain components such as TiO ₂ , SO ₃ , and P ₂ O ₅ as necessary. Among these, E glass (non-alkali glass) is more preferable. Such flat cross-section glass fibers are preferably subjected to a surface treatment with a known surface treatment agent such as a silane coupling agent, a titanate coupling agent, or an aluminate coupling agent from the viewpoint of improving mechanical strength. In addition, those that have been subjected to bundling treatment with olefin resin, styrene resin, acrylic resin, polyester resin, epoxy resin, urethane resin, etc. are preferable. From the viewpoint of mechanical strength, epoxy resin and urethane resin are preferred. Particularly preferred. The amount of the sizing agent attached to the flat cross-section glass fibers subjected to the bundling treatment is preferably 0.1 to 3 wt%, more preferably 0.2 to 1 wt%, in 100 wt% of the flat cross-section glass fibers.

(Plate filler)
Examples of the plate filler used in the composition of the present invention include smectite minerals such as mica, talc, clay, and montmorillonite. Such plate-like fillers include those coated with metal or metal oxide. The plate-like filler of the present invention is preferably at least one plate-like filler selected from the group consisting of mica, talc, and graphite. The mica used in the present invention is preferably in the form of a powder having an average particle size of 10 to 700 μm from the viewpoint of securing rigidity. Mica is a pulverized product of silicate mineral containing aluminum, potassium, magnesium, sodium, iron and the like. Mica includes muscovite, phlogopite, biotite, and artificial mica. Any mica can be used in the present invention, but muscovite is more rigid than phlogopite or biotite. Yes, muscovite is preferable in terms of rigidity. In addition, since phlogopite and biotite contain a larger amount of Fe in the main component than muscovite, their own hue becomes blackish, and muscovite is also suitable for various coloring. In addition, muscovite is advantageous in that artificial mica (natural phlogopite with OH group substituted by F) is expensive. Accordingly, muscovite is preferred in the present invention from various points of view.

  In addition, as a pulverization method in the production of mica, a dry pulverization method of pulverizing raw mica ore with a dry pulverizer, and coarsely pulverizing mica ore with a dry pulverizer, followed by adding a grinding aid such as water to a slurry state There is a wet pulverization method in which the main pulverization is performed with a wet pulverizer, followed by dehydration and drying. The lower limit of the average particle size of mica is preferably 10 μm or more as measured by the microtrack laser diffraction method, while the upper limit is 700 μm or less as the average particle size measured by the vibration screening method. preferable. It is preferable that the microtrack laser diffraction method is performed by using a vibration sieving method with a 325 mesh pass for 95% by weight or more of mica. For mica having a larger particle size, the vibration sieving method is generally used. In the vibration sieving method of the present invention, first, sieving is carried out for 10 minutes using a JIS standard standard sieve in which 100 g of mica powder to be used is stacked in the order of openings using a vibration sieve device. In this method, the particle size distribution is obtained by measuring the weight of the powder remaining on each sieve. The weight average particle diameter measured by the vibration sieving method is preferably in the range of 50 to 700 μm, and more preferably in the range of 50 to 400 μm because the impact strength is excellent. Such an effect of the particle size is particularly preferably exhibited in mica obtained using muscovite as a raw material. Those exceeding 700 μm are rare, and molding defects such as gate clogging during molding tend to occur, which is not preferable. On the other hand, pulverization of less than 10 μm is not economical because it requires an extremely large number of man-hours. As the thickness of mica, one having a thickness measured by observation with an electron microscope of 0.01 to 10 μm can be used. Further, such mica may be surface-treated with a silane coupling agent or the like, or may be granulated with a sizing agent such as various resins such as urethane resins or higher fatty acid esters.

Talc used in the present invention is a scaly particle having a layered structure, and is chemically hydrous magnesium silicate, generally represented by the chemical formula 4SiO ₂ · 3MgO · 2H ₂ O, usually the SiO ₂ 56-65 wt%, the MgO 28 to 35 wt%, and a _{H 2} O about 5 wt%. As other minor components, Fe ₂ O ₃ is 0.03 to 1.2% by weight, Al ₂ O ₃ is 0.05 to 1.5% by weight, CaO is 0.05 to 1.2% by weight, K ₂ O. Is 0.2 wt% or less, Na ₂ O is 0.2 wt% or less, and the specific gravity is about 2.7. The particle size of talc shown here is the particle size at a 50% stacking rate determined from the particle size distribution measured by the Andreazen pipette method measured according to JIS M8016. The particle diameter is preferably 0.3 to 15 μm, more preferably 0.5 to 10 μm. In addition, there is no particular limitation on the production method when pulverizing such talc from raw stone, and axial flow mill method, annular mill method, roll mill method, ball mill method, jet mill method, container rotary compression shearing mill method, etc. Can be used. Furthermore, the talc after pulverization is preferably classified by various classifiers and has a uniform particle size distribution. There are no particular restrictions on the classifier, impactor type inertial force classifier (variable impactor, etc.), Coanda effect type inertial force classifier (elbow jet, etc.), centrifugal field classifier (multistage cyclone, microplex, dispersion separator) , Accucut, Turbo Classifier, Turboplex, Micron Separator, and Super Separator). Further, such talc is preferably in an agglomerated state in terms of its handleability and the like, and as such a production method, there are a method by deaeration compression, a method of compression using a sizing agent, and the like. In particular, the method by deaeration and compression is preferred because it is simple and does not include unnecessary sizing agent resin components in the composition of the present invention.

  The content of component C is preferably 0 to 100 parts by weight, more preferably 5 to 80 parts by weight, and still more preferably 10 to 50 parts by weight with respect to 100 parts by weight of component A. When the component C exceeds 100 parts by weight, fluidity is lowered and extrudability is deteriorated.

(D component: flame retardant)
Various compounds known as flame retardants can be blended in the thermoplastic resin composition of the present invention. The compounding of the compound used as a flame retardant not only improves the flame retardancy but also provides, for example, an improvement in antistatic properties, fluidity, rigidity, and thermal stability based on the properties of each compound.

  Examples of such flame retardants include (1) organometallic salt flame retardants (for example, alkali (earth) organic sulfonate metal salts, borate metal salt flame retardants, stannate metal salt flame retardants, etc.), (2) Organophosphorous flame retardants (for example, monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, and phosphonic acid amide compounds), (3) silicone flame retardants comprising silicone compounds, and (4) halogens And flame retardant (for example, brominated epoxy resin, brominated polystyrene, brominated polycarbonate (including oligomers), brominated polyacrylate, chlorinated polyethylene, etc.).

(1) Organometallic salt-based flame retardant An organic metal salt-based flame retardant is advantageous in that heat resistance is substantially maintained and antistatic properties can be imparted. The organometallic salt flame retardant most advantageously used in the present invention is a fluorine-containing organometallic salt compound. The fluorine-containing organometallic salt compound of the present invention refers to a metal salt compound comprising an anion component composed of an organic acid having a fluorine-substituted hydrocarbon group and a cation component composed of a metal ion. More preferred specific examples include metal salts of fluorine-substituted organic sulfonic acids, metal salts of fluorine-substituted organic sulfates, and metal salts of fluorine-substituted organic phosphates. Fluorine-containing organometallic salt compounds can be used alone or in combination of two or more. Among them, a metal salt of a fluorine-substituted organic sulfonic acid is preferable, and a metal salt of a sulfonic acid having a perfluoroalkyl group is particularly preferable. Here, the carbon number of the perfluoroalkyl group is preferably in the range of 1-18, more preferably in the range of 1-10, and still more preferably in the range of 1-8.

  The metal constituting the metal ion of the organometallic salt flame retardant is an alkali metal or an alkaline earth metal. Examples of the alkali metal include lithium, sodium, potassium, rubidium and cesium. Examples of the alkaline earth metal include beryllium. , Magnesium, calcium, strontium and barium. More preferred is an alkali metal. Accordingly, a preferred organometallic salt flame retardant is an alkali metal perfluoroalkyl sulfonate. Among such alkali metals, rubidium and cesium are suitable when transparency requirements are higher, but these are not general-purpose and difficult to purify, resulting in disadvantages in terms of cost. is there. On the other hand, although lithium and sodium are advantageous in terms of cost and flame retardancy, they may be disadvantageous in terms of transparency. In consideration of these, the alkali metal in the perfluoroalkylsulfonic acid alkali metal salt can be properly used, but perfluoroalkylsulfonic acid potassium salt having an excellent balance of properties is most suitable in any respect. Such potassium salts and alkali metal salts of perfluoroalkylsulfonic acid composed of other alkali metals can be used in combination.

  Such alkali metal perfluoroalkylsulfonates include potassium trifluoromethanesulfonate, potassium perfluorobutanesulfonate, potassium perfluorohexanesulfonate, potassium perfluorooctanesulfonate, sodium pentafluoroethanesulfonate, perfluorobutanesulfone. Acid sodium, sodium perfluorooctane sulfonate, lithium trifluoromethane sulfonate, lithium perfluorobutane sulfonate, lithium perfluoroheptane sulfonate, cesium trifluoromethane sulfonate, cesium perfluorobutane sulfonate, cesium perfluorooctane sulfonate, Cesium perfluorohexane sulfonate, rubidium perfluorobutane sulfonate, and perful B hexane sulfonate rubidium, and these may be used in combination of at least one or two. Of these, potassium perfluorobutanesulfonate is particularly preferred.

  The fluorine-containing organometallic salt preferably has a fluoride ion content as measured by ion chromatography of 50 ppm or less, more preferably 20 ppm or less, and even more preferably 10 ppm or less. The lower the fluoride ion content, the better the flame retardancy and light resistance. The lower limit of the fluoride ion content can be substantially zero, but is practically preferably about 0.2 ppm in view of the balance between the refining man-hour and the effect. Such alkali metal salt of perfluoroalkylsulfonic acid having a fluoride ion content is purified, for example, as follows. The perfluoroalkylsulfonic acid alkali metal salt is dissolved in 2 to 10 times by weight of the metal salt in ion-exchanged water in the range of 40 to 90 ° C. (more preferably 60 to 85 ° C.). The alkali metal salt of perfluoroalkylsulfonic acid is a method of neutralizing perfluoroalkylsulfonic acid with an alkali metal carbonate or hydroxide, or perfluoroalkylsulfonyl fluoride with an alkali metal carbonate or hydroxide. It is produced by a neutralizing method (more preferably by the latter method). The ion-exchanged water is particularly preferably water having an electric resistance value of 18 MΩ · cm or more. The solution in which the metal salt is dissolved is stirred at the above temperature for 0.1 to 3 hours, more preferably 0.5 to 2.5 hours. Thereafter, the liquid is cooled to 0 to 40 ° C, more preferably in the range of 10 to 35 ° C. Crystals precipitate upon cooling. The precipitated crystals are removed by filtration. This produces a suitable purified perfluoroalkylsulfonic acid alkali metal salt.

  The content of the fluorine-containing organometallic salt compound is preferably 0.005 to 1.0 part by weight, more preferably 0.01 to 0.7 part by weight, based on the total of 100 parts by weight of component A and component C, Preferably it is 0.01-0.5 weight part. Within such a range, the effects expected from the blending of the fluorine-containing organic metal salt (for example, flame retardancy and antistatic properties) are exhibited, and the adverse effect on the light resistance of the polycarbonate resin composition is reduced, which is preferable. .

  In addition, as an organic metal salt flame retardant other than the above-mentioned fluorine-containing organic metal salt compound, a metal salt of an organic sulfonic acid not containing a fluorine atom is suitable. Examples of the metal salt include an alkali metal salt of an aliphatic sulfonic acid, an alkaline earth metal salt of an aliphatic sulfonic acid, an alkali metal salt of an aromatic sulfonic acid, and an alkaline earth metal salt of an aromatic sulfonic acid (any Also does not contain a fluorine atom).

  Preferable examples of the aliphatic sulfonic acid metal salt include an alkali (earth) metal salt of an alkyl sulfonate, and these can be used alone or in combination of two or more (here, alkali The (earth) metal salt is used to include both alkali metal salts and alkaline earth metal salts). Preferred examples of the alkane sulfonic acid used for the alkali (earth) metal salt of the alkyl sulfonate include methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid, butane sulfonic acid, methyl butane sulfonic acid, hexane sulfonic acid, and heptane. Examples thereof include sulfonic acid and octanesulfonic acid, and these can be used alone or in combination of two or more.

  The aromatic sulfonic acid used in the aromatic (earth) metal salt of aromatic sulfonate includes monomeric or polymeric aromatic sulfide sulfonic acid, aromatic carboxylic acid and ester sulfonic acid, monomeric or polymeric sulfonic acid. Aromatic ether sulfonic acid, aromatic sulfonate sulfonic acid, monomeric or polymeric aromatic sulfonic acid, monomeric or polymeric aromatic sulfonic acid, aromatic ketone sulfonic acid, heterocyclic sulfonic acid, Examples include at least one acid selected from the group consisting of sulfonic acids of aromatic sulfoxides and condensates of methylene type bonds of aromatic sulfonic acids, and these are used alone or in combination of two or more. be able to.

  Specific examples of the aromatic (earth) metal salt of an aromatic sulfonate include, for example, disodium diphenyl sulfide-4,4′-disulfonate, dipotassium diphenyl sulfide-4,4′-disulfonate, potassium 5-sulfoisophthalate, Sodium 5-sulfoisophthalate, polysodium polyethylene terephthalate polysulfonate, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, polysodium poly (2,6-dimethylphenylene oxide) polysulfonate Poly (1,3-phenylene oxide) polysulfonic acid polysodium, poly (1,4-phenylene oxide) polysulfonic acid polysodium, poly (2,6-diphenylphenylene oxide) polysulfonic acid poly Lithium, poly (2-fluoro-6-butylphenylene oxide) polysulfonate, potassium sulfonate of benzenesulfonate, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, dipotassium p-benzenedisulfonate, naphthalene-2 , 6-disulfonic acid dipotassium, biphenyl-3,3'-disulfonic acid calcium, diphenylsulfone-3-sulfonic acid sodium, diphenylsulfone-3-sulfonic acid potassium, diphenylsulfone-3,3'-disulfonic acid dipotassium, diphenylsulfone Α, α, α-trifluoroacetophenone sodium 4-sulfonate, dipotassium benzophenone-3,3′-disulfonate, Nene-2,5-disulfonate, dipotassium thiophene-2,5-disulfonate, calcium thiophene-2,5-disulfonate, sodium benzothiophenesulfonate, potassium diphenylsulfoxide-4-sulfonate, naphthalene Examples thereof include a formalin condensate of sodium sulfonate and a formalin condensate of sodium anthracene sulfonate.

  On the other hand, the alkali (earth) metal salt of sulfate ester may include, in particular, the alkali (earth) metal salt of sulfate ester of monovalent and / or polyhydric alcohols. Alcohol sulfates include methyl sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, polyoxyethylene alkylphenyl ether sulfate, pentaerythritol mono, di, tri, tetrasulfate, and lauric acid monoglyceride. And sulfuric acid esters of palmitic acid monoglyceride and stearic acid monoglyceride sulfate. The alkali (earth) metal salts of these sulfates are preferably alkali (earth) metal salts of lauryl sulfate.

  Examples of other alkali (earth) metal salts include alkali (earth) metal salts of aromatic sulfonamides such as saccharin, N- (p-tolylsulfonyl) -p-toluenesulfonimide, N Examples include-(N'-benzylaminocarbonyl) sulfanilimide and alkali (earth) metal salts of N- (phenylcarboxyl) sulfanilimide.

  Among the above, preferable metal salts of organic sulfonic acids not containing fluorine atoms are aromatic (earth) metal salts of aromatic sulfonates, and potassium salts are particularly preferable. The content of the aromatic (earth) alkali sulfonate metal salt is 0.005 to 1 part by weight, more preferably 0.01 to 0.7, based on a total of 100 parts by weight of the component A and the component C. Part by weight, more preferably 0.02 to 0.5 part by weight.

(2) Organophosphorous flame retardant As the organophosphorous flame retardant of the present invention, an aryl phosphate compound is suitable. This is because such a phosphate compound is generally excellent in hue and hardly adversely affects high light reflectivity. Moreover, since the phosphate compound has a plasticizing effect, it is advantageous in that the moldability of the resin composition of the present invention can be improved. As the phosphate compound, various known phosphate compounds as conventional flame retardants can be used, and more preferably, one or more phosphate compounds represented by the following general formula (4) can be mentioned.

（式（４）中のＸは、二価フェノールから誘導される二価の有機基を表し、Ｒ^１、Ｒ^２、Ｒ^３、およびＲ^４はそれぞれ一価フェノールから誘導される一価の有機基を表し、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の整数を表す。）

(X in Formula (4) represents a divalent organic group derived from a dihydric phenol, and R ¹ , R ² , R ³ , and R ⁴ are each a monovalent organic group derived from a monohydric phenol. Represents a group, j, k, l and m are each independently 0 or 1, and n represents an integer of 0 to 5.)

  The phosphate compound of the above formula may be a mixture of compounds having different n numbers, in which case the average n number is preferably 0.5 to 1.5, more preferably 0.8 to 1. 2, More preferably, it is 0.95-1.15, Most preferably, it is the range of 1-1.14.

  Preferable specific examples of the dihydric phenol for deriving X include hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4 -Hydroxyphenyl) ketone and bis (4-hydroxyphenyl) sulfide are exemplified, among which resorcinol, bisphenol A, and dihydroxydiphenyl are preferable.

Preferable specific examples of the monohydric phenol for deriving R ¹ , R ² , R ³ , and R ⁴ include phenol, cresol, xylenol, isopropylphenol, butylphenol, and p-cumylphenol. Are phenol and 2,6-dimethylphenol.

  The monohydric phenol may be substituted with a halogen atom. Specific examples of the phosphate compound having a group derived from the monohydric phenol include tris (2,4,6-tribromophenyl) phosphate and tris. Examples include (2,4-dibromophenyl) phosphate, tris (4-bromophenyl) phosphate, and the like.

On the other hand, specific examples of the phosphate compound not substituted with a halogen atom include monophosphate compounds such as triphenyl phosphate and tri (2,6-xylyl) phosphate, and resorcinol bisdi (2,6-xylyl) phosphate). Preferred are phosphate oligomers mainly composed of phosphate oligomers, phosphate oligomers mainly composed of 4,4-dihydroxydiphenyl bis (diphenyl phosphate), and phosphate oligomers mainly composed of bisphenol A bis (diphenyl phosphate). Indicates that it may contain a small amount of other components having different degrees of polymerization, and more preferably, the component of n = 1 in the formula (4) is 80% by weight or more, more preferably 85% by weight or more, and still more preferably Contains over 90% by weight Are shown.).
The content of the organophosphorus flame retardant is 1 to 20 parts by weight, preferably 2 to 15 parts by weight, more preferably 3 to 12 parts by weight, based on 100 parts by weight of the total of the A component and the C component. .

(3) Silicone-based flame retardant The silicone compound used as the silicone-based flame retardant of the present invention improves flame retardancy by a chemical reaction during combustion. As the compound, various compounds conventionally proposed as flame retardants for aromatic polycarbonate resins can be used. The silicone compound binds itself during combustion or binds to a component derived from the resin to form a structure, or gives a flame retardant effect to the polycarbonate resin by a reduction reaction during the structure formation. It is considered. Therefore, it is preferable that a group having high activity in such a reaction is contained, and more specifically, a predetermined amount of at least one group selected from an alkoxy group and a hydrogen (ie, Si—H group) is contained. preferable. As a content rate of this group (alkoxy group, Si-H group), the range of 0.1-1.2 mol / 100g is preferable, the range of 0.12-1 mol / 100g is more preferable, 0.15-0. The range of 6 mol / 100 g is more preferable. Such a ratio can be determined by measuring the amount of hydrogen or alcohol generated per unit weight of the silicone compound by the alkali decomposition method. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a methoxy group.

Generally, the structure of a silicone compound is constituted by arbitrarily combining the following four types of siloxane units. That is,
M units: (CH ₃ ) ₃ SiO _1/2 , H (CH ₃ ) ₂ SiO _1/2 , H ₂ (CH ₃ ) SiO _1/2 , (CH ₃ ) ₂ (CH ₂ = CH) SiO _1/2 Monofunctional siloxane units such as (CH ₃ ) ₂ (C ₆ H ₅ ) SiO _1/2 , (CH ₃ ) (C ₆ H ₅ ) (CH ₂ ═CH) SiO _1/2 ,
D unit: (CH ₃ ) ₂ SiO, H (CH ₃ ) SiO, H ₂ SiO, H (C ₆ H ₅ ) SiO, (CH ₃ ) (CH ₂ ═CH) SiO, (C ₆ H ₅ ) ₂ SiO Bifunctional siloxane units such as
T unit: (CH ₃ ) SiO _3/2 , (C ₃ H ₇ ) SiO _3/2 , HSiO _3/2 , (CH ₂ ═CH) SiO _3/2 , (C ₆ H ₅ ) SiO _3/2 etc. A trifunctional siloxane unit of
Q unit: a tetrafunctional siloxane unit represented by SiO ₂ .

Specifically, the structure of the silicone compound used in the silicone-based flame retardant is represented by the following formulas: D _n , T _p , M _m D _n , M _m T _p , M _m Q _q , M _m D _n T _{p , M m D n Q q,} M m T p Q q, M m D n T p Q q, D n T p, D n Q q, include _{D n} T p _{Q q.} Among these, preferable structures of the silicone compound are M _m D _n , M _m T _p , M _m D _n T _p , and M _m D _n Q _q , and more preferable structures are M _m D _n or M _m D _n. T _p .

Here, the coefficients m, n, p, and q in the above formulas are integers of 1 or more representing the degree of polymerization of each siloxane unit, and the sum of the coefficients in each formula is the average degree of polymerization of the silicone compound. . This average degree of polymerization is preferably in the range of 3 to 150, more preferably in the range of 3 to 80, still more preferably in the range of 3 to 60, and particularly preferably in the range of 4 to 40. The better the range, the better the flame retardancy. Further, as described later, a silicone compound containing a predetermined amount of an aromatic group is excellent in transparency and hue.
When any of m, n, p, and q is a numerical value of 2 or more, the siloxane unit with the coefficient can be two or more types of siloxane units having different hydrogen atoms or organic residues to be bonded. .

  The silicone compound may be linear or have a branched structure. The organic residue bonded to the silicon atom is preferably an organic residue having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. Specific examples of such an organic residue include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a decyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, And aralkyl groups such as tolyl groups. More preferably, they are a C1-C8 alkyl group, an alkenyl group, or an aryl group. As the alkyl group, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, and a propyl group is particularly preferable.

  Further, the silicone compound used as the silicone flame retardant preferably contains an aryl group. More preferably, the ratio (aromatic group amount) of the aromatic group represented by the following general formula (5) is 10 to 70% by weight (more preferably 15 to 60% by weight).

（式（５）中、Ｘはそれぞれ独立にＯＨ基、炭素数１〜２０の一価の有機残基を示す。ｎは０〜５の整数を表わす。さらに式（５）中においてｎが２以上の場合はそれぞれ互いに異なる種類のＸを取ることができる。）

(In formula (5), each X independently represents an OH group or a monovalent organic residue having 1 to 20 carbon atoms. N represents an integer of 0 to 5. Further, in formula (5), n is 2) In these cases, different types of X can be taken.)

The silicone compound used as the silicone-based flame retardant may contain a reactive group in addition to the Si-H group and the alkoxy group. Examples of the reactive group include an amino group, a carboxyl group, an epoxy group, and a vinyl group. Examples thereof include a group, a mercapto group, and a methacryloxy group.
As the silicone compound having a Si—H group, a silicone compound containing at least one of structural units represented by the following general formulas (6) and (7) is preferably exemplified.

（式（６）および式（７）中、Ｚ^１〜Ｚ^３はそれぞれ独立に水素原子、炭素数１〜２０の一価の有機残基、または下記一般式（８）で示される化合物を示す。α^１〜α^３はそれぞれ独立に０または１を表わす。ｍ１は０もしくは１以上の整数を表わす。さらに式（６）中においてｍ１が２以上の場合の繰返し単位はそれぞれ互いに異なる複数の繰返し単位を取ることができる。）

(In formula (6) and formula (7), Z ^{1 to} Z ³ each independently represent a hydrogen atom, a monovalent organic residue having 1 to 20 carbon atoms, or a compound represented by the following general formula (8). Α ^{1 to} α ³ each independently represents 0 or 1. m1 represents 0 or an integer of 1 or more, and in Formula (6), when m1 is 2 or more, the repeating unit is a plurality of different repeating units. Can take units.)

（式（８）中、Ｚ^４〜Ｚ^８はそれぞれ独立に水素原子、炭素数１〜２０の一価の有機残基を示す。α^４〜α^８はそれぞれ独立に０または１を表わす。ｍ２は０もしくは１以上の整数を表わす。さらに式（８）中においてｍ２が２以上の場合の繰返し単位はそれぞれ互いに異なる複数の繰返し単位を取ることができる。）

(In formula (8), Z ^{4 to} Z ⁸ each independently represent a hydrogen atom or a monovalent organic residue having 1 to 20 carbon atoms. Α ^{4 to} α ⁸ each independently represents 0 or 1. m 2 Represents 0 or an integer greater than or equal to 1. Furthermore, in formula (8), when m2 is 2 or more, the repeating unit may take a plurality of different repeating units.

  Examples of the silicone compound having an alkoxy group in the silicone compound used for the silicone flame retardant include at least one compound selected from compounds represented by the general formula (9) and the general formula (10).

（式（９）中、β^１はビニル基、炭素数１〜６のアルキル基、炭素数３〜６のシクロアルキル基、並びに炭素数６〜１２のアリール基およびアラルキル基を示す。γ^１、γ^２、γ^３、γ^４、γ^５、およびγ^６は炭素数１〜６のアルキル基およびシクロアルキル基、並びに炭素数６〜１２のアリール基およびアラルキル基を示し、少なくとも１つの基がアリール基またはアラルキル基である。δ^１、δ^２、およびδ^３は炭素数１〜４のアルコキシ基を示す。）

(In formula (9), β ¹ represents a vinyl group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group and aralkyl group having 6 to 12 carbon atoms. Γ ¹ , γ ² , γ ³ , γ ⁴ , γ ⁵ , and γ ⁶ represent an alkyl group and a cycloalkyl group having 1 to ⁶ carbon atoms, and an aryl group and an aralkyl group having 6 to 12 carbon atoms, and at least one group is aryl. And δ ¹ , δ ² , and δ ³ are each an alkoxy group having 1 to 4 carbon atoms.)

（式（１０）中、β^２およびβ^３はビニル基、炭素数１〜６のアルキル基、炭素数３〜６のシクロアルキル基、並びに炭素数６〜１２のアリール基およびアラルキル基を示す。γ^７、γ^８、γ^９、γ^１０、γ^１１、γ^１２、γ^１３およびγ^１４は炭素数１〜６のアルキル基、、炭素数３〜６のシクロアルキル基、並びに炭素数６〜１２のアリール基およびアラルキル基を示し、少なくとも１つの基がアリール基またはアラルキルである。δ^４、δ^５、δ^６、およびδ^７は炭素数１〜４のアルコキシ基を示す。）

(In formula (10), β ² and β ³ represent a vinyl group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group and an aralkyl group having 6 to 12 carbon atoms. γ ⁷ , γ ⁸ , γ ⁹ , γ ¹⁰ , γ ¹¹ , γ ¹² , γ ^13, and γ ¹⁴ are each an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and 6 to 12 carbon atoms. And at least one group is an aryl group or an aralkyl group, and δ ⁴ , δ ⁵ , δ ⁶ , and δ ⁷ represent an alkoxy group having 1 to 4 carbon atoms.)

  The content of the silicone-based flame retardant is 0.01 to 10 parts by weight, more preferably 0.05 to 7 parts by weight, still more preferably 0.1 based on a total of 100 parts by weight of the component A and the component C. ~ 5 parts by weight.

(4) Halogen flame retardant As the halogen flame retardant of the present invention, brominated polycarbonate (including oligomers) is particularly suitable. Brominated polycarbonate has excellent heat resistance and can greatly improve flame retardancy. In the brominated polycarbonate used in the present invention, the structural unit represented by the following general formula (11) is at least 60 mol%, preferably at least 80 mol%, particularly preferably substantially the following general formula. A brominated polycarbonate compound comprising the structural unit represented by (11).

（式（１１）中、Ｘは臭素原子、Ｒは炭素数１〜４のアルキレン基、炭素数１〜４のアルキリデン基または−ＳＯ_２−である。）

(In Formula (11), X is a bromine atom, R is an alkylene group having 1 to 4 carbon atoms, an alkylidene group having 1 to 4 carbon atoms, or —SO ₂ —).

In the formula (11), R preferably represents a methylene group, an ethylene group, an isopropylidene group, —SO ₂ —, and particularly preferably an isopropylidene group.

  The brominated polycarbonate has a small number of remaining chloroformate groups and preferably has a terminal chlorine content of 0.3 ppm or less, more preferably 0.2 ppm or less. The amount of terminal chlorine is determined by dissolving a sample in methylene chloride, adding 4- (p-nitrobenzyl) pyridine and allowing it to react with terminal chlorine (terminal chloroformate). -3200). When the amount of terminal chlorine is 0.3 ppm or less, the thermal stability of the polycarbonate resin composition becomes better, and molding at a higher temperature becomes possible. As a result, a polycarbonate resin composition that is superior in molding processability is provided.

The brominated polycarbonate preferably has a small number of remaining hydroxyl terminals. More specifically, the amount of terminal hydroxyl groups is preferably 0.0005 mol or less, more preferably 0.0003 mol or less with respect to 1 mol of the structural unit of brominated polycarbonate. The amount of terminal hydroxyl groups can be determined by dissolving a sample in deuterated chloroform and measuring it by ¹ H-NMR method. Such a terminal hydroxyl group amount is preferable because the thermal stability of the polycarbonate resin composition is further improved.

  The specific viscosity of the brominated polycarbonate is preferably in the range of 0.015 to 0.1, more preferably in the range of 0.015 to 0.08. The specific viscosity of the brominated polycarbonate is calculated according to the above-described specific viscosity calculation formula used for calculating the viscosity average molecular weight of the polycarbonate resin which is the component A of the present invention.

  The content of the halogen-based flame retardant is from 0.1 to 20 parts by weight, more preferably from 0.5 to 15 parts by weight, and even more preferably from 1 to 10 parts, based on a total of 100 parts by weight of the component A and the component C. Parts by weight.

(E component: phosphite compound)
Examples of the phosphite compound of the present invention include triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite. Phyto, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di- n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, diste Ril 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, bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite, phenylbisphenol A Examples include pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, and dicyclohexyl pentaerythritol diphosphite.

  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- Examples include butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite and 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite.

  Among such phosphite compounds, pentaerythritol diphosphite compounds represented by the following general formula (12) are preferable, and distearyl pentaerythritol diphosphite and bis (2,4-di-tert-butylphenyl) pentaerythritol di Phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is particularly preferred.

［式中Ｒ_１およびＲ_２はそれぞれ独立して、水素、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基ないしアルキルアリール基、炭素数７〜３０のアラルキル基、炭素数４〜２０のシクロアルキル基、および炭素数１５〜２５の２−（４−オキシフェニル）プロピル置換アリール基からなる群より選択される基を示す。尚、シクロアルキル基およびアリール基は、アルキル基で置換されていてもよい。］

[Wherein R ₁ and R ₂ are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group or alkylaryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or 4 carbon atoms. A group selected from the group consisting of a cycloalkyl group having 20 to 20 carbon atoms and a 2- (4-oxyphenyl) propyl-substituted aryl group having 15 to 25 carbon atoms. In addition, the cycloalkyl group and the aryl group may be substituted with an alkyl group. ]

The content of the phosphite compound of the present invention is preferably from 0.001 to 2 parts by weight, more preferably from 0.001 to 1 part by weight, based on 100 parts by weight of the total of the A component and the C component. 5 parts by weight is more preferable. When the content of the phosphite compound is less than 0.001 part by weight, the melt heat stability of the resin composition is lowered, and when it exceeds 2 parts by weight, the obtained melt heat stability effect is saturated, and this effect Is not preferred because it cannot be obtained.
Such phosphite compounds can be used alone or in combination of two or more.

(F component: phosphate compound having a molecular weight of 300 or less)
Specific examples of the phosphate compound having a molecular weight of 300 or less of the present invention include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl cresyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate. , Tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate and the like, among which trialkyl phosphates such as tributyl phosphate and trimethyl phosphate are preferable. When the molecular weight exceeds 300, such a phosphate compound is not preferable because dispersion in the resin is deteriorated and the effect as a stabilizer is reduced. Such phosphate compounds can be used alone or in combination of two or more.

  The content of the phosphate compound having a molecular weight of 300 or less of the present invention is preferably 0.001 to 2 parts by weight, more preferably 0.001 to 1 part by weight, based on 100 parts by weight of the total of the A component and the C component. More preferred is 001 to 0.5 parts by weight. When the content of the phosphate compound is less than 0.001 part by weight, the melt heat stability of the resin composition is lowered, and when it exceeds 2 parts by weight, the obtained melt heat stability effect is saturated, and the blending effect Is not preferable because

(Other ingredients)
(Hindered phenolic antioxidant)
As the hindered phenol-based antioxidant, various compounds that are usually blended in a resin can be used. Examples of such hindered phenol compounds include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-tert -Butyl-6- (3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylamino) Methyl) 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) Ru-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-thiodie Renbis- [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, 1,3,5-trimethyl -2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) iso Cyanurate, 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-tris2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, tetrakis [methylene-3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionate] methane, triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, triethylene glycol-N-bis-3- (3- tert-butyl-4-hydroxy-5-methylphenyl) acetate, 3,9-bis [2 {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) acetyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, tetrakis [Methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris (3-tert-butyl-4-hydroxy Examples include -5-methylbenzyl) benzene and tris (3-tert-butyl-4-hydroxy-5-methylbenzyl) isocyanurate.

  Among the above compounds, tetrakis [methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, octadecyl-3- (3,5-di-tert-butyl-) is used in the present invention. 4-hydroxyphenyl) propionate, and 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4 , 8,10-Tetraoxaspiro [5,5] undecane is preferably used. In particular, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxa Spiro [5,5] undecane is preferred. The said hindered phenolic antioxidant can be used individually or in combination of 2 or more types.

  The blending amount of the hindered phenol-based antioxidant is preferably 0.005 to 1 part by weight, more preferably 0.01 to 0.3 part by weight, based on 100 parts by weight of the total of the A component and the C component, respectively. It is.

(Other heat stabilizers)
In the thermoplastic resin composition of the present invention, other heat stabilizers other than the above-mentioned E component, F component and hindered phenol antioxidant can also be blended. Such other heat stabilizers are preferably used in combination with any of these stabilizers and antioxidants, and particularly preferably used in combination with both. Examples of such other heat stabilizers include lactone stabilizers represented by a reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene (such stabilizers). Is described in detail in JP-A-7-233160). Such a compound is commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS) and can be used. Furthermore, a stabilizer obtained by mixing the compound with various phosphite compounds and hindered phenol compounds is commercially available. For example, Irganox HP-2921 manufactured by the above company is preferably exemplified. In the present invention, such a premixed stabilizer can also be used. The blending amount of the lactone stabilizer is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight, based on 100 parts by weight of the total of the A component and the C component.

  Other stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. Illustrated. Such a stabilizer is particularly effective when the resin composition is applied to rotational molding. The amount of the sulfur-containing stabilizer is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight, based on a total of 100 parts by weight of component A and component C. .

(Fluorine-containing anti-dripping agent)
The thermoplastic resin composition of the present invention can contain a fluorine-containing anti-dripping agent. By using such a fluorine-containing anti-dripping agent in combination with the above flame retardant, better flame retardancy can be obtained. Examples of such a fluorine-containing anti-drip agent include a fluorine-containing polymer having a fibril-forming ability. Examples of such a polymer include polytetrafluoroethylene and tetrafluoroethylene copolymers (for example, tetrafluoroethylene / hexafluoropropylene copolymer). Polymer, etc.), partially fluorinated polymers as shown in US Pat. No. 4,379,910, polycarbonate resins produced from fluorinated diphenols, and the like, preferably polytetrafluoroethylene (hereinafter referred to as PTFE). May be called).

Polytetrafluoroethylene (fibrillated PTFE) having fibril-forming ability 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. Its number average molecular weight ranges from 1.5 million to tens of millions. The lower limit is more preferably 3 million. The number average molecular weight is calculated based on the melt viscosity of polytetrafluoroethylene at 380 ° C. as disclosed in JP-A-6-145520. That is, the fibrillated PTFE preferably has a melt viscosity at 380 ° C. measured by the method described in this publication in the range of 10 ⁷ to 10 ¹³ poise, more preferably in the range of 10 ⁸ to 10 ¹² poise. .

  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. Further, as disclosed in JP-A-6-145520, those having a structure having such a fibrillated PTFE as a core and a low molecular weight polytetrafluoroethylene as a shell are also preferably used.

  Examples of commercially available fibrillated PTFE include Teflon (registered trademark) 6J from Mitsui DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500, F-201L from Daikin Chemical Industries, Ltd., and the like. Commercially available aqueous dispersions of fibrillated PTFE include: Fluon AD-1, AD-936 manufactured by Asahi IC Fluoropolymers, Fluon D-1, D-2 manufactured by Daikin Industries, Ltd., Mitsui A representative example is Teflon (registered trademark) 30J manufactured by DuPont Fluorochemical Co., Ltd.

  As a mixed form of fibrillated PTFE, (1) a method in which an aqueous dispersion of fibrillated PTFE and an aqueous dispersion or solution of an organic polymer are mixed and co-precipitated to obtain a co-agglomerated mixture (JP-A-60-258263). (2) A method of mixing an aqueous dispersion of fibrillated PTFE and dried organic polymer particles (Japanese Patent Laid-Open No. 4-272957). Described method), (3) A method in which an aqueous dispersion of fibrillated PTFE and an organic polymer particle solution are uniformly mixed, and the respective media are simultaneously removed from the mixture (Japanese Patent Laid-Open Nos. 06-220210, (Method described in Japanese Patent Application Laid-Open No. 08-188653), (4) A method of polymerizing monomers forming an organic polymer in an aqueous dispersion of fibrillated PTFE (Method described in JP-A-9-95583), and (5) an aqueous dispersion of PTFE and an organic polymer dispersion are uniformly mixed, and then a vinyl monomer is further polymerized in the mixed dispersion. Thereafter, those obtained by a method for obtaining a mixture (a method described in JP-A No. 11-29679) can be used. Commercial products of these fibrillated PTFE in the mixed form include “Metablene A3750, A3800” (trade name) manufactured by Mitsubishi Rayon Co., Ltd., “BLENDEX B449” (trade name) manufactured by GE Specialty Chemicals, and Shine Polymer Co., Ltd. “Shinepoly SN3307” (trade name) and the like are exemplified.

  In order to more effectively utilize the good mechanical strength of the thermoplastic resin composition of the present invention, the fibrillated PTFE is preferably finely dispersed as much as possible. As a means of achieving such fine dispersion, the above mixed form of fibrillated PTFE is advantageous. A method of directly supplying an aqueous dispersion in a melt kneader is also advantageous for fine dispersion. However, in the case of the aqueous dispersion form, consideration is required in that the hue is slightly deteriorated. The proportion of fibrillated PTFE in the mixed form is preferably 10 to 80% by weight, more preferably 15 to 75% by weight, in 100% by weight of the mixture. When the ratio of fibrillated PTFE is in such a range, good dispersibility of fibrillated PTFE can be achieved. The content of the fluorine-containing anti-dripping agent of the present invention is preferably 0.01 to 3 parts by weight, more preferably 0.02 to 2 parts by weight, more preferably 100 parts by weight of the total of the A component and the C component. 0.05 to 1.5 parts by weight. When the content of the fluorine-containing anti-dripping agent exceeds 3 parts by weight, the appearance of the molded product is deteriorated. The content of fibrillated PTFE is preferably 0.001 to 1 part by weight, and more preferably 0.1 to 0.7 part by weight with respect to 100 parts by weight of the total of component A and component C.

(UV absorber)
The thermoplastic resin composition of the present invention can contain an ultraviolet absorber. Specific examples of the ultraviolet absorber of the present invention include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4 in the benzophenone series. -Benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridolate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2, 2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-Benzoyl-4-hydroxy-2- Examples include methoxyphenyl) methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2′-carboxybenzophenone.

  Specific examples of the ultraviolet absorber include, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole in the benzotriazole series. 2- (2-hydroxy-3,5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2′- Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) ) Benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazol 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5- tert-butylphenyl) benzotriazole, 2- (2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2'-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p -Phenylenebis (1,3-benzoxazin-4-one), and 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, and 2- (2'-Hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole and co-polymerized with the monomer 2 such as a copolymer with a possible vinyl monomer and a copolymer of 2- (2′-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole with a vinyl monomer copolymerizable with the monomer Examples include polymers having a -hydroxyphenyl-2H-benzotriazole skeleton.

  Specific examples of the ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol and 2- (4) in hydroxyphenyltriazine series. , 6-Diphenyl-1,3,5-triazin-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxy Phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-propyloxyphenol, and 2- (4,6-diphenyl-1,3,5-triazine-2- Yl) -5-butyloxyphenol and the like. Furthermore, the phenyl group of the above exemplary compounds such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol is 2,4-dimethyl. Examples of the compound are phenyl groups.

  As the ultraviolet absorber, specifically, in the cyclic imino ester type, for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) ) Bis (3,1-benzoxazin-4-one), 2,2 ′-(2,6-naphthalene) bis (3,1-benzoxazin-4-one) and the like.

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

  Further, the ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, whereby the ultraviolet-absorbing monomer and / or the light-stable monomer having a hindered amine structure, and an alkyl (meth) acrylate. A polymer type ultraviolet absorber obtained by copolymerization with a monomer such as may be used. Preferred examples of the UV-absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of (meth) acrylate. The

Among them, benzotriazole and hydroxyphenyltriazine are preferable from the viewpoint of ultraviolet absorption ability, and cyclic imino ester and cyanoacrylate are preferable from the viewpoint of heat resistance and hue. You may use the said ultraviolet absorber individually or in mixture of 2 or more types.
The content of the ultraviolet absorber is preferably 0.01 to 2 parts by weight, more preferably 0.02 to 2 parts by weight, still more preferably 0.03 to 3 parts by weight based on the total of 100 parts by weight of the component A and the component C. 1 part by weight, most preferably 0.05 to 0.5 part by weight.

(Release agent)
The thermoplastic resin composition of the present invention is a fatty acid ester, polyolefin wax, silicone compound, fluorine compound, paraffin wax, beeswax, etc. for the purpose of improving productivity during molding and improving dimensional accuracy of the molded product. A known release agent can also be blended.
Such fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids. Such an aliphatic alcohol may be a monohydric alcohol or a dihydric or higher polyhydric alcohol. Moreover, carbon number of this alcohol becomes like this. Preferably it is 3-32, More preferably, it is 5-30. On the other hand, the aliphatic carboxylic acid is preferably an aliphatic carboxylic acid having 3 to 32 carbon atoms, more preferably 10 to 30 carbon atoms. Of these, saturated aliphatic carboxylic acids are preferred. The fatty acid ester of the present invention is preferable in that all esters (full esters) are excellent in thermal stability at high temperatures. The acid value in the fatty acid ester of the present invention is preferably 20 or less (can take substantially 0). The hydroxyl value of the fatty acid ester is more preferably in the range of 0.1-30. Further, the iodine value of the fatty acid ester is preferably 10 or less (can take substantially 0). These characteristics can be obtained by a method defined in JIS K 0070.

Examples of the polyolefin wax include an ethylene homopolymer having a molecular weight of preferably 1,000 to 10,000, or a copolymer of ethylene and an α-olefin having 3 to 60 carbon atoms. The molecular weight is a number average molecular weight measured in terms of standard polystyrene by GPC (gel permeation chromatography) method. The upper limit of the number average molecular weight is more preferably 6,000, and still more preferably 3,000. The carbon number of the α-olefin component in the polyolefin wax is preferably 60 or less, more preferably 40 or less. More preferred specific examples include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and the like. The proportion of the α-olefin having 3 to 60 carbon atoms is preferably 20 mol% or less, more preferably 10 mol% or less. What is marketed as what is called polyethylene wax is used suitably.
The content of the above releasing agent is preferably 0.005 to 5 parts by weight, more preferably 0.01 to 4 parts by weight, and still more preferably 0.00 based on a total of 100 parts by weight of the component A and the component C. 02 to 3 parts by weight.

(Dye and pigment)
The thermoplastic resin composition of the present invention can further provide molded products containing various dyes and pigments and exhibiting various design properties. Examples of dyes used in the present invention include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as bitumen, perinone dyes, quinoline dyes, quinacridone dyes, Examples thereof include dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, the resin composition of this invention can mix | blend a metallic pigment, and can also obtain a better metallic color. As the metallic pigment, aluminum powder is suitable. In addition, by blending a fluorescent brightening agent or other fluorescent dyes that emit light, a better design effect utilizing the luminescent color can be imparted.

Examples of the fluorescent dye (including a fluorescent brightening agent) used in the present invention include a coumarin fluorescent dye, a benzopyran fluorescent dye, a perylene fluorescent dye, an anthraquinone fluorescent dye, a thioindigo fluorescent dye, and a xanthene fluorescent dye. And xanthone fluorescent dyes, thioxanthene fluorescent dyes, thioxanthone fluorescent dyes, thiazine fluorescent dyes, and diaminostilbene fluorescent dyes. Among these, coumarin fluorescent dyes, benzopyran fluorescent dyes, and perylene fluorescent dyes are preferable because they have good heat resistance and little deterioration during molding of the polycarbonate resin.
The content of the dye / pigment is preferably 0.00001 to 1 part by weight, more preferably 0.00005 to 0.5 part by weight based on 100 parts by weight of the total of the A component and the C component.

(Compound with heat-absorbing ability)
The thermoplastic fat composition of the present invention can contain a compound having a heat ray absorbing ability. Such compounds include phthalocyanine-based near-infrared absorbers, metal oxide-based near-infrared absorbers such as ATO, ITO, iridium oxide and ruthenium oxide, and metal boride-based near infrared rays such as lanthanum boride, cerium boride and tungsten boride. Preferred examples include various metal compounds having excellent near-infrared absorption ability such as an absorber, and carbon filler. As such a phthalocyanine-based near infrared absorber, for example, MIR-362 manufactured by Mitsui Chemicals, Inc. is commercially available and easily available. Examples of the carbon filler include carbon black, graphite (including both natural and artificial) and fullerene, and carbon black and graphite are preferable. These can be used alone or in combination of two or more. The content of the phthalocyanine-based near-infrared absorber is preferably 0.0005 to 0.2 parts by weight, more preferably 0.0008 to 0.1 parts by weight, based on 100 parts by weight of the total of component A and component C. 0.001 to 0.07 part by weight is more preferable. The content of the metal oxide near-infrared absorber, the metal boride-based near infrared absorber, and the carbon filler is preferably in the range of 0.1 to 200 ppm (weight ratio) in the resin composition of the present invention. A range of ˜100 ppm is more preferable.

(White pigment for high light reflection)
The thermoplastic resin composition of the present invention can be provided with a light reflection effect by blending a white pigment for high light reflection. As such a white pigment, a titanium dioxide (particularly titanium dioxide treated with an organic surface treating agent such as silicone) pigment is particularly preferred. The content of the white pigment for high light reflection is preferably 3 to 30 parts by weight and more preferably 8 to 25 parts by weight based on 100 parts by weight of the total of the A component and the C component. Two or more kinds of white pigments for high light reflection can be used in combination.

(Antistatic agent)
The thermoplastic resin composition of the present invention may require antistatic performance, and in such a case, an antistatic agent is preferably included. Examples of the antistatic agent include (1) aryl sulfonic acid phosphonium salts represented by dodecylbenzenesulfonic acid phosphonium salts, organic sulfonic acid phosphonium salts such as alkyl sulfonic acid phosphonium salts, and tetrafluoroboric acid phosphonium salts. Examples thereof include phosphonium borate salts. The content of the phosphonium salt is suitably 5 parts by weight or less, preferably 0.05 to 5 parts by weight, more preferably 1 to 3.5 parts by weight, based on a total of 100 parts by weight of component A and component C. Parts, more preferably in the range of 1.5 to 3 parts by weight.

  Examples of the antistatic agent include: (2) lithium organic sulfonate, organic sodium sulfonate, organic potassium sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate. And organic sulfonate alkali (earth) metal salts. Such metal salts are also used as flame retardants as described above. More specific examples of such metal salts include metal salts of dodecylbenzene sulfonic acid and metal salts of perfluoroalkane sulfonic acid. The content of the organic sulfonate alkali (earth) metal salt is suitably 0.5 parts by weight or less, preferably 0.001 to 0.3 parts by weight, based on the total of 100 parts by weight of component A and component C. Parts, more preferably 0.005 to 0.2 parts by weight. In particular, alkali metal salts such as potassium, cesium, and rubidium are preferable.

  Examples of the antistatic agent include (3) organic sulfonic acid ammonium salts such as alkyl sulfonic acid ammonium salt and aryl sulfonic acid ammonium salt. The ammonium salt is suitably 0.05 parts by weight or less based on 100 parts by weight of component A. Examples of the antistatic agent include (4) a polymer containing a poly (oxyalkylene) glycol component such as polyether ester amide as a constituent component. The polymer is suitably 5 parts by weight or less based on a total of 100 parts by weight of the A component and the C component.

(Elastomer)
In the thermoplastic composition of the present invention, an elastomer can be used in a small proportion within a range in which the effects of the present invention are exhibited. Examples of the elastomer include isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, and MBS (methyl methacrylate / sterene / butadiene) rubber which is a core-shell type elastomer. And MAS (methyl methacrylate / acrylonitrile / styrene) rubber.

  In addition, in the 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. In the thermoplastic resin composition of the present invention, a flow modifier, an antibacterial agent, a dispersant such as liquid paraffin, a photocatalytic antifouling agent and a photochromic agent can be blended.

(Manufacture of thermoplastic resin composition)
Arbitrary methods are employ | adopted in order to manufacture the thermoplastic resin composition of this invention. For example, each component and optionally other components can be premixed and then melt-kneaded and pelletized. Examples of the premixing means include a Nauter mixer, a V-type blender, a Henschel mixer, a mechanochemical apparatus, and an extrusion mixer. In the preliminary mixing, granulation can be performed by an extrusion granulator or a briquetting machine depending on the case. After the preliminary mixing, the mixture is melt-kneaded by a melt-kneader represented by a vent type twin-screw extruder and pelletized by a device such as a pelletizer. Other examples of the melt kneader include a Banbury mixer, a kneading roll, and a constant-temperature stirring vessel, but a vent type twin screw extruder is preferred. In addition, each component and optionally other components can be independently supplied to a melt-kneader represented by a twin-screw extruder without being premixed.
The thermal conductivity of the resin composition obtained by the above method is in the range of 0.3 to 0.8 W / m · K, preferably 0.35 to 0.7 W / mK, and 0.4 to 0.6 W / mK is more preferable.

The thermoplastic resin composition of the present invention obtained as described above can be usually produced by injection molding the pellets produced as described above to produce various products. Furthermore, the resin melt-kneaded by an extruder can be directly made into a sheet, a film, a profile extrusion molded product, a direct blow molded product, and an injection molded product without going through pellets.
In such injection molding, not only a normal molding method but also an injection compression molding, an injection press molding, a gas assist injection molding, a foam molding (including those by injection of a supercritical fluid), an insert molding, depending on the purpose as appropriate. A molded product can be obtained using an injection molding method such as in-mold coating molding, heat insulating mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultrahigh-speed injection molding. The advantages of these various molding methods are already widely known. In addition, either a cold runner method or a hot runner method can be selected for molding.

  Moreover, the thermoplastic resin composition of the present invention can also be used in the form of various shaped extruded products, sheets, films and the like by extrusion molding. 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. The resin composition of the present invention can be formed into a molded product by rotational molding, blow molding or the like. Furthermore, various surface treatments can be performed on the molded article made of the thermoplastic resin composition of the present invention. Surface treatment here refers to a new layer on the surface of resin molded products such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot dipping, etc.), painting, coating, printing, etc. A method used for ordinary polycarbonate resin is applicable. Specific examples of the surface treatment include various surface treatments such as hard coat, water / oil repellent coat, ultraviolet absorption coat, infrared absorption coat, and metalizing (evaporation).

  Since the thermoplastic resin composition of the present invention has the advantage of having a specific thermal conductivity and excellent molding cycleability without impairing the properties of the resin, various electronic / electric equipment, OA equipment, vehicle parts, machinery It is useful for various applications such as parts, other agricultural materials, transport containers, playground equipment, and miscellaneous goods, and the cost reduction effect is particularly significant in camera parts that require precision molding with a particularly high processing cost rate, especially camera barrels. The above effect is exceptional.

  The form of the present invention 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.

  Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to these. In addition, the measurement of the various characteristics in an Example was based on the following method. The following raw materials were used as raw materials.

(1) Thermal conductivity Based on the unsteady heat ray method (probe method) described in JIS R 2618, it was measured with a rapid thermal conductivity meter QTM-500 manufactured by Kyoto Electronics Industry Co., Ltd. (test piece shape: 150 mm × 75mm x 5mm). In addition, the test piece was shape | molded by the cylinder temperature of 300 degreeC and the mold temperature of 100 degreeC with the injection molding machine (Sumitomo Heavy Industries, Ltd. SG-150U).
(2) Cooling time The cooling time was gradually shortened at the time of molding the test piece, and the cooling time (shortest cooling time) at which sprue was removed when the mold was opened due to insufficient cooling was measured.
(3) Impact resistance characteristics In accordance with ISO 179, Charpy impact strength without notch was measured. In addition, the test piece was shape | molded by the cylinder temperature of 300 degreeC and the mold temperature of 100 degreeC with the injection molding machine (Sumitomo Heavy Industries, Ltd. SG-150U).
(4) Flame Retardant Properties An injection molding machine (Nissei Plastic Industry Co., Ltd. NEX50-5E, screw diameter Φ22) is molded at a cylinder temperature of 300 ° C. and a mold temperature of 100 ° C. The UL94 rank was evaluated using the test piece.

[Examples 1-8, Comparative Examples 1-3]
Various additives other than the C component shown in Table 1 were blended in the A component and the B component in each blending amount, mixed in a blender, and then melt-kneaded using a vent type twin screw extruder to obtain pellets. The various additives used were prepared in advance with a pre-mixture with the component A in advance with a concentration of 10 times the blending amount as a guide, and the whole was mixed by a blender. The vent type twin-screw extruder used was TEX-30XSST (completely meshing, rotating in the same direction, two-thread screw) manufactured by Nippon Steel Works. The extrusion conditions were a discharge rate of 20 kg / h, a screw rotation speed of 150 rpm, and a vent vacuum of 3 kPa. The extrusion temperature was 280 ° C. from the first supply port to the second supply port, and 300 ° C. from the second supply port to the die part. did. In addition, C component was supplied from the 2nd supply port using the side feeder of the said extruder, and the additives other than the remaining A component, B component, and C component were supplied to the extruder from the 1st supply port. The first supply port here is a supply port farthest from the die, and the second supply port is a supply port located between the die of the extruder and the first supply port. The obtained pellets were dried at 100 ° C. for 6 hours with a hot air circulating dryer, and then various test specimens were injection molded using an injection molding machine to evaluate various properties. The results are shown in Table 1. In addition, the content of each component indicated by symbols in Table 1 is as follows.

(A component)
A-1: Linear polycarbonate resin powder having a viscosity average molecular weight of 22400 (“Panlite L-1225WP” (trade name) manufactured by Teijin Chemicals Ltd.)
A-2: Liquid crystalline polyester (“Vectra A-950RX” (trade name) manufactured by Polyplastics Co., Ltd.)
A-3: Acrylonitrile-styrene-butadiene copolymer (“Santac UT-61” (trade name) manufactured by Nippon Air & L Co., Ltd.), bulk polymerization, about 80% by weight of free AS polymer component and ABS polymer component (Acetone insoluble gel content) About 20% by weight, butadiene rubber component content is about 15% by weight of the total)
(B component)
B-1: Expanded graphite subjected to thermal expansion treatment (“EN-250HT” (trade name) manufactured by Nishimura Graphite Co., Ltd., average particle size 350 μm)
(Other than B component)
B-2: Natural graphite (“No. 5098” manufactured by Nishimura Graphite Co., Ltd., average particle size 350 μm)
(C component)
C: Flat section chopped glass fiber (“CSG 3PA-830” (trade name) manufactured by Nitto Boseki Co., Ltd., major axis 28 μm, minor diameter 7 μm, cut length 3 mm, epoxy sizing agent)
(D component)
D-1: Phosphoric acid ester mainly composed of resornol [di (2,6-dimethylphenyl) phosphate] (“PX-200” (trade name) manufactured by Daihachi Chemical Industry Co., Ltd.)
D-2: Potassium perfluorobutanesulfonate (manufactured by Dainippon Ink Chemical Co., Ltd. “Megafac F-114P” (trade name))
(E component)
E: Distearyl pentaerythritol diphosphite (Adeka Stub PEP-8 (trade name) manufactured by Asahi Denka Kogyo Co., Ltd.)
(F component)
F: Phosphorus stabilizer (“TMP” (trade name) manufactured by Daihachi Chemical Industry Co., Ltd.)

  From the above table, the thermoplastic resin, the graphite subjected to thermal expansion treatment, and a reinforcing filler as necessary, and the thermal conductivity of the obtained thermoplastic resin composition is 0.3 to 0.8 W / m · K. It can be seen that the thermoplastic resin composition characterized by being in this range is a thermoplastic resin composition having improved molding cycle performance without impairing the properties of the resin.

Claims (13)

  (A) thermoplastic resin (component A), (B) graphite subjected to thermal expansion treatment (component B) and, if necessary, (C) reinforcing filler (component C) and having a thermal conductivity of 0 A thermoplastic resin composition characterized by being in the range of 3 to 0.8 W / m · K.   2. The thermoplastic resin composition according to claim 1, comprising 1 to 8 parts by weight of the B component with respect to 100 parts by weight of the total of 100 to 50 parts by weight of the A component and 0 to 50 parts by weight of the C component. .   The thermoplastic resin composition according to claim 1 or 2, wherein the B component is graphite that has been subjected to compression treatment of graphite subjected to thermal expansion treatment having a specific volume of 100 cc / g or more and then pulverized.   The thermoplastic resin composition according to any one of claims 1 to 3, wherein the component A is a thermoplastic resin containing 50 wt% or more of the (A-1) aromatic polycarbonate resin (component A-1).   The A component is a thermoplastic resin containing 1 to 40 parts by weight of (A-2) liquid crystal polyester resin (A-2 component) with respect to 100 parts by weight of the A-1 component. Thermoplastic resin composition.   The A-2 component is a liquid crystalline polyester resin containing a repeating unit derived from p-hydroxybenzoic acid and a repeating unit derived from 6-hydroxy-2-naphthoic acid. Thermoplastic resin composition.   The thermoplastic resin composition according to any one of claims 1 to 6, comprising 0.005 to 20 parts by weight of (D) a flame retardant (D component) with respect to 100 parts by weight of the total of A component and C component.   The thermoplastic resin composition according to any one of claims 1 to 7, comprising 0.001 to 2 parts by weight of (E) a phosphite compound (E component) with respect to 100 parts by weight of the total of A component and C component. The thermoplastic resin composition according to claim 8, wherein the E component is a pentaerythritol diphosphite compound represented by the following general formula (1).

[Wherein R ₁ and R ₂ are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group or alkylaryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or 4 carbon atoms. A group selected from the group consisting of a cycloalkyl group having 20 to 20 carbon atoms and a 2- (4-oxyphenyl) propyl-substituted aryl group having 15 to 25 carbon atoms. In addition, the cycloalkyl group and the aryl group may be substituted with an alkyl group. ]   The thermoplastic resin according to any one of claims 1 to 9, comprising 0.001 to 2 parts by weight of a phosphate compound (F component) having a molecular weight of 300 or less with respect to a total of 100 parts by weight of component A and component C. Resin composition.   The thermoplastic resin composition according to claim 10, wherein the F component is a trialkyl phosphate compound.   A camera part formed by molding the thermoplastic resin composition according to claim 1.   The camera component according to claim 12, wherein the camera component is a camera barrel.