JP2015059138A - Flame retardant glass fiber-reinforced polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant glass fiber-reinforced polycarbonate resin composition excellent in toughness, shock resistance and fire resistance, further having suppressed reduction of shock strength and fire resistance by photo deterioration and moisture and heat deterioration.SOLUTION: There is provided a flame-retardant glass fiber-reinforced polycarbonate resin composition containing 100 pts.wt. of a resin component consisting of (A) an aromatic polycarbonate resin (A component) of 0 to 99 wt.% and (B) a polycarbonate-polydiorganosiloxane polymer resin (B component) of 1 to 10 wt.%, 5 to 50 pts.wt. of (C) a phosphazene compound (C component) and 40 to 220 pts.wt. of a flat cross section glass fiber having an average of a major axis of the fiber cross section of 10 to 50 μm and an average of a ratio between the major axis and a minor axis (major axis/minor axis) of 3 to 8 (D component).

Description

  The present invention relates to a flame retardant glass fiber reinforced polycarbonate resin composition which is based on a polycarbonate resin and a polycarbonate-polyorganosiloxane copolymer resin reinforced with flat cross-section glass fibers, and which has excellent rigidity and impact strength and flame retardancy. About. More specifically, the present invention relates to a flame retardant glass fiber reinforced polycarbonate resin composition that suppresses reductions in impact strength and flame retardancy due to light degradation and also suppresses impact strength and flame retardance degradation due to wet heat degradation.

  Aromatic polycarbonate resins are excellent in mechanical properties, dimensional accuracy, electrical properties, thermal properties, and the like, and are widely used as engineer plastics in various fields such as electrical, electronic equipment, automobile, and OA fields. Among them, in recent years, along with the reduction in size and weight of products, the thickness of products has been reduced for applications such as office automation equipment and home appliances, and materials that have both high rigidity, high impact strength, and high flame resistance. Is needed. In addition, in these products, due to the diversification of the usage environment including indoors and outdoors and the improvement of the utilization rate of recycled materials through closed recycling, the properties required for the materials include higher rigidity and higher impact due to thinner products. Therefore, there is a need for a material that is not only highly flame-retardant but also has excellent durability with little deterioration even in long-term use. More specifically, there is a demand for a material having high rigidity, high impact strength, high flame retardancy, and less reduction in impact strength and flame retardance due to light degradation and wet heat degradation.

  In order to solve such a problem, Patent Document 1 proposes an aromatic polycarbonate resin composition having improved mechanical strength and flame retardancy, which comprises a polycarbonate resin, glass fibers having a specific cross-sectional shape, and an organic phosphate ester system. Yes. However, since the blending amount of the glass fiber is increased in order to impart rigidity, the flame retardancy is impaired due to the influence of the blending amount of the glass fiber, and the high flame retardance with a thin wall is not satisfied. In addition, when phosphoric acid ester-based phosphorus compounds are used, it is easy to cause a decrease in impact strength due to plasticization of polycarbonate resin or a decrease in impact strength due to wet heat deterioration. It was insufficient and unsatisfactory to achieve both reduction in flame resistance and impact strength, impact strength due to light degradation and wet heat degradation, and suppression of flame retardancy.

  In Patent Documents 2 to 4, a fragrance having improved flame retardancy, hydrolysis resistance and impact strength comprising polycarbonate resin and phosphazene compound, or polycarbonate resin, phosphazene compound and rubber-reinforced styrene, polycarbonate resin, phosphazene compound and fluorine compound. A group polycarbonate resin composition and the like have been proposed. However, the description about the effect of suppressing the flame retardance due to light degradation and wet heat degradation is insufficient, and the addition of the phosphazene compound does not reduce the impact strength and flame retardancy due to the required light degradation and wet heat degradation. It was not satisfactory for suppression and was not satisfactory.

  Patent Document 5 proposes an aromatic polycarbonate resin composition having improved light resistance, flame retardancy, and mechanical strength, comprising a polycarbonate resin, a phosphazene compound, rubber-reinforced styrene, and an ultraviolet absorber. However, although there is insufficient description on the effect of suppressing the flame retardancy due to wet heat deterioration, and the effect of suppressing light deterioration by the addition of an ultraviolet absorber is seen, the hue after light deterioration due to the effect of rubber-reinforced styrene The change was extremely large, and it was not satisfactory because it was insufficient for suppressing the reduction in impact strength and flame retardance due to the required light degradation and wet heat degradation.

  On the other hand, it is known to introduce a polycarbonate-polyorganosiloxane copolymer into an aromatic polycarbonate resin in order to improve durability, impact strength and flame retardancy. In Patent Documents 6 to 9, mechanical strength and impact resistance which are lowered by introducing a polycarbonate-polyorganosiloxane copolymer into an aromatic polycarbonate resin and adding glass fibers and flat cross-section glass fibers are improved. Aromatic polycarbonate resin compositions and the like have been proposed. However, in the compositions described in these patent documents, data indicating suppression of reduction in impact strength and flame retardancy due to light degradation and wet heat degradation due to addition of a phosphazene compound is not disclosed, and due to required light degradation and wet heat degradation. It was insufficient to suppress the impact strength and flame retardancy and was not satisfactory.

JP 2007-70468 A JP2013-1801A JP 2007-45907 A JP 7-292233 A JP 2000-351893 A Japanese Patent Laid-Open No. 55-160052 Japanese Patent Laid-Open No. 2-173061 JP-A-7-26149 JP 2012-116915 A

  An object of the present invention is to provide a flame retardant glass fiber reinforced polycarbonate resin composition that is excellent in rigidity, impact strength, and flame retardancy, and further suppresses a decrease in impact strength and flame retardancy due to light degradation and wet heat degradation. There is.

  As a result of intensive studies to achieve the above object, the present inventors have obtained a resin composition comprising a polycarbonate resin, a polycarbonate-polydiorganosiloxane copolymer resin, a phosphazene compound, and a flat cross-section glass fiber, which has a desired rigidity, It has been found that the flame retardant glass fiber reinforced polycarbonate resin composition is excellent in impact strength and flame retardancy, and further suppressed in impact strength due to light degradation and wet heat degradation, and the flame retardancy is reduced. . According to the present invention, 100 parts by weight of a resin component comprising (A) an aromatic polycarbonate resin (component A) 0 to 99% by weight and (B) a polycarbonate-polydiorganosiloxane copolymer resin (component B) 1 to 100% by weight On the other hand, (C) phosphazene compound (component C) 5 to 50 parts by weight, and (D) 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 It is achieved by a flame retardant glass fiber reinforced polycarbonate resin composition containing 40 to 220 parts by weight of a flat cross section glass fiber (component D) of 3 to 8.

Hereinafter, the details of the present invention will be described.
(A component: polycarbonate resin)
The aromatic polycarbonate resin used as the component A in the present invention is obtained by reacting a dihydric phenol and a carbonate precursor. Examples of the reaction method include an interfacial polymerization method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

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

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

  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.

  Among 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 and the like 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. (1) 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 (3) 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 an aromatic polycarbonate resin by interfacial polymerization of the dihydric phenol and the carbonate precursor, a catalyst, a terminal terminator, an antioxidant for preventing the dihydric phenol from being oxidized, if 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 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- [ 1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol and other trisphenols, tetra (4- Droxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their Acid chloride and the like, and 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable, and 1,1 , 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 0.01-2 mol%, More preferably, it is 0.05-1.2 mol%, Most preferably, it is 0.05-1.0 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. The content is preferably 0.001 to 2 mol%, more preferably 0.005 to 1.2 mol%, and particularly preferably 0.01 to 1.0 mol%. 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.

  Reaction methods 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 resin of the present invention, include various documents and patent publications. This is a well-known method.

The viscosity-average molecular weight of the aromatic polycarbonate resin as the component A (Mv) is not particularly limited, preferably ^{1.0 × 10 4 ~5 × 10 4} , more preferably 1.1 × ¹⁰ 4 ~3 × 10 ⁴ , more preferably 1.2 × 10 ^{4 to} 2.4 × 10 ⁴ .
With an aromatic 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.

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 resin 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]
From the obtained specific viscosity (η _SP ), the viscosity average molecular weight Mv is calculated by the following formula.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ Mv ^0.83
c = 0.7

  In addition, calculation of the viscosity average molecular weight of the resin component which consists of the aromatic polycarbonate resin of this invention and a polycarbonate polydiorganosiloxane copolymer resin is performed in the following way. 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. The 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 Mv is calculated from the specific viscosity in the same manner as described above.

(B component: Polycarbonate-polydiorganosiloxane copolymer resin)
The polycarbonate-polydiorganosiloxane copolymer resin used as the B component in the present invention is obtained by reacting a dihydric phenol and a carbonate precursor, and is a divalent phenol represented by the following general formula (1). And a copolymer resin prepared by copolymerizing a hydroxyaryl-terminated polydiorganosiloxane represented by the following general formula (3).

[In General Formula (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or 6 to 6 carbon atoms. 20 cycloalkyl groups, cycloalkoxy groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, aryl groups having 3 to 14 carbon atoms, aryloxy groups having 3 to 14 carbon atoms, carbon atoms Represents a group selected from the group consisting of an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. E and f are each an integer of 1 to 4, and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula (2). .

(In the general formula (2), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, carbon Represents a group selected from the group consisting of an aryl group having 3 to 14 atoms and an aralkyl group having 7 to 20 carbon atoms, and R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, or a carbon atom having 1 to 18 carbon atoms. Alkyl groups, alkoxy groups having 1 to 10 carbon atoms, cycloalkyl groups having 6 to 20 carbon atoms, cycloalkoxy groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, and 3 carbon atoms. -14 aryl group, aryloxy group having 6 to 10 carbon atoms, aralkyl group having 7 to 20 carbon atoms, aralkyloxy group having 7 to 20 carbon atoms, nitro group, aldehyde group, cyano group and Represents a group selected from the group consisting of carboxyl groups, and when there are a plurality of them, they may be the same or different, g is an integer of 1 to 10, and h is an integer of 4 to 7).

In (the general formula ^{(3), R 3, R} 4, R 5, R 6, R 7 and ^{R 8} are each independently a hydrogen atom, substituted 6-12 alkyl group carbon atoms or from 1 to 12 carbon atoms Or an unsubstituted aryl group, R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and p is a natural number Q is 0 or a natural number, and p + q is a natural number less than 100. X is a divalent aliphatic group having 2 to 8 carbon atoms.)

  Examples of the dihydric phenol represented by the general formula (1) include 4,4′-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1 -Bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis ( 4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxy-3,3′-biphenyl) propane, 2,2-bis (4-hydroxy-3-isopropylphenyl) propane 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-biphenyl (4-hydroxyphenyl) octane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis ( 3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 4,4′-dihydroxy Diphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldipheny Ether, 4,4′-sulfonyldiphenol, 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfide, 2,2′-dimethyl-4,4′-sulfonyldiphenol, 4,4 '-Dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 4,4'- Dihydroxy-3,3′-diphenyldiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-diphenyldiphenyl sulfide, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis (4-hydroxyphenyl) Enyl) cyclohexane, 1,3-bis (4-hydroxyphenyl) cyclohexane, 4,8-bis (4-hydroxyphenyl) tricyclo [5.2.1.02,6] decane, 4,4 ′-(1, 3-adamantanediyl) diphenol, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, and the like.

  Among them, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4′-sulfonyldiphenol, 2,2′-dimethyl- 4,4′-sulfonyldiphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis { 2- (4-hydroxyphenyl) propyl} benzene is preferred, especially 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4 Hydroxyphenyl) cyclohexane (BPZ), 4,4'-sulfonyl diphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is preferred. Among them, 2,2-bis (4-hydroxyphenyl) propane having excellent strength and good durability is most preferable. Moreover, you may use these individually or in combination of 2 or more types.

As the hydroxyaryl-terminated polydiorganosiloxane represented by the general formula (3), for example, the following compounds are preferably used.

  The hydroxyaryl-terminated polydiorganosiloxane (3) is a phenol having an olefinically unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, or 2-methoxy-4-allylphenol. It is easily produced by hydrosilylation reaction at the end of a polysiloxane chain having a degree of polymerization of. Of these, (2-allylphenol) -terminated polydiorganosiloxane and (2-methoxy-4-allylphenol) -terminated polydiorganosiloxane are preferred, and (2-allylphenol) -terminated polydimethylsiloxane, especially (2-methoxy-4) -Allylphenol) -terminated polydimethylsiloxane is preferred. In order to achieve high transparency, the degree of diorganosiloxane polymerization (p + q) of the hydroxyaryl-terminated polydiorganosiloxane (3) is preferably less than 100. The degree of polymerization of the diorganosiloxane (p + q) is more preferably 5 to 70, further preferably 20 to 60, particularly preferably 30 to 60, and most preferably 35 to 40. If it is less than the lower limit of such a suitable range, the flame retardancy and impact resistance will decrease due to light degradation and wet heat degradation, and if it exceeds the upper limit of such a suitable range, the flame retardancy after light degradation and wet heat degradation will be reduced. It may not be demonstrated stably.

The content of the polydiorganosiloxane derived from component B in the resin composition is preferably 0.05 to 5.00% by weight. The polydiorganosiloxane component content is more preferably 0.05 to 4.00% by weight, still more preferably 0.10 to 3.00% by weight. When the amount is less than the lower limit of the preferable range, the flame retardancy is not sufficiently exhibited. When the upper limit of the preferable range is exceeded, the flame retardancy and weld strength may not be stably exhibited. Such diorganosiloxane polymerization degree and polydiorganosiloxane content can be calculated by ¹ H-NMR measurement.

In the method of the present invention, only one hydroxyaryl-terminated polydiorganosiloxane (3) may be used, or two or more may be used.
In addition, within a range not interfering with the method of the present invention, other comonomer other than the dihydric phenol (1) and hydroxyaryl-terminated polydiorganosiloxane (3) is 10% by weight or less based on the total weight of the copolymer. It can also be used in combination.

In the method of the present invention, a mixed solution containing an oligomer having a terminal chloroformate group by the reaction of a dihydric phenol (1) and a carbonic acid ester forming compound in a mixed solution of an organic solvent insoluble in water and an aqueous alkaline solution in advance. To prepare.
In producing the oligomer of the dihydric phenol (1), the whole amount of the dihydric phenol (1) used in the method of the present invention may be converted into an oligomer at one time, or a part of the dihydric phenol (1) is used as a post-added monomer in the latter stage interface. You may add to a polycondensation reaction as a reaction raw material. The post-added monomer is added to allow the subsequent polycondensation reaction to proceed rapidly, and it is not necessary to add it when it is not necessary.

Although the method of this oligomer production | generation reaction is not specifically limited, Usually, the method performed in a solvent in presence of an acid binder is suitable.
The use ratio of the carbonate-forming compound may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. Moreover, when using gaseous carbonate ester-forming compounds, such as phosgene, the method of blowing this into a reaction system can be employ | adopted suitably.

  Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. The use ratio of the acid binder may be appropriately determined in consideration of the stoichiometric ratio (equivalent) of the reaction as described above. Specifically, it is preferable to use 2 equivalents or a slightly excess amount of acid binder with respect to the number of moles of dihydric phenol (1) used for forming the oligomer (usually 1 mole corresponds to 2 equivalents). .

  As said solvent, what is necessary is just to use a solvent inert to various reaction, such as what is used for manufacture of a well-known polycarbonate, individually or as a mixed solvent. Typical examples include hydrocarbon solvents such as xylene, halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. In particular, a halogenated hydrocarbon solvent such as methylene chloride is preferably used.

  The reaction pressure for oligomer formation is not particularly limited, and any of normal pressure, pressurization, and reduced pressure may be used, but it is usually advantageous to carry out the reaction under normal pressure. The reaction temperature is selected from the range of −20 to 50 ° C., and in many cases, heat is generated with the polymerization, so it is desirable to cool with water or ice. Although the reaction time depends on other conditions and cannot be defined unconditionally, it is usually carried out in 0.2 to 10 hours. The pH range of the oligomer formation reaction is the same as the known interfacial reaction conditions, and the pH is always adjusted to 10 or more.

  In the present invention, after obtaining a mixed solution containing the dihydric phenol (1) oligomer having a terminal chloroformate group in this way, the hydroxyaryl represented by the general formula (3) is stirred while stirring the mixed solution. The terminal polydiorganosiloxane (3) is added at a rate of 0.01 molar equivalent / min or less with respect to the charged amount of the dihydric phenol (1), and the hydroxyaryl-terminated polydiorganosiloxane (3) and the oligomer are interfacially polycondensed. To obtain a polycarbonate-polydiorganosiloxane copolymer resin. While the present invention is not limited by any theory, the conventional process involves reacting BPA with a hydroxyaryl-terminated polydiorganosiloxane monomer to react phosgene with a mixture of BPA and hydroxyaryl-terminated polydiorganosiloxane monomer. Due to the sex difference, a block copolymer having a long chain length composed of only one monomer is likely to be formed. Furthermore, a structure in which a hydroxyaryl-terminated polydiorganosiloxane monomer is bonded via a short-chain BPA oligomer tends to be formed. On the other hand, since the concentration of the hydroxyaryl-terminated polydiorganosiloxane monomer can be reduced by the process of the present invention, it is difficult to form a structure in which the hydroxyaryl-terminated polydiorganosiloxane monomer is bonded through a short-chain BPA oligomer. It is done. Thereby, it is presumed that a copolymer forming an aggregated structure with a small dispersion of the polydiorganosiloxane domain size is obtained. When the addition rate of the hydroxyaryl-terminated polydiorganosiloxane (3) is faster than 0.01 molar equivalent / min, the specification of the size of the polydiorganosiloxane domain dispersed therein in the molded article of the polycarbonate-polydiorganosiloxane copolymer resin obtained This is not preferable because the chemical dispersion exceeds 40% and the transparency deteriorates. When the addition rate of the hydroxyaryl-terminated polydiorganosiloxane (3) is slower than 0.0001 molar equivalent / min, the polydiorganosiloxane component content of the resulting copolymer resin is decreased, and the molecular weight tends to vary. . Therefore, the lower limit of the addition rate of the hydroxyaryl-terminated polydiorganosiloxane (3) is substantially 0.0001 molar equivalent / min. Moreover, in order to improve uniform dispersibility, it is desirable to add the hydroxyaryl-terminated polydiorganosiloxane (3) as a solution. The concentration of the solution is desirably dilute within a range that does not inhibit the reaction.

  In performing the interfacial polycondensation reaction, an acid binder may be appropriately added in consideration of the stoichiometric ratio (equivalent) of the reaction. Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. Specifically, when a part of the hydroxyaryl-terminated polydiorganosiloxane (3) or dihydric phenol (1) used as a post-added monomer is added to the reaction stage as described above, It is preferable to use 2 equivalents or an excess amount of alkali relative to the total number of moles of the monohydric phenol (1) and the hydroxyaryl-terminated polydiorganosiloxane (3) (usually 1 mole corresponds to 2 equivalents).

  The polycondensation by the interfacial polycondensation reaction between the oligomer of the dihydric phenol (1) and the hydroxyaryl-terminated polydiorganosiloxane (3) is performed by vigorously stirring the above mixed solution. In such a polymerization reaction, a terminal terminator or a molecular weight modifier is usually used. Examples of the terminal terminator include compounds having a monohydric phenolic hydroxyl group. In addition to ordinary phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, etc., long-chain alkylphenols, aliphatic carboxylic acids Examples include chloride, aliphatic carboxylic acid, hydroxybenzoic acid alkyl ester, hydroxyphenylalkyl acid ester, alkyl ether phenol and the like. The amount used is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, based on 100 mol of all dihydric phenol compounds used, and it is naturally possible to use two or more compounds in combination. is there. In order to accelerate the polycondensation reaction, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt may be added. The reaction time of such a polymerization reaction needs to be relatively long in order to improve transparency. Preferably it is 30 minutes or more, More preferably, it is 50 minutes or more. If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added.

A branching agent can be used in combination with the above dihydric phenol compound to form a branched polycarbonate-polydiorganosiloxane. Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate-polydiorganosiloxane copolymer 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- [1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol, etc. Trisphenol, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenone Examples thereof include tetracarboxylic acids and acid chlorides thereof, among which 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are included. 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferable. The ratio of the polyfunctional compound in the branched polycarbonate-polydiorganosiloxane copolymer resin is preferably 0.001 to 1 mol%, more preferably 0.005 to 0 in the total amount of the aromatic polycarbonate-polydiorganosiloxane copolymer resin. 0.9 mol%, more preferably 0.01 to 0.8 mol%, particularly preferably 0.05 to 0.4 mol%. Such a branched structure amount can be calculated by ¹ H-NMR measurement.

  The reaction pressure can be any of reduced pressure, normal pressure, and increased pressure. Usually, it can be suitably carried out at normal pressure or about the pressure of the reaction system. The reaction temperature is selected from the range of −20 to 50 ° C., and in many cases, heat is generated with the polymerization, so it is desirable to cool with water or ice. Since the reaction time varies depending on other conditions such as the reaction temperature, it cannot be generally specified, but it is usually performed in 0.5 to 10 hours.

In some cases, the obtained polycarbonate-polydiorganosiloxane copolymer resin is appropriately subjected to physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, crosslinking treatment, partial decomposition treatment, etc.) to obtain a desired reduction. It can also be obtained as a polycarbonate-polydiorganosiloxane copolymer resin having a viscosity [η _SP / c].
The obtained reaction product (crude product) can be recovered as a polycarbonate-polydiorganosiloxane copolymer resin having a desired purity (purity) by performing various post-treatments such as a known separation and purification method.

The viscosity-average molecular weight (Mv) of the polycarbonate-polydiorganosiloxane copolymer resin as the component B is not particularly limited, but is preferably 1.0 × 10 ^{4 to} 5 × 10 ⁴ , more preferably 1.1 × 10. ^{4 to} 3 × 10 ⁴ , more preferably 1.2 × 10 ^{4 to} 2.4 × 10 ⁴ . With a polycarbonate-polydiorganosiloxane copolymer 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 a polycarbonate-polydiorganosiloxane copolymer resin having a viscosity average molecular weight exceeding 5 × 10 ⁴ is inferior in versatility in that it has poor fluidity during injection molding.

  The average size of the polydiorganosiloxane domain in the polycarbonate-polydiorganosiloxane copolymer resin molded article is preferably in the range of 1 to 40 nm. The average size is more preferably 1 to 30 nm, still more preferably 5 to 25 nm. If the amount is less than the lower limit of the preferable range, the impact resistance and flame retardancy are not sufficiently exhibited, and if the upper limit of the preferable range is exceeded, the transparency may not be stably exhibited. Furthermore, even if the average domain size of the polydiorganosiloxane domain is within a suitable range, if the normalized dispersion exceeds 40%, transparency may not be exhibited. The normalized dispersion of such polydiorganosiloxane domain size is preferably 40% or less, more preferably 30% or less. Thereby, the polycarbonate resin composition excellent in coexistence of transparency, impact resistance, and flame retardancy is provided.

  The average domain size and the normalized dispersion of the polydiorganosiloxane domain of the polycarbonate-polydiorganosiloxane copolymer resin molded product in the present invention were evaluated by a small angle X-ray scattering method (SAXS). The small-angle X-ray scattering method is a method for measuring diffuse scattering / diffraction generated in a small-angle region within a scattering angle (2θ) <10 °. In this small-angle X-ray scattering method, if there are regions with different electron densities of about 1 to 100 nm in the substance, the X-ray diffuse scattering is measured by the difference in electron density. The particle diameter of the measurement object is obtained based on the scattering angle and the scattering intensity. In the case of a polycarbonate-polydiorganosiloxane copolymer resin having an aggregate structure in which a polydiorganosiloxane domain is dispersed in a polycarbonate polymer matrix, X-ray diffuse scattering occurs due to the difference in electron density between the polycarbonate matrix and the polydiorganosiloxane domain. The scattering intensity I at each scattering angle (2θ) in the range where the scattering angle (2θ) is less than 10 ° is measured, the small-angle X-ray scattering profile is measured, the polydiorganosiloxane domain is a spherical domain, and the particle size distribution varies. Assuming that there is a particle size, a simulation is performed using a commercially available analysis software from the temporary particle size and the temporary particle size distribution model to obtain the average size and particle size distribution (normalized dispersion) of the polydiorganosiloxane domain. According to the small-angle X-ray scattering method, the average size and particle size distribution of the polydiorganosiloxane domain dispersed in the polycarbonate polymer matrix, which cannot be accurately measured by observation with a transmission electron microscope, can be accurately, simply, and reproducibly reproduced. Can be measured. The average domain size means the number average of individual domain sizes. Normalized dispersion means a parameter in which the spread of the particle size distribution is normalized by the average size. Specifically, it is a value obtained by normalizing the dispersion of the polydiorganosiloxane domain size with the average domain size, and is represented by the following formula (1).

上記式（１）において、σはポリジオルガノシロキサンドメインサイズの標準偏差、Ｄａｖは平均ドメインサイズである。

In the above formula (1), σ is the standard deviation of the polydiorganosiloxane domain size, and Dav is the average domain size.

  The terms “average domain size” and “normalized dispersion” used in connection with the present invention are the measurement of the 1.0 mm thickness of the three-stage plate produced by the method described in the Examples by the small angle X-ray scattering method. The measured values obtained by In addition, the analysis was performed using an isolated particle model that does not take into account the interparticle interaction (interparticle interference).

  The total light transmittance of a 2 mm thick molded article made of the polycarbonate-polydiorganosiloxane copolymer resin of the present invention is preferably 88% or more. The haze of a 2 mm-thick molded product made of the polycarbonate-polydiorganosiloxane copolymer resin of the present invention is preferably 0.3 to 20%. Such haze is more preferably 0.5 to 10%, further preferably 0.6 to 5%, and particularly preferably 0.7 to 2%.

  The term “total light transmittance” as used in connection with the present invention indicates the level of transparency and means the ratio of transmitted light to incident light according to method E308 of ASTM-D1003-61. The term “haze” used in connection with the present invention indicates the level of transparency and means the percentage (%) of transmitted light that deviates from the incident light beam by forward scattering as it passes through the specimen (ASTM−). D1003-61). That is, the higher the total light transmittance and the lower the haze, the better the transparency.

In addition, the polycarbonate-polydiorganosiloxane copolymer resin of the present invention can be blended with various flame retardants and reinforcing filler additives that are usually blended with the polycarbonate resin as long as the effects of the present invention are not impaired.
Content of B component is 1-100 weight% in the total 100 weight% of A component and B component, Preferably it is 3-90 weight%, More preferably, it is 5-80 weight%. If the content of the B component is less than 1% by weight, not only the flame retardancy is lowered, but also the impact strength and flame retardancy are lowered due to light degradation and wet heat degradation.

(C component: phosphazene compound)
The flame retardant glass fiber reinforced polycarbonate resin composition of the present invention contains a phosphazene compound as the C component. Such a phosphazene compound contains a phosphorus atom and a nitrogen atom in the molecule, so that the flame retardant glass fiber reinforced polycarbonate resin composition has flame retardancy, impact strength due to light degradation and wet heat degradation, reduced flame retardancy, The effect which suppresses the deterioration of a hue can be provided. When a compound other than a phosphazene compound, such as a phosphate ester or a condensed phosphate ester, is used as the phosphorus flame retardant, the impact strength is reduced by plasticizing the polycarbonate resin. Phosphorus compounds other than phosphazene compounds are added to the polycarbonate resin to cause reduction in impact strength, flame retardancy, and hue due to light deterioration and wet heat deterioration. The phosphazene compound is not particularly limited as long as it does not contain a halogen atom and has a phosphazene structure in the molecule. Here, the phosphazene structure represents a structure represented by the formula: -P (R2) = N- [wherein R2 is an organic group]. The phosphazene compound is represented by general formulas (4) and (5).

（式中、Ｘ_１、Ｘ_２、Ｘ_３、Ｘ_４は、水素、水酸基、アミノ基、またはハロゲン原子を含まない有機基を表す。また、ｎは３〜１０の整数を表す）。

(Wherein X ₁ , X ₂ , X ₃ and X ₄ represent hydrogen, a hydroxyl group, an amino group, or an organic group not containing a halogen atom, and n represents an integer of 3 to 10).

In the above formulas (4) and (5), examples of the organic group not containing a halogen atom represented by X ₁ , X ₂ , X ₃ , or X ₄ include an alkoxy group, a phenyl group, an amino group, and an allyl group. Is mentioned.
Among these, as the phosphazene compound, a cyclic phenoxyphosphazene represented by the general formula (6) is preferable.

〔式中ｎは３〜２５の整数を示す。Ｐｈはフェニル基を示す。〕

[Wherein n represents an integer of 3 to 25. Ph represents a phenyl group. ]

Commercially available phosphazene compounds include SPS-100, SPE-100, SPR-100, SA-100, SPB-100, SPB-100L (above, manufactured by Otsuka Chemical Co., Ltd.), FP-100, and FP. -110 (above, manufactured by Fushimi Pharmaceutical). In the present invention, it is allowed to contain other components as long as the function of the phosphazene compound is not hindered.
Content of C component is 5-50 weight part with respect to a total of 100 weight part of A component and B component, Preferably it is 7-40 weight part, and 10-30 weight part is more preferable. If the blending amount of component C is less than 5 parts by weight, the effect of flame retardancy is difficult to obtain, and if it exceeds 50 parts by weight, there arises a problem that strand breakage or surging occurs during kneading extrusion and productivity is lowered.

(D component: flat cross-section glass fiber)
The glass fiber used as D component of this invention is a flat cross-section glass fiber. The average value of the major axis of the fiber cross section of the flat cross-section glass fiber of the present invention is 10 to 50 μm, preferably 15 to 40 μm, more preferably 20 to 35 μm. Further, the average value of the ratio of the major axis to the minor axis (major axis / minor axis) is 3 to 8, preferably 3.2 to 8, and more preferably 3.2 to 6. When using flat cross-section glass fibers with an average ratio of major axis to minor axis within this range, anisotropy and weld strength are greatly improved compared to the case of using non-circular cross-section fibers of less than 3. The flammability 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. is there. 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 flame retardant glass fiber reinforced polycarbonate resin composition used in 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 by 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 the flat cross-section glass fiber, and it is not particularly 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 obtained by bundling with olefin resin, styrene resin, acrylic resin, polyester resin, epoxy resin, urethane resin or the like are preferable, and epoxy resin is particularly preferable from the viewpoint of weld strength. There are various types of epoxy resins used for the convergence treatment. Examples thereof include epoxy resins such as bisphenol / epichlorohydrin type epoxy resin, glycidyl ether type epoxy resin, tetraepoxy resin, novolac type epoxy resin, glycidyl amine, epoxy alkyl ester, and epoxidized unsaturated compound. When the sizing agent is other than an epoxy resin, the weld strength may be inferior to that when an epoxy resin is used. The amount of sizing agent attached to the flat cross-section glass fibers is preferably 0.1 to 3 wt%, more preferably 0.2 to 1 wt% in 100 wt% of the flat cross-section glass fibers. If the amount of sizing agent attached is less than 0.1% by weight, it is difficult for the sizing agent to be present uniformly on the flat cross-section glass fiber, and its function is not fully exhibited. Can not.

  The content of component D is 40 to 220 parts by weight, preferably 45 to 200 parts by weight, more preferably 50 to 150 parts by weight, based on 100 parts by weight of the total of component A and component B. If the content of the D component is less than 40 parts by weight, the rigidity and strength are not sufficiently exhibited, and if it exceeds 220 parts by weight, the flame retardancy is lost, or strand breakage or surging occurs during kneading extrusion, resulting in a decrease in productivity. The problem arises.

(E component: adhesion improver)
The adhesion improver used as the E component of the present application is a compound that improves the adhesion between the A and B components and the flat cross-section glass fiber that is the D component. Among them, an organic compound having at least one functional group selected from the group consisting of an epoxy group and a carboxylic acid group in one molecule is preferably used.

  In the present invention, the above organic compound is preferably contained in order to remarkably develop the weld strength improving effect which is the effect of the present invention. The flame-retardant glass fiber reinforced polycarbonate resin composition of the present invention can strengthen the adhesiveness of the flat cross-section glass fibers that are the A component, the B component, and the D component by blending the above organic compound. As a result, the weld strength improving effect is remarkably exhibited.

  The epoxy group-containing compound is not particularly limited as long as it is an organic compound containing an epoxy group, and examples thereof include polymers of glycidyl group-containing vinyl units. Specific examples of glycidyl group-containing vinyl-based units include glycidyl methacrylate, glycidyl itaconate, diglycidyl itaconate, allyl glycidyl ether, styrene-4-glycidyl ether or 4-glycidyl styrene, etc., and improved impact resistance and weld strength. From the viewpoint of large glycidyl methacrylate, glycidyl methacrylate is most preferably used.

  The carboxylic acid group-containing compound is not particularly limited as long as it is an organic compound containing a carboxylic acid group, but from the viewpoint of resistance to flame retardants, heat resistance, compatibility with the A component and the B component, polybutylene terephthalate, Aromatic polyester resins such as polyethylene terephthalate and polyarylate are preferable, and polybutylene terephthalate is most preferably used from the viewpoint of excellent impact resistance and fluidity.

  The polybutylene terephthalate resin and the polyethylene terephthalate resin preferably used in the present invention include aromatic dicarboxylic acids in which 70 mol% or more of 100 mol% of the dicarboxylic acid component among the dicarboxylic acid component and diol component forming the polyester is aromatic dicarboxylic acid. The aromatic polyester resin is preferably an aromatic polyester resin, more preferably 90 mol% or more, and most preferably 99 mol% or more of an aromatic dicarboxylic acid. Examples of this dicarboxylic acid include terephthalic acid, isophthalic acid, adipic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4,4-stilbene dicarboxylic acid, 4,4-biphenyldicarboxylic acid Acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4-diphenyl ether dicarboxylic acid, 4,4- Examples thereof include diphenoxyethanedicarboxylic acid, 5-Na sulfoisophthalic acid, and ethylene-bis-p-benzoic acid. These dicarboxylic acids can be used alone or in admixture of two or more. In addition to the above aromatic dicarboxylic acid, the aromatic polyester resin of the present invention can be copolymerized with an aliphatic dicarboxylic acid component of less than 30 mol%. Specific examples thereof include adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and the like. Examples of the diol component of the present invention include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, trans- or cis-2,2, 4,4-tetramethyl-1,3-cyclobutanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3 -Cyclohexanedimethanol, decamethylene glycol, cyclohexanediol, p-xylenediol, bisphenol A, tetrabromobisphenol A, tetrabromobisphenol A-bis (2-hydroxyethyl ether) and the like. These can be used alone or in admixture of two or more. In addition, it is preferable that the dihydric phenol in a diol component is 30 mol% or less.

  About the manufacturing method of polybutylene terephthalate resin and polyethylene terephthalate resin used in the present invention, in the presence of a polycondensation catalyst containing titanium, germanium, antimony, etc. It is carried out by polymerizing the diol component and discharging by-produced water or lower alcohol out of the system. Examples of germanium-based polymerization catalysts include germanium oxides, hydroxides, halides, alcoholates, phenolates, and the like, and more specifically, germanium oxide, germanium hydroxide, germanium tetrachloride, tetramethoxygermanium, and the like. Can be illustrated. Further, in the present invention, compounds such as manganese, zinc, calcium, magnesium, etc., which are used in a transesterification reaction that is a prior stage of a conventional polycondensation, can be used together, and after completion of the transesterification reaction, phosphoric acid or phosphorous acid. Such a catalyst can be deactivated and polycondensed with an acid compound or the like. Furthermore, the production method of the polybutylene terephthalate resin and the polyethylene terephthalate resin can be either batch type or continuous polymerization type.

The molecular weight of the polybutylene terephthalate resin and polyethylene terephthalate resin used as the E component of the present invention is not particularly limited, but the intrinsic viscosity measured at 25 ° C. using o-chlorophenol as a solvent is 0.4 to 1.5. It is preferable that it is 0.5-1.2 especially preferably.
The amount of terminal carboxyl groups of the polybutylene terephthalate resin and polyethylene terephthalate resin used in the present invention is preferably 5 to 75 eq / ton, more preferably 5 to 70 eq / ton, and further preferably 7 to 65 eq / ton. .

The aromatic polyarylate resin used in the present invention is obtained from an aromatic dicarboxylic acid or a derivative thereof and a dihydric phenol or a derivative thereof. The aromatic dicarboxylic acid used for the preparation of the polyarylate may be any one as long as it reacts with a dihydric phenol to give a satisfactory polymer, and one or a mixture of two or more are used.
Preferred aromatic dicarboxylic acid components include terephthalic acid and isophthalic acid. A mixture thereof may also be used.

  Specific examples of the dihydric phenol component include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, and 2,2-bis (4- Hydroxy-3,5-dichlorophenyl) propane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'- Dihydroxydiphenylmethane, 2,2′-bis (4hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4, 4'-dihydroxydiphenyl, hydroquinone, etc. are mentioned. These dihydric phenol components are para-substituted products, but other isomers may be used, and ethylene glycol, propylene glycol, neopentyl glycol and the like may be used in combination with the dihydric phenol component.

  Among these, preferred polyarylate resins include those in which the aromatic dicarboxylic acid component is composed of terephthalic acid and isophthalic acid, and the divalent phenol component is composed of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A). It is done. The ratio of terephthalic acid to isophthalic acid is preferably terephthalic acid / isophthalic acid = 9/1 to 9/1 (molar ratio), particularly preferably 7/3 to 3/7 in terms of melt processability and performance balance.

  Other typical polyarylate resins include those in which the aromatic dicarboxylic acid component is composed of terephthalic acid and the dihydric phenol component is composed of bisphenol A and hydroquinone. The ratio of bisphenol A and hydroquinone is preferably bisphenol A / hydroquinone = 50/50 to 70/30 (molar ratio), more preferably 55/45 to 70/30, and still more preferably 60/40 to 70/30. .

  The viscosity average molecular weight of the polyarylate resin in the present invention is preferably in the range of about 7,000 to 100,000 in view of physical properties and extrusion processability. The polyarylate resin can be selected from any polymerization method of interfacial polycondensation and transesterification.

  The phenoxy resin in the present invention is a polymer having a main chain linked by a polyaddition structure of an aromatic diol and an aromatic diglycidyl ether, and has an average of more than 1 and less than 2 epoxy groups in the molecule. On the other hand, the epoxy resin conventionally used as a hydrolysis inhibitor has two or more epoxy groups in the molecule. These hydrolysis inhibitors contain two or more epoxy groups, and when the epoxy equivalent is small, there is a concern about deterioration of molding processability due to thickening and deterioration of the appearance of the molded product. Moreover, there is a concern that oligomers having a small molecular weight may adversely affect heat resistance and flame retardancy. That is, these conventional hydrolysis inhibitors are excellent in hydrolysis resistance and heat resistance, have no deterioration in molding processability and appearance of molded products, and have high flame retardance. On the other hand, by using a phenoxy resin, it is possible to obtain a molded product having excellent hydrolysis resistance and heat resistance, no deterioration in molding processability and appearance of the molded product, and high flame retardancy.

  Phenoxy resins are conventionally used in solution or without solvent using (1) condensation / polyaddition reaction of aromatic diol and epihalohydrin, and (2) polyaddition reaction of aromatic diol and aromatic diglycidyl ether. It can be obtained by condensation and polyaddition by a known method.

  Examples of the aromatic diol include hydroquinone, resorcin, 4,4′-dihydroxybiphenyl, 4,4′-dihydroxydiphenyl ketone, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxy). Phenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2 -Bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) ) Propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propa 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis {2- (4-hydroxyphenyl) propyl} benzene, 2,2-bis (4-hydroxyphenyl) -1, Examples thereof include 1,1,3,3,3-hexafluoropropane. Examples of the aromatic diglycidyl ether include hydroquinone diglycidyl ether, resorcin diglycidyl ether, bisphenol S diglycidyl ether, bisphenol K diglycidyl ether, bisphenol diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, Methylhydroquinone diglycidyl ether, chlorohydroquinone diglycidyl ether, 4,4'-dihydroxydiphenyl oxide diglycidyl ether, 2,6-dihydroxynaphthalenediglycidyl ether, dichlorobisphenol A diglycidyl ether, tetrachlorobisphenol A diglycidyl ether, tetra Bromobisphenol A diglycidyl ether, bisphenol AC Diglycidyl ether, bisphenol L diglycidyl ether, and bisphenol V diglycidyl ether. One of these dihydroxy compounds and / or diglycidyl ether compounds may be used alone, or two or more thereof may be used in combination as a copolymer. Among such phenoxy resins, a phenoxy resin obtained from bisphenol A and epichlorohydrin is particularly preferable because it has a bisphenol A skeleton and is believed to increase the affinity with an aromatic polycarbonate.

  The weight average molecular weight of the phenoxy resin in the present invention is preferably 10,000 to 100,000, more preferably 25,000 to 85,000, and particularly preferably 40,000 to 60,000. When the weight average molecular weight is less than 10,000, the heat resistance and flame retardancy are deteriorated, and when it is greater than 100,000, the hydrolysis resistance is deteriorated and it is difficult to produce industrially. . The weight average molecular weight in the present invention is a value measured by gel permeation chromatography (GPC) using tetrahydroxyfuran as a solvent and converted by a calibration curve using standard polystyrene.

  Furthermore, the epoxy equivalent of the phenoxy resin in the present invention is preferably 1,000 g / eq to 10,000 g / eq, more preferably 3,000 g / eq to 10,000 g / eq, and 5,000 g / eq to 10,000 g / eq. eq is particularly preferred. When the epoxy equivalent is less than 1,000 g / eq, the heat resistance and flame retardancy deteriorate when the weight average molecular weight is less than 10,000, and when the weight average molecular weight is greater than 10,000, aggregates are formed on the surface of the molded product. The appearance is deteriorated. In addition, when the epoxy equivalent is greater than 10,000 g / eq, hydrolysis resistance deteriorates regardless of the weight average molecular weight, which is not preferable. The epoxy equivalent in the present invention is a method in which a phenoxy compound is dissolved in pyridine, 0.05N hydrochloric acid is added and heated at 45 ° C., followed by back titration with 0.05N caustic soda using a mixture of thymol blue and cresol red as an indicator. It can ask for.

  The content of component E is preferably 5 to 25 parts by weight, more preferably 5 to 20 parts by weight, and even more preferably 5 to 15 parts by weight with respect to 100 parts by weight of the total of component A and component B. . If the content of component E is less than 5 parts by weight, a resin composition having excellent weld strength may not be obtained. If it exceeds 25 parts by weight, flame retardancy may be impaired.

(F component: Fluorine-containing anti-dripping agent)
Examples of the fluorine-containing anti-dripping agent that is the F component of the present invention include a fluorine-containing polymer having a fibril-forming ability. Examples of such a polymer include polytetrafluoroethylene and tetrafluoroethylene copolymers (for example, tetrafluoroethylene). Ethylene / hexafluoropropylene copolymer, etc.), partially fluorinated polymers as shown in US Pat. No. 4,379,910, polycarbonate resins produced from fluorinated diphenols, and the like. Among them, polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is preferable.

  PTFE having a fibril forming ability has a very high molecular weight, and tends to be bonded to each other by an external action such as shearing force to form a fiber. The molecular weight is 1 million to 10 million, more preferably 2 million to 9 million in the number average molecular weight determined from the standard specific gravity. Such PTFE can be used in solid form or in the form of an aqueous dispersion. In addition, PTFE having such fibril forming ability can improve the dispersibility in the resin, and it is also possible to use a PTFE mixture in a mixed form with other resins in order to obtain better flame retardancy and mechanical properties. is there.

  Examples of commercially available PTFE having such fibril forming ability include Teflon (registered trademark) 6J from Mitsui DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500 and F-201L from Daikin Industries, Ltd. Commercially available PTFE aqueous dispersions include Asahi IC Fluoropolymers' full-on AD-1, AD-936, Daikin Kogyo's full-on D-1 and D-2, Mitsui Dupont Fluoro A typical example is Teflon (registered trademark) 30J manufactured by Chemical Corporation.

  As a mixed form of PTFE, (1) a method in which an aqueous dispersion of PTFE and an aqueous dispersion or solution of an organic polymer are mixed and co-precipitated to obtain a co-aggregated mixture (Japanese Patent Laid-Open No. 60-258263, (Method described in JP-A-63-154744), (2) Method of mixing an aqueous dispersion of PTFE and dried organic polymer particles (Method described in JP-A-4-272957) (3) A method in which an aqueous dispersion of PTFE and an organic polymer particle solution are uniformly mixed, and the respective media are simultaneously removed from the mixture (Japanese Patent Laid-Open Nos. 06-220210, 08-188653, etc.) Described method), (4) a method of polymerizing monomers forming an organic polymer in an aqueous dispersion of PTFE (a method described in JP-A-9-95583), and (5) A method in which an aqueous dispersion of PTFE and an organic polymer dispersion are uniformly mixed, and a vinyl monomer is further polymerized in the mixed dispersion, and then a mixture is obtained (described in JP-A-11-29679, etc.). Those obtained by (Method) can be used. Commercially available products of PTFE in these mixed forms include “Metablene A3750” (trade name) manufactured by Mitsubishi Rayon Co., Ltd., “BLENDEX B449” (trade name) manufactured by GE Specialty Chemicals, and “SN3307” manufactured by Shine Polymer. And so on.

  As a ratio of PTFE in the mixed form, 1 to 60% by weight of PTFE is preferable in 100% by weight of the PTFE mixture, and more preferably 5 to 55% by weight. When the ratio of PTFE is within such a range, good dispersibility of PTFE can be achieved. In addition, the ratio of the said D component shows the quantity of a net fluorine-containing dripping inhibitor, and in the case of mixed form PTFE, it shows a net PTFE quantity.

  The content of the F component is preferably 0.01 to 1 part by weight, more preferably 0.05 to 0.8 part by weight with respect to 100 parts by weight of the total of the A component and the B component. 1-0.5 weight part is further more preferable. When the blending amount of the F component is less than 0.01 parts by weight, a sufficient flame retardancy assisting effect may not be exhibited, and when it exceeds 1 part by weight, it falls outside the category of non-halogen.

(G component: silicate compound)
The silicate compound used as the G component of the present invention is a compound comprising at least a metal oxide component and a SiO ₂ component, and orthosilicate, disilicate, cyclic silicate, chain silicate, and the like are suitable. The silicate compound of G component takes a crystalline state, and the shape of the crystal can take various shapes such as a fiber shape and a plate shape.
The silicate compound may be a compound oxide, an oxyacid salt (consisting of an ionic lattice), or a solid solution. The compound oxide may be a combination of two or more of a single oxide, and a single oxide and an oxyacid. Any of two or more combinations with a salt may be used, and also in the solid solution, any of a solid solution of two or more metal oxides and a solid solution of two or more oxyacid salts may be used.

The silicate compound may be a hydrate. The form of crystal water in the hydrate is entered as hydrogen silicate ion as Si—OH, entered ionic as hydroxide ion (OH—) with respect to the metal cation, and as H ₂ O molecules in the structure gap. Any form of entry may be used.
As the silicate compound, an artificial synthetic product corresponding to a natural product can be used. As the artificial compound, silicate compounds obtained from various conventionally known methods, for example, various synthesis methods using a solid reaction, a hydrothermal reaction, an ultrahigh pressure reaction, and the like can be used.
Specific examples of the silicate compound in each metal oxide component (MO) include the following. Here, the notation in parentheses is the name of a compound having such a silicate compound as a main component, and means that the compound in parentheses can be used as the exemplified metal salt.

As those containing K ₂ O in the _{component, K 2 O · SiO 2,} K 2 O · 4SiO 2 · H 2 O, K 2 O · Al 2 O 3 · 2SiO 2 ( _{Karushiraito), K} 2 O · Al ₂ O ₃ · 4SiO ₂ (leucite), and _{K 2 O · Al 2 O 3} · 6SiO 2 ( orthoclase), and the like.
As comprising Na ₂ O in the _component, Na ₂ O · SiO _2, and its _{hydrates, Na 2 O · 2SiO 2,} 2Na 2 O · SiO 2, Na 2 O · 4SiO 2, Na 2 O · 3SiO _{2 · 3H 2 O, Na 2} O · Al 2 O 3 · 2SiO 2, Na 2 O · Al 2 O 3 · 4SiO 2 ( _{jadeite), 2Na 2 O · 3CaO ·} 5SiO 2, 3Na 2 O · 2CaO · 5SiO _2, and _{Na 2 O · Al 2 O 3} · 6SiO 2 ( albite), and the like.
Li ₂ O and as including the components _{thereof, Li 2 O · SiO 2,} 2Li 2 O · SiO 2, Li 2 O · SiO 2 · H 2 O, 3Li 2 O · 2SiO 2, Li 2 O · Al 2 Examples include O ₃ · 4SiO ₂ (petalite), Li ₂ O · Al ₂ O ₃ · 2SiO ₂ (eucryptite), and Li ₂ O · Al ₂ O ₃ · 4SiO ₂ (spodumene).
As those containing BaO into its _components, and the like _{BaO · SiO 2, 2BaO · SiO} 2, BaO · Al 2 O 3 · 2SiO 2 ( celsian), and BaO _· TiO _{2 ·} 3SiO 2 (Bentoaito).

As including CaO its components, 3CaO · _SiO 2 (alite cement clinker compounds), 2CaO · SiO ₂ (belite cement clinker _{compounds), 2CaO · MgO · 2SiO 2} ( O Keruma night), 2CaO · Al ₂ O ₃ · SiO ₂ (Gerlenite), solid solution of akermanite and gehlenite (Merilite), CaO · SiO ₂ (Wollastonite (including both α-type and β-type)), CaO · MgO · 2SiO _{2 (Jiopusaido), CaO · MgO · SiO 2} ( ash magnesia _{olivine), 3CaO · MgO · 2SiO 2} ( _{Meruuinaito), CaO · Al 2 O 3} · 2SiO 2 ( anorthite), 5CaO · 6SiO ₂ · 5H ₂ O (Tobermorite, other 5CaO · 6SiO ₂ · 9H ₂ O Tobermorite group hydrates such as 2CaO · SiO ₂ · H ₂ O (Hillebrandite), and wollastonite group hydrates such as 6CaO · 6SiO ₂ · H ₂ O (zonotolite) _{things, 2CaO · SiO 2 · 2H 2} O gyro light group hydrates such (gyro _{lights), CaO · Al 2 O 3} · 2SiO 2 · H 2 O ( _{Rosonaito), CaO · FeO · 2SiO 2} ( Hedenki stone) , 3CaO · 2SiO _{2 (Chirukoanaito), 3CaO · Al 2 O 3} · 3SiO 2 ( _{Guroshura), 3CaO · Fe 2 O 3} · 3SiO 2 ( Andhra _{Daito), 6CaO · 4Al 2 O 3} · FeO · SiO 2 ( Pureokuro Aito), as well as clinozoite, olivine, olivine, vesuvite, onite , Scottite, and augite.

Furthermore, Portland cement can be mentioned as a silicate compound containing CaO as its component. The type of Portland cement is not particularly limited, and any of normal, early strength, ultra-early strength, moderate heat, sulfate resistance, white, and the like can be used. Further, various mixed cements such as blast furnace cement, silica cement, fly ash cement and the like can be used as the F component.
Moreover, blast furnace slag, a ferrite, etc. can be mentioned as a silicate compound which contains other CaO in the component.

As what contains ZnO in its component, ZnO.SiO ₂ , 2ZnO.SiO ₂ (trothite), 4ZnO.2SiO ₂ .H ₂ O (heteropolar ore) and the like can be mentioned.
As including MnO into its _components, such as _{MnO · SiO 2, 2MnO · SiO} 2, CaO · 4MnO · 5SiO 2 ( rhodonite) and Coe write the like.
As the component containing FeO, FeO · SiO ₂ (ferrosilite), 2FeO · SiO ₂ (iron olivine), 3FeO · Al ₂ O ₃ · 3SiO ₂ (almandin), and 2CaO · 5FeO · 8SiO ₂ · H ₂ O (Tetsuakuchinosene) and the like can be mentioned.
Examples of those containing CoO as a component include CoO.SiO ₂ and 2CoO.SiO ₂ .

MgO · SiO ₂ (steatite, enstatite), 2MgO · SiO ₂ (forsterite), 3MgO · Al ₂ O ₃ · 3SiO ₂ (birop), 2MgO · 2Al ₂ O ₃ · 5SiO _{2 (cordierite), 2MgO · 3SiO 2 · 5H} 2 O, 3MgO · 4SiO 2 · H 2 O ( _{talc), 5MgO · 8SiO 2 · 9H} 2 O ( _{attapulgite), 4MgO · 6SiO 2 · 7H} 2 O (Sepiolite), 3MgO · 2SiO ₂ · 2H ₂ O (Chrysolite), 5MgO · 2CaO · 8SiO ₂ · H ₂ O (Translucentite), 5MgO · Al ₂ O ₃ · 3SiO ₂ · 4H ₂ O (Chlorite) _{, K 2 O · 6MgO · Al} 2 O 3 · 6SiO 2 · 2H 2 O ( phlogopite), _Na 2 O · _{MgO · 3Al 2 O 3 · 8SiO} 2 · H 2 O ( melee stone), as well as magnesium tourmaline, linearity stone, Kamintonsen stone, vermiculite, etc. smectite and the like.

As containing Fe ₂ O ₃ on the _component, and a Fe ₂ O 3 · SiO _2.
As those containing ZrO ₂ into its _components, ZrO 2 · SiO ₂ (zircon) and AZS refractory and the like.
As containing Al ₂ O ₃ on the _{component, Al 2 O 3 · SiO 2} ( sillimanite, under-leucite, _{kyanite), 2Al 2 O 3 · SiO} 2, Al 2 O 3 · 3SiO 2, 3Al 2 O 3 2SiO ₂ (mullite), Al ₂ O ₃ · 2SiO ₂ · 2H ₂ O (kaolinite), Al ₂ O ₃ · 4SiO ₂ · H ₂ O (pyrophyllite), Al ₂ O ₃ · 4SiO ₂ · H ₂ O _{(bentonite), K 2 O · 3Na 2} O · 4Al 2 O 3 · 8SiO 2 ( _{nepheline), K 2 O · 3Al 2} O 3 · 6SiO 2 · 2H 2 O ( muscovite, sericite), _{K 2} O.6MgO.Al ₂ O ₃ .6SiO ₂ .2H ₂ O (phlogobite), various zeolites, fluorine phlogopite, biotite, and the like can be given.
Among the silicate compounds, talc, mica, and wollastonite are particularly suitable.

(talc)
In the present invention, talc is hydrous magnesium silicate in terms of chemical composition, generally represented by the chemical formula 4SiO ₂ .3MgO.2H ₂ O, and is usually scaly particles having a layered structure. thereof include a SiO ₂ 56 to 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. As for the particle diameter of talc, the average particle diameter measured by the sedimentation method is 0.1 to 15 μm (more preferably 0.2 to 12 μm, still more preferably 0.3 to 10 μm, particularly preferably 0.5 to 5 μm). A range is preferable. Furthermore, it is particularly preferable to use talc having a bulk density of 0.5 (g / cm 3) or more as a raw material. The average particle size of talc refers to D50 (median diameter of particle size distribution) measured by an X-ray transmission method which is one of liquid phase precipitation methods. As a specific example of an apparatus for performing such a measurement, Sedigraph 5100 manufactured by Micromeritics Inc. can be cited.

In addition, there is no particular restriction on the manufacturing method when talc is crushed from raw stone, and the axial flow mill method, the annular mill method, the roll mill method, the ball mill method, the jet mill method, and the container rotary compression shearing mill method are used. can do. Further, the talc after pulverization is preferably classified by various classifiers and having 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, talc is preferably in an agglomerated state in view of its handleability, and examples of such production methods include a method using degassing compression and a method using compression using a sizing agent. In particular, the degassing compression method is preferable in that the sizing agent resin component which is simple and unnecessary is not mixed into the resin composition of the present invention.

(Mica)
As the mica, those having an average particle diameter measured by a microtrack laser diffraction method of 10 to 100 μm can be preferably used. More preferably, the average particle size is 20 to 50 μm. If the average particle diameter of mica is less than 10 μm, the effect of improving the rigidity is not sufficient, and if it exceeds 100 μm, the rigidity of the rigidity is not sufficiently improved, and the mechanical strength such as impact characteristics is not significantly lowered. Mica having a thickness measured by observation with an electron microscope of 0.01 to 1 μm can be preferably used. More preferably, the thickness is 0.03 to 0.3 μm. The aspect ratio is preferably 5 to 200, more preferably 10 to 100. The mica used is preferably mascobite mica, and its Mohs hardness is about 3. Muscovite mica can achieve higher rigidity and strength than other mica such as phlogopite, and solves the problems of the present invention at a better level. The mica may be pulverized by either dry pulverization or wet pulverization. The dry pulverization method is more inexpensive and more general, but the wet pulverization method is effective for pulverizing mica more thinly and finely, and as a result, the effect of improving the rigidity of the resin composition becomes higher.

(Wollastonite)
The fiber diameter of wollastonite is preferably from 0.1 to 10 μm, more preferably from 0.1 to 5 μm, still more preferably from 0.1 to 3 μm. The aspect ratio (average fiber length / average fiber diameter) is preferably 3 or more. The upper limit of the aspect ratio is 30 or less. Here, the fiber diameter is obtained by observing the reinforcing filler with an electron microscope, obtaining individual fiber diameters, and calculating the number average fiber diameter from the measured values. The electron microscope is used because it is difficult for an optical microscope to accurately measure the size of a target level. For the fiber diameter, for the image obtained by observation with an electron microscope, the filler for which the fiber diameter is to be measured is randomly extracted, the fiber diameter is measured near the center, and the number average fiber is obtained from the obtained measured value. Calculate the diameter. The observation magnification is about 1000 times, and the number of measurement is 500 or more (600 or less is suitable for work). On the other hand, the measurement of average fiber length observes a filler with an optical microscope, calculates | requires individual length, and calculates a number average fiber length from the measured value. Observation with an optical microscope begins with the preparation of a dispersed sample so that the fillers do not overlap each other. Observation is performed under the condition of 20 times the objective lens, and the observed image is taken as image data into a CCD camera having about 250,000 pixels. The obtained image data is calculated by using a program for obtaining the maximum distance between two points of the image data using an image analysis device. Under such conditions, the size per pixel corresponds to a length of 1.25 μm, and the number of measurement is 500 or more (600 or less is suitable for work).

The wollastonite of the present invention is a magnetic separator that reflects the iron content mixed in the raw material ore and the iron content mixed due to equipment wear when pulverizing the raw material ore in order to sufficiently reflect the inherent whiteness in the resin composition. It is preferable to remove as much as possible. It is preferable that the iron content in wollastonite is 0.5% by weight or less in terms of Fe ₂ O ₃ by such magnetic separator processing.
Silicate compounds (more preferably, talc, mica, wollastonite) are preferably not surface-treated, but are surface-treated with various surface treatment agents such as silane coupling agents, higher fatty acid esters, and waxes. It may be. Furthermore, it may be granulated with a sizing agent such as various resins, higher fatty acid esters, and waxes.
The content of the G component is preferably 0.1 to 10 parts by weight, more preferably 1 to 10 parts by weight, and further preferably 2 to 8 parts by weight with respect to 100 parts by weight of the total of the A component and the B component. is there. If the content of the G component is less than 0.1 parts by weight, sufficient flame retardancy may not be obtained, and if it exceeds 10 parts by weight, weld strength and impact resistance may be reduced.

(Other additives)
In the resin composition of the present invention, various stabilizers for releasing the molecular weight and stabilizing the hue at the time of molding, a release agent, a colorant, a filler other than the D component and the G component can be used.

(I) Stabilizer Various well-known stabilizers can be mix | blended with the resin composition of this invention. Examples of the stabilizer include phosphorus stabilizers, hindered phenol antioxidants, ultraviolet absorbers, and light stabilizers.

(I-1) Phosphorus stabilizer Examples of the phosphorous stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphine. Among these, phosphorous acid, phosphoric acid, phosphonous acid, and phosphonic acid, triorganophosphate compounds, and acid phosphate compounds are particularly preferable. The organic group in the acid phosphate compound includes any of mono-substituted, di-substituted, and mixtures thereof. Any of the following exemplified compounds corresponding to the compound is similarly included.

  Triorganophosphate compounds include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, tridodecyl phosphate, trilauryl phosphate, tristearyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, diphenyl Examples include cresyl phosphate, diphenyl monoorthoxenyl phosphate, and tributoxyethyl phosphate. Among these, trialkyl phosphate is preferable. The carbon number of the trialkyl phosphate is preferably 1 to 22, more preferably 1 to 4. A particularly preferred trialkyl phosphate is trimethyl phosphate.

  Examples of the acid phosphate compound include methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, octyl acid phosphate, decyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, behenyl acid phosphate Nonylphenyl acid phosphate, cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxy polyethylene glycol acid phosphate, bisphenol A acid phosphate, and the like. Among these, long-chain dialkyl acid phosphates having 10 or more carbon atoms are effective for improving thermal stability, and the acid phosphate itself is preferable because of high stability.

  Examples of the phosphite compound include triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl Monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butyl) Phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, distearyl Taerythritol 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 penta Examples include erythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, and dicyclohexylpentaerythritol 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.

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

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

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

  Suitable phosphorus stabilizers are a triorganophosphate compound, an acid phosphate compound, and a phosphite compound represented by the following general formula (7). It is particularly preferable to add a triorganophosphate compound.

（式（７）中、ＲおよびＲ’は炭素数６〜３０のアルキル基または炭素数６〜３０のアリール基を表し、互いに同一であっても異なっていてもよい。）

(In Formula (7), R and R ′ represent an alkyl group having 6 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and may be the same as or different from each other.)

  As described above, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite is preferable as the phosphonite compound, and the stabilizer containing phosphonite as a main component is Sandostab P-EPQ (trademark, manufactured by Clariant). ) And Irgafos P-EPQ (trademark, manufactured by CIBA SPECIALTY CHEMICALS) and both can be used.

  Among the above formulas (7), more preferred phosphite compounds are distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di). -Tert-butyl-4-methylphenyl) pentaerythritol diphosphite, and bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite.

(I-2) Hindered phenolic antioxidant As the hindered phenolic compound, various compounds that are usually blended in resins 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.

  It is preferable that either a phosphorus stabilizer or a hindered phenol antioxidant is blended. In particular, a phosphorus stabilizer is preferably blended, and a triorganophosphate compound is more blended. The content of the phosphorus-based stabilizer and the hindered phenol-based antioxidant is preferably 0.005 to 1 part by weight, more preferably 0.01 to 1 part on the basis of 100 parts by weight of the total of the component A and the component B, respectively. 0.3 parts by weight.

(I-3) Ultraviolet Absorber The resin composition of the present invention can contain an ultraviolet absorber. Since the resin composition of the present invention also has a good hue, such a hue can be maintained for a long time even when used outdoors by blending an ultraviolet absorber.

  In the benzophenone series, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-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 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) ) Methane, 2- Dorokishi -4-n-dodecyloxy benzoin phenone, and such as 2-hydroxy-4-methoxy-2'-carboxy benzophenone may be exemplified.

  In the benzotriazole series, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-Dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2′-methylenebis [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-chlorobenzotriazole, 2- (2-hydroxy-3,5 Di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole, 2- ( 2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2'-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis (1,3-benzoxazine-4 -One), and 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, and 2- (2'-hydroxy-5-methacryloxy) Copolymerization of ethylphenyl) -2H-benzotriazole with vinyl monomer copolymerizable with the monomer And 2- (2′-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole and a copolymer of vinyl monomer copolymerizable with the monomer, 2-hydroxyphenyl-2H-benzotriazole skeleton A polymer having

  In the hydroxyphenyl triazine series, for example, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol, 2- (4,6-diphenyl-1,3,5) -Triazin-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxyphenol, 2- (4,6-diphenyl) -1,3,5-triazin-2-yl) -5-propyloxyphenol and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-butyloxyphenol Illustrated. 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.

  In the cyclic imino ester system, for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) bis (3,1-benzoxazine) -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, based on the total of 100 parts by weight of the component A and the component B. To 1 part by weight, most preferably 0.05 to 0.5 part by weight.

(I-4) Other Heat Stabilizers The resin composition of the present invention may contain other heat stabilizers other than the above phosphorus stabilizers and hindered phenol antioxidants. 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 the 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 content 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 B 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 B. .

(Ii) Mold Release Agent The resin composition of the present invention is further made of a fatty acid ester, a polyolefin wax, a silicone compound, a fluorine compound (polyfluoroethylene) for the purpose of improving productivity during molding and improving dimensional accuracy of a molded product. Fluorine oil represented by alkyl ether, etc.), known release agents such as paraffin wax and beeswax can also be blended. Since the resin composition of the present invention has good fluidity, the pressure propagation is good and a molded article with uniform strain can be obtained. On the other hand, in the case of a molded product having a complicated shape that increases the mold release resistance, the molded product may be deformed at the time of release. The compounding of the specific component solves such a problem without impairing the properties of the resin composition.

  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.

As the polyolefin wax, an ethylene homopolymer having a molecular weight of 1,000 to 10,000, a homopolymer or copolymer of an α-olefin having 3 to 60 carbon atoms, or ethylene and a carbon atom having 3 to 3 carbon atoms. A copolymer with 60 α-olefins is exemplified. 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. A suitable polyolefin wax is an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 60 carbon atoms. 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 release agent is preferably 0.005 to 5 parts by weight, more preferably 0.01 to 4 parts by weight, and still more preferably 0, based on a total of 100 parts by weight of the component A and the component B. 0.02 to 3 parts by weight.

(Iii) Dye and Pigment The resin composition of the present invention can further provide a molded product containing various dyes and pigments and exhibiting various design properties. As dyes and pigments used in the present invention, 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. Also, aluminum powder is suitable as a pigment such as carbon black, titanium oxide, barium sulfate, calcium carbonate, aluminum hydroxide, silicon dioxide, and calcium fluoride, and a metallic pigment. 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 resin molding.
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 B component.

(Iv) Compound having heat absorption ability The resin composition of the present invention may contain a compound having heat absorption ability. Such compounds include phthalocyanine-based near-infrared absorbers, metal oxide-based near-infrared absorbers such as ATO, ITO, iridium oxide, ruthenium oxide, and immonium oxide, and metal borides such as lanthanum boride, cerium boride, and tungsten boride. Preferable examples include various metal compounds having excellent near-infrared absorptivity such as a system and tungsten oxide near-infrared 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 comprises (A) an aromatic polycarbonate resin (component A) 0 to 99% by weight and (B) a polycarbonate-polydiorganosiloxane copolymer resin (component B) 1 to 100% by weight. 0.0005 to 0.2 parts by weight based on 100 parts by weight in total is preferable, 0.0008 to 0.1 parts by weight is more preferable, and 0.001 to 0.07 parts by weight is even 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.

(V) Light diffusing agent The resin composition of the present invention can be provided with a light diffusing effect by blending a light diffusing agent. Examples of the light diffusing agent include polymer fine particles, inorganic fine particles having a low refractive index such as calcium carbonate, and composites thereof. Such polymer fine particles are fine particles already known as light diffusing agents for thermoplastic resins. More preferably, acrylic crosslinked particles having a particle size of several μm, silicone crosslinked particles represented by polyorganosilsesquioxane, and the like are exemplified. Examples of the shape of the light diffusing agent include a spherical shape, a disk shape, a column shape, and an indefinite shape. Such spheres need not be perfect spheres, but include deformed ones, and such columnar shapes include cubes. A preferred light diffusing agent is spherical, and the more uniform the particle size is. The content of the light diffusing agent is preferably 0.005 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, and still more preferably 0.01, based on the total of 100 parts by weight of the component A and the component B. ~ 3 parts by weight. Two or more light diffusing agents can be used in combination.

(Vi) White pigment for high light reflection The 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 B component. Two or more kinds of white pigments for high light reflection can be used in combination.

(Vii) Antistatic agent The resin composition of the present invention may require further antistatic performance, and in such a case, it is preferable to include an antistatic agent. 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 B. 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 B. 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 the total of the A component, B component and C component. 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 the total of 100 parts by weight of the component A and the component B.

(Viii) Other additives The resin composition of the present invention includes A component, thermoplastic resin other than B component, other flow modifiers, antibacterial agents, dispersants such as liquid paraffin, photocatalytic antifouling agent, and A photochromic agent etc. can be mix | blended. Examples of such other resins include polyamide resins, polyimide resins, polyetherimide resins, polystyrene resins, MS resins (copolymer resins mainly composed of methyl methacrylate and styrene), polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylenes. Sulfide resin, polysulfone resin, polyolefin resin such as polyethylene, polypropylene, polystyrene resin, acrylonitrile / styrene copolymer (AS resin), polymethacrylate resin, phenol resin, epoxy resin, cyclic polyolefin resin, polylactic acid resin, polycaprolactone resin, In addition, a resin such as a thermoplastic fluororesin (represented by, for example, polyvinylidene fluoride resin) can be used.

(Production of flame retardant glass fiber reinforced polycarbonate resin composition)
Arbitrary methods are employ | adopted in order to manufacture the flame-retardant glass fiber reinforced polycarbonate resin composition of this invention. For example, A component, B component, C component, D component and optionally other additives are necessary after thoroughly mixing using premixing means such as V-type blender, Henschel mixer, mechanochemical device, extrusion mixer, etc. Depending on the process, the pre-mixture is granulated with an extruding granulator or briquetting machine, then melt kneaded with a melt kneader represented by a vent type twin screw extruder, and then pelletized with a pelletizer. Can be mentioned.
In addition, a method of supplying each component independently to a melt kneader represented by a vent type twin screw extruder, or a part of each component is premixed and then supplied to the melt kneader independently of the remaining components. The method of doing is also mentioned. Examples of the method of premixing a part of each component include a method in which components other than the component A are premixed in advance and then mixed with the component A or directly supplied to the extruder.

  As a premixing method, for example, when a component having a powder form is included as the component A, a part of the powder and an additive to be blended are mixed to produce a master batch of the additive diluted with the powder. A method using a master batch can be mentioned. As a premixing method, for example, when a component having a powder form is included as the component A, a part of the powder and an additive to be blended are mixed to produce a master batch of the additive diluted with the powder. A method using a master batch can be mentioned. Furthermore, the method etc. which supply D component, C component, G component, and arbitrary components independently from the middle of a melt extruder are mentioned. In addition, when there exists a liquid thing in the component to mix | blend, what is called a liquid injection apparatus or a liquid addition apparatus can be used for supply to a melt extruder.

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

  The resin extruded as described above is directly cut into pellets, or after forming strands, the strands are cut with a pelletizer to be pelletized. When it is necessary to reduce the influence of external dust during pelletization, it is preferable to clean the atmosphere around the extruder. Furthermore, in the manufacture of such pellets, various methods already proposed for polycarbonate resin for optical discs are used to narrow the shape distribution of pellets, reduce miscuts, and reduce fine powder generated during transportation or transportation. In addition, it is possible to appropriately reduce bubbles (vacuum bubbles) generated inside the strands and pellets. By these prescriptions, it is possible to increase the molding cycle and reduce the occurrence rate of defects such as silver. Moreover, although the shape of a pellet can take common shapes, such as a cylinder, a prism, and a spherical shape, it is a cylinder more suitably. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and still more preferably 2 to 3.3 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and still more preferably 2.5 to 3.5 mm.

  The flame-retardant glass fiber reinforced polycarbonate resin composition of the present invention can be produced in various products by usually injection-molding pellets produced as described above to obtain molded products. In such injection molding, not only ordinary molding methods but also injection compression molding, injection press molding, gas assist injection molding, foam molding (including a method of injecting a supercritical fluid), insert molding, in-mold coating molding, heat insulation Examples thereof include mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding. In addition, either a cold runner method or a hot runner method can be selected for molding.

  The flame retardant glass fiber reinforced polycarbonate resin composition of the present invention can also be used in the form of various shaped extrusions, 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. Further, the flame-retardant glass fiber reinforced polycarbonate resin composition of the present invention can be formed into a molded product by rotational molding or blow molding.

  As a result, a flame retardant glass fiber reinforced polycarbonate resin composition and a molded product having good mechanical strength, weld strength and flame retardancy, and suppressed impact strength and flame retardancy due to light degradation and wet heat degradation. Provided. That is, according to the present invention, a resin component 100 comprising (A) an aromatic polycarbonate resin (component A) 0 to 99% by weight and (B) a polycarbonate-polydiorganosiloxane copolymer resin (component B) 1 to 100% by weight. (C) 5 to 50 parts by weight of phosphazene compound (component C), (D) The average value of the major axis of the fiber cross section is 10 to 50 μm, and the ratio of the major axis to the minor axis (major axis / minor axis) There is provided a molded article obtained by melt-molding a resin composition which is a flame-retardant glass fiber reinforced polycarbonate resin composition consisting of 40 to 220 parts by weight of a flat cross-section glass fiber (D component) having 3 to 8.

  Molded articles in which the resin composition of the present invention is used include various electronic / electric equipment parts, camera parts, OA equipment parts, precision machine parts, machine parts, vehicle parts, other agricultural materials, transport containers, playground equipment, miscellaneous goods, etc. It is useful for various housings, particularly housings for computers, notebooks, ultrabooks, tablets, and mobile phones, and the industrial effects that it produces are exceptional. Furthermore, various surface treatments can be performed on the molded article made of the 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). Hard coat is a particularly preferred and required surface treatment. In addition, since the resin composition of the present invention has improved metal adhesion, application of vapor deposition and plating is also preferable. The molded product thus provided with the metal layer can be used for electromagnetic wave shielding parts, conductive parts, antenna parts, and the like. Such parts are particularly preferably sheet-like and film-like.

  The flame retardant glass fiber reinforced polycarbonate resin composition of the present invention is excellent in rigidity, impact strength, and flame retardancy, and further has the characteristics of suppressing the impact strength and flame retardance due to light degradation and wet heat degradation. As described above, it is widely useful in various fields such as buildings, building materials, agricultural materials, marine materials, vehicles, electrical / electronic devices, machinery, and especially, computers, notebooks, ultrabooks, tablets, and mobile phones. Useful for telephone housings. Therefore, the industrial effect exhibited by the present invention is extremely great.

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

(1) Evaluation of flame retardant glass fiber reinforced polycarbonate resin composition (1) Flexural modulus Measured according to ISO 178 (measurement condition 23 ° C.). The test piece was molded by an injection molding machine (SG-150U, manufactured by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 280 ° C. and a mold temperature of 70 ° C. The larger this value, the better the rigidity of the resin composition.

(2) Charpy impact strength A test piece (dimensions: length 80 mm × width 10 mm × thickness 4 mm) molded under the same conditions as in (1) above is compliant with ISO 179 in an atmosphere at a temperature of 23 ° C. and a relative humidity of 50% RH. The notched Charpy impact strength was measured by the method. The larger this value, the better the impact resistance of the resin composition.

(3) Flame retardance Based on UL94 standard, UL94 rank was evaluated by thickness 0.5mm and 0.8mm. The test piece was molded by an injection molding machine (SG-150U, manufactured by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 280 ° C. and a mold temperature of 70 ° C.

(4) Light resistance The bending elastic modulus, the notched Charpy impact strength and the flame retardancy after the ultraviolet irradiation under the following conditions were measured by the same method as in the above (1) to (3).
(Xenon arc irradiation conditions)
Equipment used: Atlas Ci4000 (manufactured by Toyo Seiki Seisakusho)
Irradiance: 0.35 W / m ² (at 340 nm)
Black panel temperature: 63 ° C
Humidity: 50% RH
Test time: 500 hours Filter: (outer) borosilicate, (inner) borosilicate

(5) Moisture and heat resistance The flexural modulus, notched Charpy impact strength and flame retardancy after wet heat treatment under the following conditions were measured by the same methods as in (1) to (3) above.
(Wet heat treatment conditions)
Equipment used: PR-3KP (Espec Corp.)
Temperature: 75 ° C
Humidity: 85% RH
Test time: 1,000 hours

[Examples 1-38, Comparative Examples 1-8]
After mixing an aromatic polycarbonate resin, a polycarbonate-polydiorganosiloxane copolymer resin, a phosphazene compound, a flat cross-section glass fiber, and various additives in the blending amounts shown in Tables 1 to 3, using a blender, a vent type twin screw extruder Was used for melt-kneading to obtain pellets. Various additives to be used were prepared in advance by premixing with a polycarbonate resin with a concentration of 10 to 100 times the blending amount as a guide, and then 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 are a discharge rate of 20 kg / h, a screw rotation speed of 150 rpm, a vent vacuum of 3 kPa, and an extrusion temperature of 280 ° C. from the first supply port to the second supply port and 290 ° C. from the second supply port to the die part. did. The reinforcing filler was supplied from the second supply port using the side feeder of the extruder, and the remaining polycarbonate resin and additives were supplied to the extruder from the first 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 in a hot air circulation dryer at 80 ° C. for 5 hours, and then a test piece for evaluation was molded using an injection molding machine. Each evaluation result was shown to Tables 1-3.

Each component of the symbol notation in Tables 1-3 is as follows.
(A component)
A-1: Aromatic polycarbonate resin [polycarbonate resin powder having a viscosity average molecular weight of 19,800 made from bisphenol A and phosgene by a conventional method, Panlite L-1225WX manufactured by Teijin Ltd.]
(B component)
B-1: Polycarbonate-polydiorganosiloxane copolymer resin (viscosity average molecular weight 19,800, PDMS amount 4.2%, PDMS polymerization degree 37)
B-2: Polycarbonate-polydiorganosiloxane copolymer resin (viscosity average molecular weight 19,800, PDMS amount 8.4%, PDMS polymerization degree 37)
B-3: Polycarbonate-polydiorganosiloxane copolymer resin (viscosity average molecular weight 19,800, PDMS amount 4.2%, PDMS polymerization degree 8)
B-4: Polycarbonate-polydiorganosiloxane copolymer resin (viscosity average molecular weight 19,800, PDMS amount 4.2%, PDMS polymerization degree 150)
(C component)
C-1: Cyclic phenoxyphosphazene (Fushimi Pharmaceutical Co., Ltd .: FP-110 (trade name))
C-2: Cross-linked phenoxyphosphazene (SPS-100 (trade name) manufactured by Otsuka Chemical Co., Ltd.)
C-3: Resorcinol bis (di-2,6-xylyl) phosphate (manufactured by Daihachi Chemical Industry Co., Ltd .: PX-200 (trade name))
C-4: Bisphenol A bis (diphenyl phosphate) (manufactured by Daihachi Chemical Industry Co., Ltd .: CR-741 (trade name))
(D component)
D-1: Flat section chopped glass fiber (manufactured by Nitto Boseki Co., Ltd .: CSG 3PA-830, major axis 28 μm, minor diameter 7 μm, cut length 3 mm, epoxy sizing agent)
D-2: chopped glass fiber having a flat cross section (manufactured by Nitto Boseki Co., Ltd .: CSG 3PA-820, major axis 28 μm, minor axis 7 μm, cut length 3 mm, urethane sizing agent)
D-3: Circular cross-section chopped glass fiber (manufactured by Nittobo Co., Ltd .; 3PE937, diameter 13 μm, cut length 3 mm, aminosilane-treated surface treatment and epoxy-based sizing agent)
(E component)
E-1: Polybutylene terephthalate (manufactured by Polyplastics Co., Ltd .: DURANEX 500FP EF202X, IV value: 0.85, terminal carboxyl group: 55 eq / ton)
E-2: Polyethylene terephthalate (manufactured by Teijin Limited: TRN-MTJ, IV value: 0.54, terminal carboxyl group: 18 eq / ton)
E-3: Glycidyl methacrylate (Mitsubrene P-1900 manufactured by Mitsubishi Rayon Co., Ltd.)
E-4: Polyarylate (IV value: 0.64, terminal carboxyl group: 10 eq / ton)
E-5: Bisphenol A type phenoxy resin (Mitsubishi Chemical Corporation: jER1256)
(F component)
F-1: Polytetrafluoroethylene having a fibril forming ability (manufactured by Daikin Industries, Ltd .: Polyflon MPA FA500)
(Other ingredients)
TAL: Talc (Hayashi Kasei Co., Ltd .: UPN HST0.8)
MAC: Mica (Kinsei Tech Co., Ltd .: KDM200)
WSN: Wollastonite (manufactured by NYCO: NYGLOS4)

Claims (10)

  (C) with respect to 100 parts by weight of a resin component consisting of (A) aromatic polycarbonate resin (component A) 0 to 99% by weight and (B) polycarbonate-polydiorganosiloxane copolymer resin (component B) 1 to 100% by weight 5 to 50 parts by weight of a phosphazene compound (component C), and (D) a flat surface having an average major axis of 10 to 50 μm and an average ratio of major axis to minor axis (major axis / minor axis) of 3 to 8 A flame retardant glass fiber reinforced polycarbonate resin composition containing 40 to 220 parts by weight of a cross-sectional glass fiber (component D).   The flame retardant glass fiber reinforced fiber according to claim 1, comprising 5 to 25 parts by weight of (E) adhesion improver (E component) with respect to 100 parts by weight of the total of A component and B component. Polycarbonate resin composition.   The flame retardant glass fiber reinforced polycarbonate resin composition according to claim 2, wherein the E component is an organic compound having one or more functional groups selected from the group consisting of epoxy groups and carboxylic acid groups in one molecule.   The flame retardant glass fiber reinforced polycarbonate resin composition according to claim 3, wherein the E component is one or more organic compounds selected from the group consisting of glycidyl methacrylate, polybutylene terephthalate, polyethylene terephthalate, polyarylate and phenoxy resin.   The flame retardant glass fiber reinforced polycarbonate resin according to any one of claims 1 to 4, wherein the content of the polydiorganosiloxane derived from component B in the resin composition is 0.05 to 5.0% by weight. Composition. The component B is a polycarbonate-polydiorganosiloxane copolymer resin comprising a polycarbonate block represented by the following general formula (1) and a polydiorganosiloxane block represented by the following general formula (3). The flame retardant glass fiber reinforced polycarbonate resin composition described in 1.

[In General Formula (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or 6 to 6 carbon atoms. 20 cycloalkyl groups, cycloalkoxy groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, aryl groups having 3 to 14 carbon atoms, aryloxy groups having 3 to 14 carbon atoms, carbon atoms Represents a group selected from the group consisting of an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. E and f are each an integer of 1 to 4, and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula (2). .

(In the general formula (2), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, carbon Represents a group selected from the group consisting of an aryl group having 3 to 14 atoms and an aralkyl group having 7 to 20 carbon atoms, and R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, or a carbon atom having 1 to 18 carbon atoms. Alkyl groups, alkoxy groups having 1 to 10 carbon atoms, cycloalkyl groups having 6 to 20 carbon atoms, cycloalkoxy groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, and 3 carbon atoms. -14 aryl group, aryloxy group having 6 to 10 carbon atoms, aralkyl group having 7 to 20 carbon atoms, aralkyloxy group having 7 to 20 carbon atoms, nitro group, aldehyde group, cyano group and Represents a group selected from the group consisting of carboxyl groups, and when there are a plurality of them, they may be the same or different, g is an integer of 1 to 10, and h is an integer of 4 to 7).

In (the general formula ^{(3), R 3, R} 4, R 5, R 6, R 7 and ^{R 8} are each independently a hydrogen atom, substituted 6-12 alkyl group carbon atoms or from 1 to 12 carbon atoms Or an unsubstituted aryl group, R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and p is a natural number Q is 0 or a natural number, and p + q is a natural number less than 100. X is a divalent aliphatic group having 2 to 8 carbon atoms.)   It contains 0.01 to 1 part by weight of (F) fluorine-containing anti-dripping agent (F component) with respect to 100 parts by weight of the total of component A and component B. The flame-retardant glass fiber reinforced polycarbonate resin composition described.   It contains 0.1 to 10 parts by weight of (G) silicate compound (G component) with respect to a total of 100 parts by weight of component A and component B. Flame retardant glass fiber reinforced polycarbonate resin composition.   The flame retardant glass fiber reinforced polycarbonate resin composition according to claim 8, wherein the G component is at least one silicate compound selected from the group consisting of talc, mica and wollastonite.   An injection molded product comprising the flame retardant glass fiber reinforced polycarbonate resin composition according to any one of claims 1 to 9.