JP2020079341A - Flame-retardant polycarbonate resin composition - Google Patents

Abstract

To provide a polycarbonate resin composition which satisfies mechanical characteristics, chemical resistance, flame retardancy, high optical reflection, and molded product appearance to a high degree.SOLUTION: The flame-retardant polycarbonate resin composition comprises, relative to 100 pts.wt. of a resin component comprising (A) 30 to 95 pts.wt. of a polycarbonate resin (A component) and (B) 70 to 5 pts.wt. of a polyester resin (B component), (C) 1 to 10 pts.wt. of an impact-modifying agent (C component), (D) 1 to 30 pts.wt. of a flame retardant (D component) containing a phosphate ester, (E) 0.05 to 2 pts.wt. of a drip inhibitor (E component), and (F) 0.1 to 30 pts.wt. of a surface-treated titanium oxide pigment (F component), the surface treatment amount of which is 3 to 8 wt.% relative to the whole pigment.SELECTED DRAWING: None

Description

  The present invention relates to a flame-retardant polycarbonate resin composition and a molded article thereof. More specifically, an impact modifier, a flame retardant containing a phosphoric acid ester, an anti-drip agent, and a titanium oxide pigment surface-treated with a specific amount of a surface treatment agent are added to a resin component composed of a polycarbonate resin and a polyester resin. Thus, the present invention relates to a polycarbonate resin composition having improved mechanical properties, chemical resistance, flame retardancy, high light reflectivity, and appearance of molded articles.

  Since the aromatic polycarbonate resin has excellent mechanical properties and thermal properties, it is used in various applications mainly in the fields of OA equipment and electronic/electric equipment by imparting flame retardancy. .. In recent years, along with thinning and weight reduction in applications such as office automation equipment and home electric appliances, there is an increasing demand for resin materials having high impact, high flame retardancy, and excellent molding appearance. In order to meet these demands, the aromatic polycarbonate resin has been studied for a resin material having a high impact and an excellent molding appearance while satisfying the requirement of UL94, which is a necessary safety standard, for making the flame retardant.

  As a method for imparting high flame retardancy to an aromatic polycarbonate resin, a halogen-based flame retardant such as a bromine compound and a flame retardant auxiliary such as antimony trioxide have been generally used in combination. However, in recent years, due to the problem of generation of harmful substances during combustion, studies on flame retardation using an organic phosphorus flame retardant that does not contain a halogen compound having bromine have become popular. For example, many proposals have been made for compositions in which an organic phosphorus flame retardant and polytetrafluoroethylene having a fibril forming ability are added to an aromatic polycarbonate resin, and the related knowledge is widely known. As a formulation for improving the toughness of an aromatic polycarbonate resin, a method of adding an impact modifier including a graft polymer is known. (See Patent Document 3) Generally, addition of a flame retardant causes a decrease in mechanical properties, and addition of an impact modifier causes a decrease in flame retardancy. Therefore, depending on the balance between the amount of the flame retardant and the impact modifier, a certain range Resin compositions having mechanical properties and flame retardancy have been provided therein. (See Patent Document 4) A resin composition having excellent chemical resistance has been proposed by further applying a polyester resin. However, when titanium oxide is added as a white pigment in an alloy system with a polyester resin, there is a problem that impact strength is significantly reduced, and a resin having excellent mechanical properties, chemical resistance, flame retardancy, and light reflectivity is present. At present, no composition has been obtained.

JP-A-2-199162 JP-A-2-115262 JP, 2009-203269, A JP, 2001-123056, A JP 2000-119500 A

  In view of the above, an object of the present invention is to provide a polycarbonate resin composition which has excellent mechanical properties, chemical resistance, flame retardancy, high light reflectivity, and appearance of a molded article at a high level.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor has found that a resin component composed of a polycarbonate resin and a polyester resin has an impact modifier, a flame retardant containing a phosphate ester, a drip inhibitor and a specific amount of surface treatment. By adding a titanium oxide pigment surface-treated with an agent, a method for obtaining a polycarbonate resin composition having improved mechanical properties, chemical resistance, flame retardancy, high light reflectivity, and molded article appearance, the present invention, It came to completion.

  According to the present invention, the above-mentioned problems are as follows: (A) Polycarbonate resin (A component) 30 to 95 parts by weight and (B) polyester resin (B component) 70 to 5 parts by weight of resin component 100 parts by weight, C) Impact modifier (C component) 1 to 10 parts by weight, (D) Phosphate ester-containing flame retardant (D component) 1 to 30 parts by weight, (E) Drip prevention agent (E component) 0.05 to Difficulty in containing 2 parts by weight and 0.1 to 30 parts by weight of (F) surface-treated titanium oxide pigment (F component) whose surface treatment amount is 3 to 8% by weight based on all pigments. Achieved by a flammable polycarbonate resin composition.

  Hereinafter, details of the present invention will be described.

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

  Typical examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis(4-hydroxyphenyl)ethane, 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-phenylenediisopropylidene)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)fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene. Be done. A preferred dihydric phenol is bis(4-hydroxyphenyl)alkane, and among them, bisphenol A is particularly preferred and widely used from the viewpoint of impact resistance.

  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, 4,4′-(m-phenylenediisopropylidene)diphenol (hereinafter sometimes abbreviated as “BPM”), 1,1-bis(4-hydroxy) as a part or all of the dihydric phenol component. 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 a dimension due to water absorption. It is suitable for applications in which changes and morphological stability are particularly demanding. These dihydric phenols other than BPA are preferably used in an amount of 5 mol% or more, particularly 10 mol% or more, based on the whole dihydric phenol component constituting the polycarbonate.

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

  These special polycarbonates may be used alone or in combination of two or more kinds. Further, these can be used as a mixture with a commonly used bisphenol A type polycarbonate.

  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.

In addition, among the various polycarbonates described above, those having a water absorption rate and a Tg (glass transition temperature) within the following ranges by adjusting the copolymerization 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 morphological stability is required.
(I) Polycarbonate having a water absorption rate of 0.05 to 0.15%, preferably 0.06 to 0.13% and a Tg of 120 to 180°C, or (ii) a Tg of 160 to 250°C, A polycarbonate having a temperature of 170 to 230° C. and 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 polycarbonate is a value obtained by measuring the water content after dipping in water at 23° C. for 24 hours in accordance with ISO62-1980 using a disc-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm. is there. Further, Tg (glass transition temperature) is a value obtained by a differential scanning calorimeter (DSC) measurement based on JIS K7121.

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

  In producing an aromatic polycarbonate resin by the interfacial polymerization method of the dihydric phenol and the carbonate precursor, a catalyst, a terminal stopper, and 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 obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, and a polyester obtained by copolymerizing an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. It includes carbonate resins, copolymerized polycarbonate resins copolymerized with difunctional alcohols (including alicyclic compounds), and polyester carbonate resins copolymerized with such difunctional carboxylic acids and difunctional alcohols. Further, it may be a mixture of two or more kinds of the obtained aromatic polycarbonate resins.

  The branched polycarbonate resin can impart anti-drip performance to the resin composition of the present invention. Examples of the trifunctional or higher-functional polyfunctional aromatic compound used in the branched polycarbonate resin include phloroglucin, phlorogluside, or 4,6-dimethyl-2,4,6-tris(4-hydrodiphenyl)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-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1, Examples thereof include 4-bis(4,4-dihydroxytriphenylmethyl)benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and acid chlorides thereof, and among them, 1,1,1-tris(4-hydroxy) Phenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferable, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferable.

  The constituent unit derived from the polyfunctional aromatic compound in the branched polycarbonate is preferably 100 mol% in total of the constituent unit derived from the dihydric phenol and the constituent unit derived from the polyfunctional aromatic compound, preferably It is 0.01 to 1 mol %, more preferably 0.05 to 0.9 mol %, and further preferably 0.05 to 0.8 mol %.

  Further, particularly 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 also preferably 100 mol% in total with the structural unit derived from the dihydric phenol, preferably. It is preferably 0.001 to 1 mol %, more preferably 0.005 to 0.9 mol %, and further preferably 0.01 to 0.8 mol %. The ratio of the branched structure can be calculated by 1H-NMR measurement.

  The aliphatic difunctional carboxylic acid is preferably α,ω-dicarboxylic acid. Examples of the aliphatic difunctional carboxylic acid include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosanedioic acid, and cyclohexanedicarboxylic acid. Preferred are alicyclic dicarboxylic acids such as An alicyclic diol is more preferable as the difunctional alcohol, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.

  The reaction modes such as the interfacial polymerization method, the melt transesterification method, the carbonate prepolymer solid phase transesterification method, and the ring-opening polymerization method of the cyclic carbonate compound, which are the production methods of the polycarbonate resin of the present invention, include various documents and patent publications. Is a well known method.

In producing the flame-retardant polycarbonate resin composition of the present invention, the viscosity average molecular weight (M) of the polycarbonate resin is not particularly limited, but is preferably 1.8×10 ^{4 to} 4.0×10 ⁴ , and more preferably It is preferably 2.0×10 ^{4 to} 3.5×10 ⁴ , and more preferably 2.2×10 ^{4 to} 3.0×10 ⁴ . With a polycarbonate resin having a viscosity average molecular weight of less than 1.8×10 ⁴ , good mechanical properties may not be obtained in some cases. On the other hand, a resin composition obtained from a polycarbonate resin having a viscosity average molecular weight of more than 4.0×10 ⁴ is inferior in versatility because it is inferior in fluidity during injection molding.

The polycarbonate resin may be obtained by mixing those having a viscosity average molecular weight outside the above range. In particular, a polycarbonate resin having a viscosity average molecular weight exceeding the above range (5×10 ⁴ ) improves the entropy elasticity of the resin. As a result, good moldability is exhibited in gas assist molding and foam molding, which are sometimes used when molding a reinforced resin material into a structural member. Such improvement in moldability is even better than the branched polycarbonate. In a more preferred embodiment, the component A is a polycarbonate resin having a viscosity average molecular weight of 7×10 ^{4 to} 3×10 ^{5 and} a component having a viscosity average molecular weight of 1×10 ^{4 to} 3×10 ⁴ . Polycarbonate resin (A-1-1 component) (hereinafter referred to as "A-1-1 component") composed of a group polycarbonate resin (A-1-1-2 component) and having a viscosity average molecular weight of 1.6 x 10 ^{4 to} 3.5 x 10 ^4. Polycarbonate resin containing a high molecular weight component" may also be used).

In such a high molecular weight component-containing polycarbonate resin (A-1-1 component), the molecular weight of the A-1-1-1 component is preferably 7×10 ⁴ to 2×10 ⁵ , and more preferably 8×10 ⁴ to 2×. 10 ⁵ , more preferably 1×10 ⁵ to 2×10 ⁵ , and particularly preferably 1×10 ^{5 to} 1.6×10 ⁵ . The molecular weight of the component A-1-1-2 is preferably 1×10 ^{4 to} 2.5×10 ⁴ , more preferably 1.1×10 ^{4 to} 2.4×10 ⁴ , and even more preferably 1.2×. 10 ^{4 to} 2.4×10 ⁴ , particularly preferably 1.2×10 ^{4 to} 2.3×10 ⁴ .

  The high-molecular weight component-containing polycarbonate resin (A-1-1 component) is prepared by mixing the above-mentioned A-1-1-1 component and A-1-1-2 component in various proportions so as to satisfy a predetermined molecular weight range. You can get it. Preferably, the A-1-1 component is 2 to 40% by weight in 100% by weight of the A-1-1 component, and more preferably 3 to 30% by weight of the A-1-1-1 component. Is more preferable, the A-1-1-1 component is 4 to 20% by weight, and particularly preferably the A-1-1-1 component is 5 to 20% by weight.

  As the method for preparing the A-1-1 component, (1) a method of independently polymerizing the A-1-1-1 component and the A-1-1-2 component and mixing them, (2) ) A method for producing an aromatic polycarbonate resin showing a plurality of polymer peaks in a molecular weight distribution chart by the GPC method in the same system, which is represented by JP-A-5-306336, is used. To satisfy the condition of the component A-1-1 of the present invention, and (3) the aromatic polycarbonate resin obtained by the production method (production method of (2)), and A produced separately. Examples include a method of mixing the 1-1-1 component and/or the A-1-1-2 component.

The viscosity average molecular weight as used in the present invention is obtained by first using a Ostwald viscometer to calculate a specific viscosity (η _SP ) calculated by the following formula from a solution prepared by dissolving 0.7 g of polycarbonate in 100 ml of methylene chloride at 20° C.
Specific viscosity (η _SP )=(t−t ₀ )/t ₀
[T ₀ is the number of seconds of methylene chloride drop, t is the number of seconds of drop of sample solution]
The viscosity average molecular weight M is calculated from the determined specific viscosity (η _SP ) by the following mathematical formula.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η]=1.23×10 ⁻⁴ M ^0.83
c=0.7

  The viscosity average molecular weight of the polycarbonate resin in the flame-retardant polycarbonate resin composition of the present invention is calculated as follows. That is, the composition is mixed with 20 to 30 times its weight of methylene chloride to dissolve the soluble component in the composition. The soluble matter is collected by Celite filtration. After that, the solvent in the obtained solution is removed. After removing the solvent, the solid is sufficiently dried to obtain a solid of a component soluble in methylene chloride. A specific viscosity at 20° C. is obtained from a solution prepared by dissolving 0.7 g of the solid in 100 ml of methylene chloride in the same manner as above, and the viscosity average molecular weight M is calculated from the specific viscosity in the same manner as above.

  A polycarbonate-polydiorganosiloxane copolymer resin can also be used as the polycarbonate resin (component A) of the present invention. The polycarbonate-polydiorganosiloxane copolymer resin is a copolymer prepared by copolymerizing a dihydric phenol represented by the following general formula (1) and a hydroxyaryl-terminated polydiorganosiloxane represented by the following general formula (3). It is preferably a polymer resin.

［上記一般式（１）において、Ｒ^１及びＲ^２は夫々独立して水素原子、ハロゲン原子、炭素原子数１〜１８のアルキル基、炭素原子数１〜１８のアルコキシ基、炭素原子数６〜２０のシクロアルキル基、炭素原子数６〜２０のシクロアルコキシ基、炭素原子数２〜１０のアルケニル基、炭素原子数６〜１４のアリール基、炭素原子数６〜１４のアリールオキシ基、炭素原子数７〜２０のアラルキル基、炭素原子数７〜２０のアラルキルオキシ基、ニトロ基、アルデヒド基、シアノ基及びカルボキシル基からなる群から選ばれる基を表し、それぞれ複数ある場合はそれらは同一でも異なっていても良く、ｅ及びｆは夫々１〜４の整数であり、Ｗは単結合もしくは下記一般式（２）で表される基からなる群より選ばれる少なくとも一つの基である。］

[In the 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 group, C6-20 cycloalkoxy group, C2-10 alkenyl group, C6-14 aryl group, C6-14 aryloxy group, carbon atom 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, and when there are a plurality of groups, they are the same or different. 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). ]

［上記一般式（２）においてＲ^１１，Ｒ^１２，Ｒ^１３，Ｒ^１４，Ｒ^１５，Ｒ^１６，Ｒ^１７及びＲ^１８は夫々独立して水素原子、炭素原子数１〜１８のアルキル基、炭素原子数６〜１４のアリール基及び炭素原子数７〜２０のアラルキル基からなる群から選ばれる基を表し、Ｒ^１９及びＲ^２０は夫々独立して水素原子、ハロゲン原子、炭素原子数１〜１８のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数６〜２０のシクロアルキル基、炭素原子数６〜２０のシクロアルコキシ基、炭素原子数２〜１０のアルケニル基、炭素原子数６〜１４のアリール基、炭素原子数６〜１０のアリールオキシ基、炭素原子数７〜２０のアラルキル基、炭素原子数７〜２０のアラルキルオキシ基、ニトロ基、アルデヒド基、シアノ基及びカルボキシル基からなる群から選ばれる基を表し、複数ある場合はそれらは同一でも異なっていても良く、ｇは１〜１０の整数、ｈは４〜７の整数である。］

[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, or a carbon atom. Represents a group selected from the group consisting of an aryl group having 6 to 14 atoms and an aralkyl group having 7 to 20 carbon atoms, wherein R ¹⁹ and R ²⁰ are each independently a hydrogen atom, a halogen atom, or a carbon atom number of 1 to 18; Alkyl group having 1 to 10 carbon atoms, cycloalkyl group having 6 to 20 carbon atoms, cycloalkoxy group having 6 to 20 carbon atoms, alkenyl group having 2 to 10 carbon atoms, and 6 carbon atoms From an aryl group having 14 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, 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. It represents a group selected from the group consisting of two or more, and when there are a plurality of groups, they may be the same or different, g is an integer of 1 to 10, and h is an integer of 4 to 7. ]

［上記一般式（３）において、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、各々独立に水素原子、炭素数１〜１２のアルキル基又は炭素数６〜１２の置換若しくは無置換のアリール基であり、Ｒ^９及びＲ^１０は夫々独立して水素原子、ハロゲン原子、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基であり、ｐは自然数であり、ｑは０又は自然数であり、ｐ＋ｑは１０〜３００の自然数である。Ｘは炭素数２〜８の二価脂肪族基である。］

[In the general formula (3), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbons or a substituent having 6 to 12 carbons. Alternatively, it is 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, 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 of 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms. ]

  Examples of the dihydric phenol (I) 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-isopropyl) Phenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(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'-dihydroxydiphenylether, 4,4' -Dihydroxy-3,3'-dimethyldiphenylether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfide, 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'-diphenyldiphenylsulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenylsulfide, 1,3-bis{2-(4-hydroxyphenyl) )Propyl}benzene, 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis(4-hydro) Xyphenyl)cyclohexane, 1,3-bis(4-hydroxyphenyl)cyclohexane, 4,8-bis(4-hydroxyphenyl)tricyclo[5.2.1.02,6]decane, 4,4'-(1, Examples thereof include 3-adamantanediyl)diphenol and 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane.

  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′-. Sulfonyldiphenol and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene are preferred. Of these, 2,2-bis(4-hydroxyphenyl)propane, which has excellent strength and good durability, is most suitable. These may be used alone or in combination of two or more.

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

  The hydroxyaryl-terminated polydiorganosiloxane (II) is a phenol having an olefinic unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, or 2-methoxy-4-allylphenol. It is easily produced by subjecting the end of the polysiloxane chain having the degree of polymerization of 1 to a hydrosilation reaction. Among them, (2-allylphenol)-terminated polydiorganosiloxane and (2-methoxy-4-allylphenol)-terminated polydiorganosiloxane are preferable, and particularly (2-allylphenol)-terminated polydimethylsiloxane and (2-methoxy-4). Preferred are allylphenol)-terminated polydimethylsiloxanes. The hydroxyaryl-terminated polydiorganosiloxane (II) preferably has a molecular weight distribution (Mw/Mn) of 3 or less. The molecular weight distribution (Mw/Mn) is more preferably 2.5 or less, still more preferably 2 or less, in order to exhibit more excellent low outgassing property and high temperature impact resistance during high temperature molding. When the amount exceeds the upper limit of the preferable range, the amount of outgas generated during high temperature molding is large and the low temperature impact resistance may be poor.

  Further, in order to realize a high degree of impact resistance, the degree of polymerization (p+q) of diorganosiloxane of hydroxyaryl-terminated polydiorganosiloxane (II) is appropriately 10 to 300. The diorganosiloxane polymerization degree (p+q) is preferably 10 to 200, more preferably 12 to 150, and still more preferably 14 to 100. Below the lower limit of this preferred range, the impact resistance, which is a characteristic of the polycarbonate-polydiorganosiloxane copolymer, will not be manifested effectively, and above the upper limit of this preferred range, poor appearance will appear.

  The content of the polydiorganosiloxane in the total weight of the polycarbonate-polydiorganosiloxane copolymer resin used as the component A is preferably 0.1 to 50% by weight. The content of the polydiorganosiloxane component is more preferably 0.5 to 30% by weight, further preferably 1 to 20% by weight. Above the lower limit of this preferred range, the impact resistance and flame retardancy are excellent, and below the upper limit of this preferred range, a stable appearance that is less susceptible to molding conditions is likely to be obtained. The polydiorganosiloxane polymerization degree and the polydiorganosiloxane content can be calculated by 1H-NMR measurement.

  In the present invention, the hydroxyaryl-terminated polydiorganosiloxane (II) may be used alone or in combination of two or more.

  Further, other than the above dihydric phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II), a comonomer other than the dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) is contained in an amount of 10% by weight or less based on the total weight of the copolymer. It can also be used together.

  In the present invention, a mixed solution containing an oligomer having a terminal chloroformate group is prepared in advance by reacting a dihydric phenol (I) with a carbonic acid ester forming compound in a mixed solution of a water-insoluble organic solvent and an alkaline aqueous solution. To do.

  In producing the oligomer of the dihydric phenol (I), the entire amount of the dihydric phenol (I) used in the method of the present invention may be converted into the oligomer at one time, or a part of the dihydric phenol (I) may be used as a post-added monomer to form a post-stage interface. You may add as a reaction raw material to a polycondensation reaction. The post-addition monomer is added in order to accelerate the subsequent polycondensation reaction, and it is not necessary to intentionally add it when it is not necessary.

  The method of this oligomer formation reaction is not particularly limited, but a method performed in a solvent in the presence of an acid binder is usually preferable.

  The proportion of the carbonic acid ester forming compound used may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. When a gaseous carbonic acid ester-forming compound such as phosgene is used, a method of blowing it into the reaction system can be suitably adopted.

  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 proportion of the acid binder used may be appropriately determined in consideration of the stoichiometric ratio (equivalent weight) of the reaction, similarly to the above. Specifically, it is preferable to use 2 equivalents or slightly excess amount of the acid binder with respect to the number of moles of dihydric phenol (I) used for forming the oligomer (usually 1 mole corresponds to 2 equivalents). ..

  As the solvent, solvents that are inert to various reactions such as those used in the production of known polycarbonates may be used alone or as a mixed solvent. Typical examples include hydrocarbon solvents such as xylene and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. Particularly, a halogenated hydrocarbon solvent such as methylene chloride is preferably used.

  The reaction pressure for oligomer formation is not particularly limited and may be normal pressure, increased pressure or reduced pressure, 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 water cooling or ice cooling is desirable. The reaction time depends on other conditions and cannot be specified unconditionally, but is usually 0.2 to 10 hours. The pH range of the oligomer formation reaction is similar to known interfacial reaction conditions, and the pH is always adjusted to 10 or higher.

  According to the present invention, a mixed solution containing an oligomer of a dihydric phenol (I) having a terminal chloroformate group is thus obtained, and then the mixed solution is stirred to have a molecular weight distribution (Mw/Mn) of 3 or less. The highly purified hydroxyaryl-terminated polydiorganosiloxane (II) represented by the general formula (4) is added to the dihydric phenol (I), and the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer are subjected to interfacial polycondensation. Thus, a polycarbonate-polydiorganosiloxane copolymer is obtained.

（上記一般式（４）において、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、各々独立に水素原子、炭素数１〜１２のアルキル基又は炭素数６〜１２の置換若しくは無置換のアリール基であり、Ｒ^９及びＲ^１０は夫々独立して水素原子、ハロゲン原子、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基であり、ｐは自然数であり、ｑは０又は自然数であり、ｐ＋ｑは１０〜３００の自然数である。Ｘは炭素数２〜８の二価脂肪族基である。）

(In the above general formula (4), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbons or a substituent having 6 to 12 carbons. Alternatively, it is 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, an alkoxy group having 1 to 10 carbon atoms, and p is a natural number. , Q is 0 or a natural number, p+q is a natural number of 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms.)

  When carrying out the interfacial polycondensation reaction, an acid binder may be appropriately added in consideration of the stoichiometric ratio (equivalent amount) 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 the hydroxyaryl-terminated polydiorganosiloxane (II) to be used or a part of the dihydric phenol (I) as described above is added as a post-added monomer to this reaction step, the amount of the post-added component It is preferable to use 2 equivalents or an excess of alkali with respect to the total number of moles of the polyhydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) (usually 1 mole corresponds to 2 equivalents).

  Polycondensation by an interfacial polycondensation reaction between an oligomer of dihydric phenol (I) and a hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the above mixed solution.

  In such a polymerization reaction, a terminal stopper or a molecular weight modifier is usually used. Examples of the terminal terminator include compounds having a monovalent phenolic hydroxyl group, and in addition to ordinary phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, etc., long-chain alkylphenol, aliphatic carboxylic acid. Examples thereof include chloride, aliphatic carboxylic acid, hydroxybenzoic acid alkyl ester, hydroxyphenylalkyl acid ester, and alkyl ether phenol. 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.

  A catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt may be added to accelerate the polycondensation reaction.

  The reaction time of the polymerization reaction is preferably 30 minutes or more, more preferably 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 give a branched polycarbonate-polydiorganosiloxane. Examples of the trifunctional or higher-functional polyfunctional aromatic compound used in the branched polycarbonate-polydiorganosiloxane copolymer resin include phloroglucin, phloroglucide, or 4,6-dimethyl-2,4,6-tris(4-hydrodiphenyl). ) 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, Trisphenol such as 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxy) Phenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acid chlorides, among others, 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 particularly preferable. .. The proportion 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. 0.99 mol%, more preferably 0.01 to 0.8 mol%, and particularly preferably 0.05 to 0.4 mol%. The amount of the branched structure can be calculated by 1H-NMR measurement.

  The reaction pressure may be any of reduced pressure, normal pressure and increased pressure, but normally, it can be preferably carried out at normal pressure or at about the self 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 water cooling or ice cooling is desirable. The reaction time varies depending on other conditions such as reaction temperature and therefore cannot be specified unconditionally, but it is usually 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 achieve the desired reduction. It can also be obtained as a polycarbonate-polydiorganosiloxane copolymer resin having a viscosity [ηSP/c].

  The obtained reaction product (crude product) can be recovered as a polycarbonate-polydiorganosiloxane copolymer resin having a desired purity (purification degree) by performing various post-treatments such as a known separation and purification method.

  The average size of the polydiorganosiloxane domains in the polycarbonate-polydiorganosiloxane copolymer resin molded article is preferably in the range of 1 to 60 nm. The average size is more preferably 3 to 55 nm, further preferably 5 to 50 nm. If it is less than the lower limit of the preferable range, impact resistance and flame retardancy may not be sufficiently exhibited, and if it exceeds the upper limit of the preferable range, impact resistance may not be stably exhibited. This provides a flame-retardant polycarbonate resin composition excellent in impact resistance and appearance.

(B component: polyester resin)
The polyester resin (component B) used in the flame-retardant polycarbonate resin composition of the present invention is a polymer obtained by a condensation reaction containing an aromatic dicarboxylic acid or its reactive derivative and a diol or its ester derivative as main components. It is preferably a copolymer.

  Examples of the aromatic dicarboxylic acid used herein include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-biphenyl ether. Dicarboxylic acid, 4,4'-biphenylmethane dicarboxylic acid, 4,4'-biphenyl sulfone dicarboxylic acid, 4,4'-biphenyl isopropylidene dicarboxylic acid, 1,2-bis(phenoxy)ethane-4,4'-dicarboxylic acid Aromatic dicarboxylic acids such as acid, 2,5-anthracene dicarboxylic acid, 2,6-anthracene dicarboxylic acid, 4,4′-p-terphenylenedicarboxylic acid and 2,5-pyridinedicarboxylic acid are preferably used, Particularly, terephthalic acid and 2,6-naphthalenedicarboxylic acid can be preferably used.

  The aromatic dicarboxylic acid may be used as a mixture of two or more kinds. If the amount is small, it is also possible to use a mixture of one or more adipic acid, azelaic acid, sebacic acid, an aliphatic dicarboxylic acid such as dodecanedioic acid, or an alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid together with the dicarboxylic acid. ..

  Examples of the diol which is a component of the polyester resin of the present invention include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, 2-methyl-1,3. -Containing aliphatic diols such as propanediol, diethylene glycol and triethylene glycol, alicyclic diols such as 1,4-cyclohexanedimethanol, and aromatic rings such as 2,2-bis(β-hydroxyethoxyphenyl)propane Examples thereof include diols and the like and mixtures thereof. If the amount is small, one or more long chain diols having a molecular weight of 400 to 6,000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc. may be copolymerized.

  The polyester resin of the present invention can be branched by introducing a small amount of a branching agent. The type of branching agent is not limited, but examples thereof include trimesic acid, trimellitic acid, trimethylolethane, trimethylolpropane, and pentaerythritol.

  Specific polyester resins include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyhexylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyethylene-1,2- In addition to bis(phenoxy)ethane-4,4′-dicarboxylate and the like, copolymerized polyester resins such as polyethylene isophthalate/terephthalate, polybutylene terephthalate/isophthalate and the like can be mentioned. Among these, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate and a mixture thereof, which are well-balanced in mechanical properties and the like, can be preferably used, and in particular, the mixed use of polyethylene terephthalate and polybutylene terephthalate has an impact. It is preferable in terms of strength and chemical resistance. The use (weight) ratio of polyethylene terephthalate and polybutylene terephthalate is preferably polyethylene terephthalate/polybutylene terephthalate in the range of 40/60 to 95/5, and particularly in the range of 50/50 to 90/10. Is preferred.

  Further, the terminal group structure of the obtained polyester resin is not particularly limited, and may be one in which the ratio of the hydroxyl group and the carboxyl group in the terminal group is large, in addition to the case where the ratio is almost the same. Further, those terminal groups may be sealed by reacting a compound having reactivity with such terminal groups.

  Regarding the method for producing such a polyester resin, in accordance with a conventional method, in the presence of a polycondensation catalyst containing titanium, germanium, antimony, etc., the dicarboxylic acid component and the diol component are polymerized while heating to produce water or a by-product. It is performed by discharging lower alcohol out of the system. For example, as the germanium-based polymerization catalyst, germanium oxide, hydroxide, halide, alcoholate, phenolate and the like can be exemplified, and more specifically, germanium oxide, germanium hydroxide, germanium tetrachloride, tetramethoxygermanium, etc. Can be illustrated. Further, in the present invention, compounds such as manganese, zinc, calcium and magnesium used in the transesterification reaction which is a prior stage of polycondensation which is conventionally known can be used in combination, and phosphoric acid or phosphorous acid can be used after the transesterification reaction. It is also possible to deactivate such a catalyst and perform polycondensation with the compound or the like.

  Regarding the molecular weight of the polyester resin, the intrinsic viscosity measured at 25° C. using o-chlorophenol as a solvent is preferably 0.4 to 1.2, and more preferably 0.65 to 1.15. ..

  The content of the B component is 70 to 5 parts by weight, preferably 50 to 10 parts by weight, and more preferably 40 to 20 parts by weight in 100 parts by weight of the total of the A component and the B component. When the content of the component B is less than 5 parts by weight, sufficient chemical resistance cannot be obtained, and when it exceeds 70 parts by weight, impact resistance and flame retardancy decrease.

(C component: impact modifier)
The flame-retardant polycarbonate resin composition of the present invention contains an impact modifier as the C component. The impact modifier is a graft copolymer obtained by copolymerizing one kind of rubber selected from the group consisting of butadiene rubber, acrylic rubber and silicone-acrylic composite rubber with a monomer copolymerizable therewith, especially The monomer is preferably at least one selected from the group consisting of a graft polymer, which is at least one compound containing a (meth)acrylic acid ester compound, and a glycidyl group-containing polyethylene copolymer, and a core-shell structure Is more preferred. The core-shell type graft polymer comprises a rubber component having a glass transition temperature of 10° C. or lower as a core, a (meth)acrylic acid ester compound, an aromatic alkenyl compound and other monomers selected from vinyl compounds copolymerizable therewith. It is a graft copolymer obtained by copolymerizing one kind or two or more kinds as a shell.

  Examples of the C component rubber component include butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, silicone-acrylic composite rubber, isobutylene-silicone composite rubber, isoprene rubber, styrene-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, Nitrile rubber, ethylene-acrylic rubber, silicone rubber, epichlorohydrin rubber, fluororubber, and those in which hydrogen is added to the unsaturated bond portion thereof can be mentioned, but from the viewpoint of concern about the generation of harmful substances during combustion. A rubber component containing no halogen atom is preferable in terms of environmental load. Further, the glass transition temperature of the rubber component is preferably −10° C. or lower, more preferably −30° C. or lower. From these points, butadiene rubber and acrylic silicone-acrylic composite rubber are particularly preferable as the rubber component. The composite rubber means a rubber obtained by copolymerizing two kinds of rubber components or a rubber obtained by polymerizing so as to have an IPN structure in which they are intertwined with each other so that they cannot be separated. In the core-shell type graft polymer, the particle diameter of the core is preferably 240 to 300 nm, more preferably 250 to 290 nm, and further preferably 260 to 280 nm in terms of weight average particle diameter. In the range of 240 to 300 nm, better impact resistance is achieved. Further, the particle size distribution is preferably a polydisperse type having two peaks, particularly preferably a polydisperse type having two peaks near 100 nm and 300 nm, and a better impact resistance than a monodisperse type having a single peak is achieved. It

  Examples of the aromatic vinyl in the vinyl compound copolymerized with the rubber component as the shell of the core-shell type graft polymer include styrene, α-methylstyrene, p-methylstyrene, alkoxystyrene and halogenated styrene. Examples of the acrylate ester include methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, octyl acrylate, and the like, and examples of the methacrylate ester include methyl methacrylate, ethyl methacrylate, butyl methacrylate. , Cyclohexyl methacrylate, octyl methacrylate, etc., and methyl methacrylate is particularly preferable. Among these, it is particularly preferable to contain a methacrylic acid ester such as methyl methacrylate as an essential component, and it is more preferable not to include an aromatic vinyl component from the viewpoint of mechanical properties and flame retardancy. This is because the core-shell type graft polymer has excellent affinity with the aromatic polycarbonate resin, so that more rubber component is present in the resin, and the good impact resistance of the aromatic polycarbonate resin is obtained. This is because it is more effectively exhibited, and as a result, the impact resistance of the resin composition is improved. More specifically, the methacrylic acid ester is contained in 100% by weight of the graft component (in the case of the core-shell type polymer, 100% by weight of the shell), preferably 10% by weight or more, and more preferably 15% by weight or more. Is preferred. The elastic polymer containing a rubber component having a glass transition temperature of 10° C. or lower may be produced by any of bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. It does not matter whether it is a single-stage graft or a multi-stage graft. Further, it may be a mixture with a copolymer having only a graft component produced as a by-product during the production. Examples of the polymerization method include a general emulsion polymerization method, a soap-free polymerization method using an initiator such as potassium persulfate, a seed polymerization method, and a two-step swelling polymerization method. Further, in the suspension polymerization method, a method in which an aqueous phase and a monomer phase are separately held and both are accurately supplied to a continuous disperser, and the particle diameter is controlled by the rotation speed of the disperser, and continuous production In the method, a method of controlling the particle size by supplying the monomer phase in an aqueous liquid having a dispersibility by passing it through a small orifice having a diameter of several to several tens of μm or a porous filter may be used. In the case of a core-shell type graft polymer, the reaction may be carried out in either a single stage or multiple stages for both the core and the shell.

  Such polymers are commercially available and can be easily obtained. For example, as the rubber component, those containing butadiene rubber as the main component are those of Metabrene E series manufactured by Mitsubishi Chemical Corporation (for example, E-875A containing methyl methacrylate as the main component as the shell component, and methyl methacrylate/styrene as the main component as the shell component). E-870A as a component). Examples of those containing acrylic rubber as a main component include W series manufactured by Mitsubishi Chemical Corporation (for example, W-600A whose shell component contains methyl methacrylate as a main component). Examples of those having a silicone-acrylic composite rubber as a main component include Metabrene S series manufactured by Mitsubishi Chemical Corporation (for example, S-2001 and S-2030 whose main shell component is methyl methacrylate).

  The content of the component C is 1 to 10 parts by weight, preferably 1.5 to 9 parts by weight, more preferably 2 to 8 parts by weight, based on 100 parts by weight of the resin component composed of the components A and B. .. If the content of the C component is less than 1 part by weight, sufficient mechanical properties cannot be obtained, and if it exceeds 10 parts by weight, the flame retardancy and the appearance of the molded product deteriorate.

(Component D: flame retardant containing phosphate ester)
Examples of the flame retardant containing a phosphoric acid ester used as the D component of the present invention include one or more phosphoric acid ester compounds represented by the following formula (5).

In the formula, X ¹ is hydroquinone, resorcinol, bis(4-hydroxydiphenyl)methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)ketone, bis(4-hydroxyphenyl)ketone. It is a group derived from hydroxyphenyl) sulfide. n ¹ is an integer of 0 to 5, or an average value of 0 to 5 in the case of a mixture of phosphoric acid esters having different numbers of n ¹ . R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are each independently derived from phenol, cresol, xylenol, isopropylphenol, butylphenol, p-cumylphenol substituted or unsubstituted with at least one halogen atom. It is a base. More preferably, X ¹ in the formula is a group derived from hydroquinone, resorcinol, bisphenol A, and dihydroxydiphenyl, n ¹ is an integer of ¹ to 3, or n ^{1 is} a different phosphoric acid. In the case of a blend of esters, it is the average value thereof, and R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are each independently a phenol or cresol in which one or more halogen atoms are substituted or more preferably unsubstituted. , A group derived from xylenol.

  Among such organic phosphate ester flame retardants, triphenyl phosphate is used as the phosphate compound, and resorcinol bis(dixylenyl phosphate) and bisphenol A bis(diphenyl phosphate) are used as the phosphate oligomer because they are excellent in hydrolysis resistance and the like. Can be used. More preferred are resorcinol bis(dixylenyl phosphate) and bisphenol A bis(diphenyl phosphate) from the viewpoint of heat resistance. This is because these materials also have good heat resistance, so that they do not have any adverse effects such as thermal deterioration or volatilization.

  The content of the D component is 1 to 30 parts by weight, more preferably 5 to 20 parts by weight, and further preferably 10 to 15 parts by weight with respect to 100 parts by weight of the resin component composed of the A component and the B component. If the content is less than 1 part by weight, flame retardancy cannot be obtained, and if it exceeds 30 parts by weight, sufficient mechanical properties cannot be obtained.

(E component: anti-drip agent)
The flame-retardant polycarbonate resin composition of the present invention contains an anti-drip agent as the E component. By containing this anti-drip agent, good flame retardancy can be achieved without impairing the physical properties of the molded product.

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

  The molecular weight of PTFE having a fibril-forming ability is extremely high, and it tends to bond PTFEs to each other by an external action such as shearing force to form a fibrous form. Its molecular weight is preferably 1,000,000 to 10,000,000, more preferably 2,000,000 to 9,000,000 in terms of the number average molecular weight obtained from standard specific gravity. In addition to the solid form, such PTFE may be used in the form of an aqueous dispersion. Further, PTFE having such fibril-forming ability improves dispersibility in a 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 manufactured by Mitsui DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500 and F-201L manufactured by Daikin Industries, Ltd., and the like. Commercially available aqueous dispersions of PTFE include Fluon AD-1 and AD-936 manufactured by Asahi IC Polymers Co., Ltd., Fluon D-1 and D-2 manufactured by Daikin Industries, Ltd., and Mitsui DuPont Fluoro. Typical examples thereof include Teflon (registered trademark) 30J manufactured by Chemical Co., Ltd.

  As the 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 (JP-A-60-258263, Japanese Unexamined Patent Publication No. 63-154744, etc.), (2) A method of mixing an aqueous dispersion of PTFE with dried organic polymer particles (the method described in Japanese Unexamined Patent Publication No. 4-272957) (3) A method in which an aqueous dispersion of PTFE and an organic polymer particle solution are uniformly mixed, and respective media are simultaneously removed from the mixture (JP-A 06-220210, JP-A 08-188653, etc.). Described method), (4) a method of polymerizing a monomer forming an organic polymer in an aqueous dispersion of PTFE (method described in JP-A-9-95583), and (5) PTFE A method of uniformly mixing the aqueous dispersion and the organic polymer dispersion, further polymerizing a vinyl monomer in the mixed dispersion, and then obtaining a mixture (method described in JP-A No. 11-29679). What was obtained by can be used. Commercially available products of these mixed forms of PTFE include "METABLEN A3800" (trade name) manufactured by Mitsubishi Rayon Co., Ltd., and "BLENDEX B449" (trade name) manufactured by GE Specialty Chemicals.

  The proportion of PTFE in the mixed form is preferably 1 to 60% by weight, and more preferably 5 to 55% by weight, based on 100% by weight of the PTFE mixture. When the proportion of PTFE is in such a range, good dispersibility of PTFE can be achieved. The ratio of the above-mentioned F component shows a net amount of the anti-drip agent, and in the case of PTFE in a mixed form, it shows a net amount of PTFE.

  The content of the E component is 0.05 to 2 parts by weight, preferably 0.1 to 1.5 parts by weight, and more preferably 0.1% to 100 parts by weight of the resin component composed of the A component and the B component. 2 to 1 part by weight. If the amount of the anti-drip agent exceeds the above range and is too small, the flame retardancy becomes insufficient. On the other hand, when the amount of the anti-drip agent exceeds the above range and is too much, not only the PTFE is deposited on the surface of the molded article and the appearance is deteriorated, but also the cost of the resin composition is increased.

  The styrene-based monomer used in the organic polymer used in the polytetrafluoroethylene-based mixture of the present invention includes an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen. Styrene optionally substituted with one or more groups selected from the group consisting of, for example, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, dimethylstyrene, ethyl-styrene, para-tert-butylstyrene. Examples include, but are not limited to, methoxystyrene, fluorostyrene, monobromostyrene, dibromostyrene, and tribromostyrene, vinylxylene, vinylnaphthalene. The styrenic monomer may be used alone or in combination of two or more.

  The acrylic monomer used in the organic polymer used in the polytetrafluoroethylene-based mixture of the present invention contains a (meth)acrylate derivative which may be substituted. Specifically, the acrylic monomer may be one or more groups selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group, and a glycidyl group. Optionally substituted (meth)acrylate derivatives such as (meth)acrylonitrile, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, hexyl (Meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate and glycidyl (meth) ) Acrylate, maleimides which may be substituted by alkyl groups having 1 to 6 carbon atoms, or aryl groups, such as maleimide, N-methyl-maleimide and N-phenyl-maleimide, maleic acid, phthalic acid and itaconic acid. However, it is not limited to these. The acrylic monomers may be used alone or in admixture of two or more. Among these, (meth)acrylonitrile is preferable.

  The amount of the acrylic monomer-derived unit contained in the organic polymer used in the coating layer is preferably 8 to 11 parts by weight, more preferably 8 to 10 parts by weight, based on 100 parts by weight of the styrene-based monomer-derived unit. Parts, more preferably 8 to 9 parts by weight. If the amount of the acrylic monomer-derived unit is less than 8 parts by weight, the coating strength may decrease, and if it is more than 11 parts by weight, the surface appearance of the molded product may be deteriorated.

  The polytetrafluoroethylene-based mixture of the present invention preferably has a residual water content of 0.5% by weight or less, more preferably 0.2 to 0.4% by weight, further preferably 0.1 to 0. It is 3% by weight. If the residual water content is more than 0.5% by weight, flame retardancy may be adversely affected.

  In the production process of the polytetrafluoroethylene-based mixture of the present invention, a coating layer containing at least one monomer selected from the group consisting of a styrene-based monomer and an acrylic monomer in the presence of an initiator. Is external to the branched polytetrafluoroethylene. Further, after the step of forming the coating layer, the residual water content is dried to 0.5% by weight or less, preferably 0.2 to 0.4% by weight, more preferably 0.1 to 0.3% by weight. It is preferable to include a step. The drying step can be performed using a method known in the art, for example, a hot air drying method or a vacuum drying method.

  The initiator used in the polytetrafluoroethylene-based mixture of the present invention can be used without limitation as long as it is used in the polymerization reaction of styrene-based and/or acrylic monomers. Examples of the initiator include, but are not limited to, cumyl hydroperoxide, di-tert-butyl peroxide, benzoyl peroxide, hydrogen peroxide, and potassium peroxide. One or more of the above initiators can be used in the polytetrafluoroethylene-based mixture of the present invention depending on the reaction conditions. The amount of the initiator is freely selected within the range used in consideration of the amount of polytetrafluoroethylene and the kind/amount of the monomer, and is 0.15 to 0. It is preferable to use 25 parts by weight.

  The polytetrafluoroethylene-based mixture of the present invention was manufactured by the following procedure by the suspension polymerization method.

  First, water and branched polytetrafluoroethylene dispersion (solid concentration: 60%, polytetrafluoroethylene particle diameter: 0.15 to 0.3 μm) were put in a reactor, and then acrylic monomer and styrene were stirred while stirring. Cumene hydroperoxide was added as a monomer and a water-soluble initiator, and the reaction was carried out at 80 to 90°C for 9 hours. After the completion of the reaction, water was removed by centrifuging for 30 minutes with a centrifuge to obtain a pasty product. Then, the paste of the product was dried with a hot air dryer at 80 to 100° C. for 8 hours. Then, the dried product was pulverized to obtain a polytetrafluoroethylene-based mixture of the present invention.

  The suspension polymerization method does not require a polymerization step by emulsion dispersion in the emulsion polymerization method exemplified in Japanese Patent No. 3469391, and thus does not require an emulsifier and an electrolyte salt for coagulating and precipitating the latex after polymerization. Further, in the polytetrafluoroethylene mixture produced by the emulsion polymerization method, since the emulsifier and the electrolyte salt in the mixture are easily mixed and difficult to remove, the emulsifier, the sodium metal ion derived from the electrolyte salt, and the potassium metal ion are reduced. It's difficult. Since the polytetrafluoroethylene-based mixture used in the present invention is produced by the suspension polymerization method, the sodium metal ion and potassium metal ion in the mixture are reduced because the emulsifier and the electrolyte salt are not used. The heat stability and hydrolysis resistance can be improved.

  Further, in the present invention, coated branched PTFE can be used as an anti-drip agent. The coated branched PTFE is a polytetrafluoroethylene-based mixture composed of branched polytetrafluoroethylene particles and an organic polymer, and is derived from an organic polymer, preferably a styrene-based monomer, outside the branched polytetrafluoroethylene. It has a coating layer made of a polymer containing a unit and/or a unit derived from an acrylic monomer. The coating layer is formed on the surface of branched polytetrafluoroethylene. Further, the coating layer preferably contains a copolymer of a styrene monomer and an acrylic monomer.

The polytetrafluoroethylene contained in the coated branched PTFE is branched polytetrafluoroethylene. When the contained polytetrafluoroethylene is not branched polytetrafluoroethylene, the effect of preventing dripping becomes insufficient when the amount of polytetrafluoroethylene added is small. The branched polytetrafluoroethylene is particulate and preferably has a particle diameter of 0.1 to 0.6 μm, more preferably 0.3 to 0.5 μm, and further preferably 0.3 to 0.4 μm. When the particle size is smaller than 0.1 μm, the surface appearance of the molded product is excellent, but it is difficult to commercially obtain polytetrafluoroethylene having a particle size smaller than 0.1 μm. If the particle size is larger than 0.6 μm, the surface appearance of the molded product may be deteriorated. The polytetrafluoroethylene used in the present invention preferably has a number average molecular weight of 1×10 ⁴ to 1×10 ⁷ , more preferably 2×10 ^{6 to} 9×10 ⁶ , and generally has a high molecular weight of polytetrafluoroethylene. Fluoroethylene is more preferable in terms of stability. Either powder or dispersion form can be used. The content of branched polytetrafluoroethylene in the coated branched PTFE is preferably 20 to 60 parts by weight, more preferably 40 to 55 parts by weight, and still more preferably 47 to 100 parts by weight based on the total weight of the coated branched PTFE. 53 parts by weight, particularly preferably 48 to 52 parts by weight, most preferably 49 to 51 parts by weight. When the proportion of the branched polytetrafluoroethylene is in such a range, good dispersibility of the branched polytetrafluoroethylene can be achieved.

(F component: titanium oxide)
The flame-retardant polycarbonate resin composition of the present invention contains titanium oxide as the F component. (In the present invention, the titanium oxide component of the titanium oxide pigment is referred to as “TiO ₂ ”, and the entire pigment including the surface treatment agent is referred to as “titanium oxide”.) The crystalline form of TiO ₂ in the F component is anatase type. , Rutile type may be used, and they may be mixed and used as required. The rutile type is more preferable in terms of initial mechanical properties and long-term weather resistance. The rutile type crystal may contain an anatase type crystal. Further, as the TiO ₂ production method, products produced by a sulfuric acid method, a chlorine method, and various other methods can be used, but the chlorine method is more preferable. Further, the titanium oxide of the present invention is not particularly limited in its shape, but a particulate one is more preferable. The titanium oxide of the present invention preferably has an average particle size of 0.1 to 0.5 μm, more preferably 0.2 to 0.3 μm. When the average particle size is smaller than 0.1 μm, appearance defects such as silver are likely to occur when highly filled, and when it is larger than 0.5 μm, the appearance may be deteriorated and mechanical properties may be deteriorated. The average particle diameter is calculated by observing the individual single particle diameter from electron microscope observation and averaging the number thereof.

  The titanium oxide as the F component is a metal-containing hydroxide consisting of at least one selected from the group consisting of aluminum, silicon, titanium, zinc and zirconium, and at least one organic material selected from a polyol, a polysiloxane and a silane coupling agent. Is preferably surface-treated with.

  When titanium oxide that has not been treated with an inorganic material is used, the affinity with the resin is low and the dispersibility may decrease.

  When titanium oxide that has not been organically treated is used, the appearance may deteriorate due to yellowing, and the reflectance of the molded product may be significantly reduced and sufficient solar reflectance may not be obtained. It may not be suitable.

  The amount of the surface treatment agent is 3.0 to 8.0% by weight, preferably 3.75 to 7.0% by weight, and more preferably 4.0 to 6.0% by weight, based on all pigments. It is a range. If the surface treatment amount is less than 3.0% by weight or exceeds 8.0% by weight, the impact strength will be significantly reduced.

  The content of the F component is 0.1 to 30 parts by weight, preferably 0.2 to 10 parts by weight, and more preferably 1.0 to 5 parts by weight with respect to 100 parts by weight of the resin component composed of the A component and the B component. Parts by weight. If the content of the F component is less than 0.1 parts by weight, a good light reflection effect cannot be obtained, and if it exceeds 30 parts by weight, impact strength and flame retardancy are remarkably reduced, and the appearance of the molded product is also deteriorated. ..

(G component: silicate mineral)
The flame-retardant polycarbonate resin composition of the present invention can contain a silicate mineral as a G component. Such a silicate mineral is a mineral composed of at least a metal oxide component and a SiO ₂ component, and orthosilicate, disilicate, cyclic silicate, and chain silicate are preferable. The silicate mineral is in a crystalline state, and the crystal can have various shapes such as fibrous and plate shapes.

  The silicate mineral may be a compound oxide, an oxyacid salt (consisting of an ionic lattice), or a solid solution compound. Further, the compound oxide is a combination of two or more kinds of single oxides, and a single oxide and oxygen. It may be any combination of two or more kinds with an acid salt, and the solid solution may be either a solid solution of two or more kinds of metal oxides or a solid solution of two or more kinds of oxyacid salts.

The silicate mineral may be a hydrate. The morphology of water of crystallization in a hydrate is that which enters as hydrogen silicate ions as Si-OH, that which enters ionically as hydroxide ions (OH ⁻ ) with respect to metal cations, and as H ₂ O molecules in the structure gap. It may be of any form.

  As the silicate mineral, an artificial synthetic product corresponding to a natural product can also be used. As the artificial synthetic product, a silicate mineral obtained by various conventionally known methods, for example, various synthetic methods utilizing solid reaction, hydrothermal reaction, ultrahigh pressure reaction and the like can be used.

  Specific examples of the silicate mineral in each metal oxide component (MO) include the following. Here, the notation in parentheses is the name of a mineral or the like containing such a silicate mineral as a main component, and means that the compounds in parentheses can be used as the exemplified metal salts.

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 (cement clinker minerals of alite), 2CaO · SiO ₂ (cement clinker minerals of _{belite), 2CaO · MgO · 2SiO 2} ( O Keruma night), 2CaO · Al ₂ O ₃ ·SiO ₂ (gerenite), solid solution of akermanite and gerhenite (melilite), CaO·SiO ₂ (wollastonite (including both α-type and β-type)), CaO·MgO· 2SiO ₂ (diopside), CaO.MgO.SiO ₂ (ash olivine olivine), 3CaO.MgO.2SiO ₂ (merwinite), CaO.Al ₂ O ₃ .2SiO ₂ (anorthite), 5CaO.6SiO ₂ .5H Tobermorite group hydrates such as ₂ O (tobermorite and other 5CaO・6SiO ₂ 9H ₂ O), wollastonite group hydrates such as 2CaO・SiO ₂・H ₂ O (hirebrandite), 6CaO・6SiO Zonotolite group hydrate such as ₂ ·H ₂ O (zonotolite), Gyrolite group hydrate such as 2CaO·SiO ₂ ·2H ₂ O (gyrolite), 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 ( Pleo black Ait), and clinoptilolite along site, Beni Ren stone, allanite, vesuvianite, Ono stone, Sukoutaito, and Ojaito and the like.

  Furthermore, Portland cement can be mentioned as a silicate mineral containing CaO as its component. The type of Portland cement is not particularly limited, and any type such as normal, early strength, super early strength, medium heat, sulfate resistance, and white can be used. Further, various mixed cements such as blast furnace cement, silica cement and fly ash cement can also be used as the B component.

  Moreover, blast furnace slag, ferrite, etc. can be mentioned as a silicate mineral containing CaO as the other component.

Examples of the material containing ZnO include ZnO.SiO ₂ , 2ZnO.SiO ₂ (troustite), and 4ZnO.2SiO ₂ .H ₂ O (heteromorphite).

As including MnO into its _components, such as _{MnO · SiO 2, 2MnO · SiO} 2, CaO · 4MnO · 5SiO 2 ( rhodonite) and Coe write the like.

FeO is included in its components as FeO·SiO ₂ (ferrocyrite), 2FeO·SiO ₂ (iron olivine), 3FeO·Al ₂ O ₃ ·3SiO ₂ (almandine), and 2CaO·5FeO·8SiO ₂ ·. H ₂ O (tetsuactinocene stone) and the like can be mentioned.

Examples of the material containing CoO include CoO.SiO ₂ and 2CoO.SiO ₂ .

Examples of the component containing MgO include MgO·SiO ₂ (steatite and enstatite), 2MgO·SiO ₂ (forsterite), 3MgO·Al ₂ O ₃ ·3SiO ₂ (bi-rope), 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 (fluorite), 5MgO·Al ₂ O ₃ /3SiO ₂ /4H ₂ O (chlorite) , K ₂ O·6MgO·Al ₂ O ₃ ·6SiO ₂ ·2H ₂ O (phlogovite), Na ₂ O·3MgO·3Al ₂ O ₃ /8SiO ₂ ·H ₂ O (lanceite), and magnesium tourmaline, straight Examples include sense, camington sense, vermiculite, and smectite.

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 (phlogovite), various zeolites, fluorophlogopite and biotite can be mentioned.

  Of the above silicate minerals, mica, talc, and wollastonite are particularly suitable.

(talc)
The talc in the present invention is a hydrous magnesium silicate in terms of chemical composition, is generally represented by the chemical formula 4SiO ₂ ·3MgO·2H ₂ O, and is usually a scaly particle having a layered structure. Specifically, it is composed of 56 to 65% by weight of SiO ₂ , 28 to 35% by weight of MgO, and about 5% by weight of H ₂ O. Other minor _Fe 2 _{O 3} as a component from 0.03 to 1.2 wt%, _Al 2 _{O 3} is 0.05 to 1.5 wt%, CaO is 0.05 to 1.2 _{wt%, K} 2 O Is 0.2 wt% or less, Na ₂ O is 0.2 wt% or less, and the like. The particle size of talc is such that the average particle size measured by the sedimentation method is 0.1 to 15 μm (more preferably 0.2 to 12 μm, further preferably 0.3 to 10 μm, and particularly preferably 0.5 to 5 μm). It is preferably in the range. Further, 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 diameter of talc refers to D50 (median diameter of particle diameter distribution) measured by an X-ray transmission method which is one of liquid phase sedimentation methods. As a specific example of an apparatus for performing such a measurement, Sedigraph 5100 manufactured by Micromeritics Inc. can be mentioned.

  In addition, there is no particular limitation on the manufacturing method when talc is crushed from rough stones, and an axial flow mill method, an annular mill method, a roll mill method, a ball mill method, a jet mill method, a container rotary compression shear mill method, etc. are used. can do. Further, the talc after pulverization is preferably classified by various classifiers and has a uniform particle size distribution. The classifier is not particularly limited, and an impactor type inertial force classifier (variable impactor etc.), a Coanda effect type inertial force classifier (elbow jet etc.), a centrifugal field classifier (multistage cyclone, microplex, dispersion separator) , Acucat, turbo classifier, turboplex, micron separator, super separator, etc.) and the like. Further, talc is preferably in an agglomerated state from the viewpoint of its handleability and the like, and as such a production method, there are a degassing compression method, a compression method using a sizing agent, and the like. In particular, the degassing compression method is preferable because it is simple and does not mix unnecessary resin components of the sizing agent into the resin composition of the present invention.

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

(Wallast Night)
The fiber diameter of wollastonite is preferably 0.1 to 10 μm, more preferably 0.1 to 5 μm, and even more preferably 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 the 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. The fiber diameter is, with respect to the image obtained by observing with an electron microscope, the filler to be measured for the fiber diameter is randomly extracted, the fiber diameter is measured in the vicinity of the central part, and the number average fiber is obtained from the obtained measurement 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, in the measurement of the average fiber length, the filler is observed with an optical microscope, the individual lengths are obtained, and the number average fiber length is calculated from the measured value. Observation with an optical microscope starts with preparing a sample in which fillers are dispersed so that they do not overlap each other. The observation is performed under the condition of 20 times the objective lens, and the observed image is captured as image data in a CCD camera having about 250,000 pixels. The fiber length is calculated using a program for obtaining the maximum distance between two points of the image data by using the obtained image data with an image analyzer. 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 sufficiently reflects the original whiteness in the resin composition, so that the iron content mixed in the raw ore and the iron content mixed by the wear of the equipment when the raw ore is crushed are separated by a magnetic separator. It is preferable to remove as much as possible. The iron content in wollastonite is preferably 0.5 wt% or less in terms of Fe ₂ O ₃ by the magnetic separator treatment.

  Silicate minerals (more preferably mica, talc, wollastonite) are preferably not surface-treated, but are surface-treated with various surface-treating agents such as silane coupling agents, higher fatty acid esters, and waxes. May be. Furthermore, it may be granulated by granulating with a sizing agent such as various resins, higher fatty acid esters, and wax.

  The content of component G is preferably 0.1 to 50 parts by weight, more preferably 0.15 to 40 parts by weight, and even more preferably 100 parts by weight of the resin component consisting of components A and B. It is 0.2 to 30 parts by weight. By adding the G component, flame retardancy and rigidity can be improved, but when it exceeds 50 parts by weight, impact resistance is significantly lost and appearance defects such as silver may occur.

(Other additives)
(I) Phosphorus stabilizer Examples of the phosphorus stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and their esters, and tertiary phosphine.

  Specifically, 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-butylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2,6-di-tert-butylphenyl)phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert. -Butyl-4-ethylphenyl)pentaerythritol diphosphite, bis{2,4-bis(1-methyl-1-phenylethyl)phenyl}pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, bis( Nonylphenyl)pentaerythritol diphosphite, and dicyclohexyl pentaerythritol diphosphite.

  Further, as another phosphite compound, one having a cyclic structure which reacts with a dihydric phenol 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)octylphosphite.

  Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Examples thereof include diisopropyl phosphate and the like, with preference given to triphenyl phosphate and trimethyl phosphate.

  Examples of the phosphonite compound include tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite and tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylenediene. Phosphonite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylenediphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite , Tetrakis(2,6-di-tert-butylphenyl)-4,3'-biphenylenediphosphonite, tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di) -N-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl) -3-Phenyl-phenylphosphonite and the like, tetrakis(di-tert-butylphenyl)-biphenylenediphosphonite and bis(di-tert-butylphenyl)-phenyl-phenylphosphonite are preferable, and tetrakis(2,2 4-di-tert-butylphenyl)-biphenylenediphosphonite and bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite are more preferred. Such a phosphonite compound is preferable because it can be used in combination with the 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.

  Examples of the tertiary phosphine include 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.

  The above phosphorus-based stabilizers may be used alone or in combination of two or more. Among the above phosphorus-based stabilizers, a phosphonite compound or a phosphite compound represented by the following general formula (6) is preferable.

（式（６）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 the formula (6), 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 or different.)

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

  Further, more preferable phosphite compounds in the above formula (6) are distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and bis(2,6-diphenylphosphite. -Tert-butyl-4-methylphenyl)pentaerythritol diphosphite, and bis{2,4-bis(1-methyl-1-phenylethyl)phenyl}pentaerythritol diphosphite.

  Distearyl pentaerythritol diphosphite is commercially available as ADEKA STAB PEP-8 (trademark, manufactured by Asahi Denka Co., Ltd.) and JPP681S (trademark, manufactured by Johoku Chemical Industry Co., Ltd.), and any of them can be used. Bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite is ADEKA STAB PEP-24G (trademark, manufactured by Asahi Denka Kogyo KK), Alkanox P-24 (trademark, manufactured by Great Lakes), Ultranox. P626 (trademark, manufactured by GE Specialty Chemicals), Doverphos S-9432 (trademark, manufactured by Over Chemical), and Irgaofos 126 and 126FF (trademark, manufactured by CIBA SPECIALTY CHEMICALS) are commercially available. Bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite is commercially available as ADEKA STAB PEP-36 (trademark, manufactured by Asahi Denka Co., Ltd.) and can be easily used. Further, bis{2,4-bis(1-methyl-1-phenylethyl)phenyl}pentaerythritol diphosphite is ADEKA STAB PEP-45 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.), and Doverphos S-9228 (trademark). , Manufactured by Dover Chemical Co., Ltd., and any of them can be used.

  The above phosphorus-based stabilizers can be used alone or in combination of two or more. The content of the phosphorus-based stabilizer is preferably 0.01 to 1.0 parts by weight, and more preferably 0.03 to 0.8 parts by weight, relative to 100 parts by weight of the resin component consisting of the components A and B. Parts, more preferably 0.05 to 0.5 parts by weight. If the content is less than 0.01 parts by weight, the effect of suppressing thermal decomposition at the time of processing may not be exhibited and mechanical properties may not be deteriorated. If it exceeds 1.0 parts by weight, mechanical properties may be deteriorated. ..

(Ii) Phenolic Stabilizer The resin composition of the present invention may contain a phenolic stabilizer. Phenolic stabilizers generally include hindered phenols, semi-hindered phenols, and less hindered phenol compounds, but hindered phenol compounds are particularly preferable from the viewpoint of heat-stabilizing the polypropylene resin. Used for. 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′-butylidene bis(3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate , 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[2-tert-butyl-4-methyl 6-(3-tert-butyl) -5-Methyl-2-hydroxybenzyl)phenyl]terephthalate, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1,- Dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'-thiobis(3-methyl) -6-tert-butylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol), bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4'- Di-thiobis(2,6-di-tert-butylphenol), 4,4'-tri-thiobis(2,6-di-tert-butylphenol) 2,2-thiodiethylenebis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy) -3,5-Di-tert-butylanilino)-1,3,5-triazine, N,N'-hexamethylenebis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-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-hydroxy) Phenyl)isocyanurate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) Isocyanurate, 1,3,5-tris2[3(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl isocyanurate, tetrakis[methylene-3-(3,5-di-tert). -Butyl-4-hydroxyphenyl)propionate]methane, triethyleneglycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, triethyleneglycol-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-5-methylbenzyl)benzene, and tris(3-tert-butyl-4-hydroxy-5-methyl) Examples thereof include benzyl) isocyanurate. Among the above compounds, tetrakis[methylene-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]methane, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate is preferably used and is excellent in suppressing deterioration of mechanical properties due to thermal decomposition during processing, and is represented by the following formula (7) (3, 3′, 3″, 5, 5′, 5 ″-Hexa-tert-butyl-a,a′,a″-(mesitylene-2,4,6-triyl)tri-p-cresol, and 1,3,5 represented by the following formula (8) -Tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione is more preferably used.

  The above-mentioned phenolic stabilizers can be used alone or in combination of two or more kinds. The content of the phenolic stabilizer is preferably 0.05 to 1.0 part by weight, more preferably 0.07 to 0.8 part by weight, based on 100 parts by weight of the resin component consisting of the component A and the component B. Parts, more preferably 0.1 to 0.5 parts by weight. If the content is less than 0.05 parts by weight, the effect of suppressing thermal decomposition during processing may not be exhibited and mechanical properties may deteriorate, and if it exceeds 1.0 parts by weight, mechanical properties may deteriorate. ..

  It is preferable that either a phosphorus-based stabilizer or a phenol-based stabilizer is blended, and the combination thereof is further preferable. When used in combination, 0.01 to 0.5 parts by weight of a phosphorus-based stabilizer and 0.01 to 0.5 parts by weight of a phenol-based stabilizer are mixed with 100 parts by weight of a resin component consisting of the components A and B. Preferably.

(Iii) Ultraviolet absorber The flame-retardant polycarbonate resin composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, in the benzophenone type, 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-sulfoxytrihydrate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4' -Tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis(5-benzoyl-4-) Examples include hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

  In the benzotriazole type, 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-benzoxazin-4-one), and 2-[2-hydroxy-3-(3,4,4). 5,6-Tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole, and vinyl monomer copolymerizable with 2-(2'-hydroxy-5-methacryloxyethylphenyl)-2H-benzotriazole and the monomer 2-Hydroxyphenyl-2H such as a copolymer of 2-(2'-hydroxy-5-acryloxyethylphenyl)-2H-benzotriazole and a vinyl-based monomer copolymerizable with the monomer Examples thereof include polymers having a benzotriazole skeleton.

  In the hydroxyphenyl triazine type, 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, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-butyloxyphenol, etc. It is illustrated. Furthermore, the phenyl group of the above exemplified compounds such as 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hexyloxyphenol is 2,4-dimethyl. A compound having a phenyl group is exemplified.

  In the cyclic imino ester system, for example, 2,2'-p-phenylenebis(3,1-benzoxazin-4-one), 2,2'-m-phenylenebis(3,1-benzoxazin-4-one) , And 2,2′-p,p′-diphenylenebis(3,1-benzoxazin-4-one) and the like.

  In the cyanoacrylate type, for example, 1,3-bis-[(2′-cyano-3′,3′-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-diphenylacryloyl)oxy] ] Methyl)propane, 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene and the like are exemplified.

  Further, the ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, so that the ultraviolet absorbing monomer and/or the photostable monomer are combined with a monomer such as an alkyl (meth)acrylate. It may be a polymer type ultraviolet absorber obtained by copolymerizing with the body. Preferred examples of the ultraviolet absorbing monomer include compounds having a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic iminoester skeleton, and a cyanoacrylate skeleton in the ester substituent of a (meth)acrylic acid ester. It

  Among the above compounds, in the present invention, the compounds represented by any of the following formulas (9), (10) and (11) are more preferably used.

The above ultraviolet absorbers can be used alone or in combination of two or more kinds.
The content of the ultraviolet absorber is preferably 0.1 to 3 parts by weight, more preferably 0.12 to 2 parts by weight, and still more preferably 100 parts by weight of the resin component consisting of the components A and B. It is 0.15 to 1 part by weight. When the content of the ultraviolet absorber is less than 0.1 parts by weight, sufficient light resistance may not be exhibited, and when it is more than 3 parts by weight, it is not preferable from the viewpoint of poor appearance due to gas generation and deterioration of physical properties.

(Iv) Hindered amine light stabilizer The flame-retardant polycarbonate resin composition of the present invention may contain a hindered amine light stabilizer. The hindered amine light stabilizer is generally called HALS (Hindered Amine Light Stabilizer) and is a compound having a 2,2,6,6-tetramethylpiperidine skeleton in its structure, for example, 4-acetoxy-2,2,6. ,6-Tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(phenylacetoxy)-2, 2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2, 2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2, 2,6,6-tetramethylpiperidine, 4-(ethylcarbamoyloxy)-2,2,6,6-tetramethylpiperidine, 4-(cyclohexylcarbamoyloxy)-2,2,6,6-tetramethylpiperidine, 4-(phenylcarbamoyloxy)-2,2,6,6-tetramethylpiperidine, bis(2,2,6,6-tetramethyl-4-piperidyl)carbonate, bis(2,2,6,6-tetra Methyl-4-piperidyl)oxalate, bis(2,2,6,6-tetramethyl-4-piperidyl)malonate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2 2,6,6-Tetramethyl-4-piperidyl)adipate, bis(2,2,6,6-tetramethyl-4-piperidyl)terephthalate, bis(1,2,2,6,6-pentamethyl-4-) Piperidyl)carbonate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)oxalate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)malonate, bis(1,2,2) 2,6,6-Pentamethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)adipate, bis(1,2,2,6,6-pentamethyl-4-) Piperidyl) terephthalate, N,N'-bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzenedicarboxamide, 1,2-bis(2,2,6,6-tetra Methyl-4-pi Peridyloxy)ethane, α,α′-bis(2,2,6,6-tetramethyl-4-piperidyloxy)-p-xylene, bis(2,2,6,6-tetramethyl-4-piperidyltrilene -2,4-dicarbamate, bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylene-1,6-dicarbamate, tris(2,2,6,6-tetramethyl-4) -Piperidyl)-benzene-1,3,5-tricarboxylate, N,N',N",N'"-tetrakis-(4,6-bis-(butyl-(N-methyl-2,2) ,6,6-Tetramethylpiperidin-4-yl)amino)-triazin-2-yl)-4,7-diazadecane-1,10-diamine, dibutylamine·1,3,5-triazine·N,N′ -Bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine polycondensate , Poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4- Piperidyl)imino}hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl)imino}], tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3 ,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tris(2,2,6,6- Tetramethyl-4-piperidyl)-benzene-1,3,4-tricarboxylate, 1-[2-{3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy}butyl]- 4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]2,2,6,6-tetramethylpiperidine, and 1,2,3,4-butanetetracarboxylic acid 1,2,2,6,6-Pentamethyl-4-piperidinol and β,β,β′,β′-tetramethyl-3,9-[2,4,8,10-tetraoxaspiro(5,5) Undecane] and a condensate with diethanol.

  Hindered amine-based light stabilizers are roughly classified into NH type (hydrogen is bonded to nitrogen atom), NR type (alkyl group (R) is bonded to nitrogen atom) according to the bonding partner of the nitrogen atom in the piperidine skeleton. There are three types of N-OR type (an alkoxy group (OR) is bonded to a nitrogen atom), but when applied to a polycarbonate resin, it is a low basic type N-R from the viewpoint of the basicity of the hindered amine light stabilizer. Type and N-OR type are more preferably used.

  Among the above compounds, the compounds represented by the following formulas (12) and (13) are more preferably used in the present invention.

  The hindered amine light stabilizers can be used alone or in combination of two or more kinds. The content of the hindered amine light stabilizer is preferably 0 to 1 part by weight, more preferably 0.05 to 1 part by weight, and even more preferably 100 parts by weight of the resin component consisting of the components A and B. The amount is 0.08 to 0.7 part by weight, particularly preferably 0.1 to 0.5 part by weight. When the content of the hindered amine-based light stabilizer is more than 1 part by weight, the appearance may be deteriorated due to gas generation and the physical properties may be deteriorated due to decomposition of the polycarbonate resin, which is not preferable. If it is less than 0.05 part by weight, sufficient light resistance may not be exhibited.

(V) Release Agent The flame-retardant polycarbonate resin composition of the present invention preferably further contains a release agent for the purpose of improving productivity during molding and reducing distortion of the molded product. Known release agents can be used as the release agent. For example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax, 1-alkene polymer, etc., which can be modified with a functional group-containing compound such as acid modification), silicone compound, fluorine compound ( Fluorine oil typified by polyfluoroalkyl ether), paraffin wax, beeswax, and the like. Among them, a fatty acid ester is mentioned as a preferable releasing agent. Such fatty acid ester is an ester of an aliphatic alcohol and an aliphatic carboxylic acid. The aliphatic alcohol may be a monohydric alcohol or a polyhydric alcohol having a valence of 2 or more. Moreover, the carbon number of the alcohol is in the range of 3 to 32, and more preferably in the range of 5 to 30. Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, ceryl alcohol, and triacontanol. Examples of such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. Polyhydric alcohols are more preferable in the fatty acid ester of the present invention.

  On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, and particularly preferably an aliphatic carboxylic acid having 10 to 22 carbon atoms. Examples of the aliphatic carboxylic acid include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, behenic acid, Mention may be made of saturated aliphatic carboxylic acids such as eicosanoic acid and docosanoic acid, and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and cetoleic acid. .. Among the above, the aliphatic carboxylic acid preferably has 14 to 20 carbon atoms. Of these, saturated aliphatic carboxylic acids are preferred. In particular, stearic acid and palmitic acid are preferable.

  The above-mentioned aliphatic carboxylic acids such as stearic acid and palmitic acid are usually produced from natural oils and fats such as animal fats and oils typified by beef tallow and lard, and vegetable oils and fats typified by palm oil and sunflower oil. Therefore, these aliphatic carboxylic acids are usually a mixture containing other carboxylic acid components having different numbers of carbon atoms. Therefore, also in the production of the fatty acid ester of the present invention, an aliphatic carboxylic acid, particularly stearic acid or palmitic acid, which is produced from such natural fats and oils and is in the form of a mixture containing other carboxylic acid components is preferably used.

  The fatty acid ester of the present invention may be either a partial ester or a total ester (full ester). However, the partial ester usually has a higher hydroxyl value and is likely to induce decomposition of the resin at a high temperature. Therefore, the full ester is more preferable. The acid value of the fatty acid ester of the present invention is preferably 20 or less, more preferably 4 to 20 and still more preferably 4 to 12 from the viewpoint of thermal stability. The acid value can be substantially zero. Further, the hydroxyl value of the fatty acid ester is more preferably in the range of 0.1 to 30. Further, the iodine value is preferably 10 or less. The iodine value can be substantially zero. These characteristics can be determined by the method specified in JIS K0070.

  The content of the release agent is preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight, and still more preferably 0.1 part by weight with respect to 100 parts by weight of the resin component consisting of the components A and B. It is from 05 to 0.5 parts by weight. In such a range, the flame-retardant polycarbonate resin composition has good releasing property and releasing property. In particular, such an amount of the fatty acid ester provides a flame-retardant polycarbonate resin composition having good releasing property and releasing roll property without impairing good hue.

(Vi) Dye/Pigment The flame-retardant polycarbonate resin composition of the present invention can further contain various dyes/pigments other than the F component to provide molded articles exhibiting various design properties. By blending a fluorescent whitening agent or a fluorescent dye that emits light other than the fluorescent whitening agent, it is possible to impart a better design effect by utilizing the emission color. It is also possible to provide a flame-retardant polycarbonate resin composition which is colored with an extremely small amount of dye and pigment and has a vivid color-forming property.

  Examples of the fluorescent dye (including a fluorescent whitening agent) used in the present invention include coumarin fluorescent dye, benzopyran fluorescent dye, perylene fluorescent dye, anthraquinone fluorescent dye, thioindigo fluorescent dye, xanthene fluorescent dye. , Xanthone-based fluorescent dyes, thioxanthene-based fluorescent dyes, thioxanthone-based fluorescent dyes, thiazine-based fluorescent dyes, and diaminostilbene-based fluorescent dyes. Among these, coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, and perylene-based fluorescent dyes, which have good heat resistance and little deterioration during molding of a polycarbonate resin, are preferable.

  As the dye other than the bluing agent and the fluorescent dye, perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as dark blue, perinone dyes, quinoline dyes, quinacridone. Examples thereof include dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Further, the resin composition of the present invention can be blended with a metallic pigment to obtain a better metallic color. As the metallic pigment, those having a metal coating or a metal oxide coating on various plate-like fillers are suitable.

  The content of the above dye/pigment is preferably 0.00001 to 1 part by weight, and more preferably 0.00005 to 0.5 part by weight, relative to 100 parts by weight of the resin component consisting of the components A and B.

(Vii) Other heat stabilizers The flame-retardant polycarbonate resin composition of the present invention may be blended with a heat stabilizer other than the above phosphorus-based stabilizer and phenol-based stabilizer. Such other heat stabilizers are preferably used in combination with any of these stabilizers and antioxidants, and particularly preferably in combination with both. Examples of such other heat stabilizers include lactone-based stabilizers (represented by such a reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene). The details are described in JP-A-7-233160). Such a compound is commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and the compound can be used. Further, stabilizers obtained by mixing the compound with various phosphite compounds and hindered phenol compounds are commercially available. For example, Irganox HP-2921 manufactured by the above company is preferably exemplified. Such premixed stabilizers can also be utilized in the present invention. The compounding amount of the lactone stabilizer is preferably 0.0005 to 0.05 part by weight, more preferably 0.001 to 0.03 part by weight, relative to 100 parts by weight of the resin component consisting of the component A and the component B. ..

  Other stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. It is illustrated. Such stabilizers are particularly effective when the resin composition is applied to rotomolding. The amount of the sulfur-containing stabilizer blended is preferably 0.001 to 0.1 part by weight, more preferably 0.01 to 0.08 part by weight, relative to 100 parts by weight of the resin component consisting of the components A and B. Is.

(Viii) Filler In the flame-retardant polycarbonate resin composition of the present invention, various fillers other than the silicate mineral which is the G component can be blended as a reinforcing filler within the range where the effect of the present invention is exhibited. . For example, calcium carbonate, glass fibers, glass beads, glass balloons, glass milled fibers, glass flakes, carbon fibers, carbon flakes, carbon beads, carbon milled fibers, graphite, vapor grown ultrafine carbon fibers (fiber diameter 0.1 μm Less), carbon nanotubes (fiber diameter is less than 0.1 μm, hollow), fullerenes, metal flakes, metal fibers, metal-coated glass fibers, metal-coated carbon fibers, metal-coated glass flakes, silica, metal oxide particles, Examples thereof include metal oxide fibers, metal oxide balloons, and various whiskers (potassium titanate whiskers, aluminum borate whiskers, basic magnesium sulfate, etc.). These reinforcing fillers may be used alone or in combination of two or more.

  The content of these fillers is preferably 0.1 to 60 parts by weight, more preferably 0.5 to 50 parts by weight, based on 100 parts by weight of the resin component consisting of the components A and B.

(Ix) Other resin or elastomer In the resin composition of the present invention, a small proportion of other resin or elastomer may be used within the range where the effect of the present invention is exhibited.

  Examples of such other resins include resins such as polyamide resin, polyimide resin, polyetherimide resin, polyurethane resin, silicone resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polymethacrylate resin, phenol resin, and epoxy resin. Be done.

  Examples of the elastomer include isobutylene/isoprene rubber, ethylene/propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer and the like.

(X) Other Additives In addition, the flame-retardant polycarbonate resin composition of the present invention may contain a small proportion of additives known per se in order to impart various functions to the molded product and improve the properties. You can The amounts of these additives to be added are usual amounts unless the object of the present invention is impaired.

  Examples of such additives include sliding agents (for example, PTFE particles), colorants (for example, pigments such as carbon black and titanium oxide, dyes), light diffusers (for example, acrylic crosslinked particles, silicone crosslinked particles, ultrathin glass flakes, carbonic acid. Calcium particles), fluorescent dyes, inorganic phosphors (for example, phosphors having aluminate as a mother crystal), antistatic agents, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (eg, fine particle titanium oxide). , Fine particle zinc oxide), a radical generator, an infrared absorber (heat ray absorber), and a photochromic agent.

  INDUSTRIAL APPLICABILITY The flame-retardant polycarbonate resin composition of the present invention has improved mechanical properties, chemical resistance, flame retardancy, high light reflectivity, and appearance of molded products. Widely useful in the field. Therefore, the industrial effect of the present invention is extremely large.

  A mode for carrying out the present invention is a collection of preferable ranges of the above-mentioned requirements, and representative examples thereof will be described in the following examples. Of course, the present invention is not limited to these forms.

  The present invention will be further described below with reference to examples. In the examples, parts are parts by weight and% are% by weight unless otherwise specified. The evaluation was carried out by the following method.

(Evaluation of thermoplastic resin composition)
(I) Appearance of molded product A molded plate (length 90 mm x width 50 mm) having a thickness of 2 mm and an arithmetic mean roughness (Ra) of 0.03 µm is used as a cylinder temperature of 260°C, a mold temperature of 60°C, and an injection speed of 30 mm/s. Molding was performed by injection molding under the conditions described above, and the presence or absence of silver streaks was observed. For the evaluation, the 10th shot immediately after purging was discarded, and the molded product up to 20 shots thereafter was used for silver streak evaluation. In addition, when the silver streak was not confirmed, it was indicated as “◯”, and when the silver streak was confirmed, it was indicated as “x”.
(Ii) Charpy impact strength Using the ISO bending test pieces obtained by the following method, the Charpy impact strength with a notch was measured according to ISO 179.
(Iii) Flame retardancy A V test was performed according to UL94 using a UL test piece obtained by the following method. In addition, the case where the judgment could not satisfy any of the criteria of V-0, V-1, and V-2 was shown as "notV".
(Iv) Chemical resistance Using an ISO tensile test piece obtained by the following method, 0.5% strain was applied by a three-point bending test method, and then impregnated with magic phosphorus (manufactured by Kao Corporation) The cloth was put on and left standing at 23° C. for 24 hours, and then it was confirmed whether or not there was a change in appearance. The evaluation was carried out according to the following criteria.
◯: No change in appearance is seen Δ: Fine cracks are seen ×: Large cracks such as fracture are seen (v) Light reflectivity 2 mm thickness used for evaluation of appearance of molded product The 45° incident total light relative reflectance of the molded plate of Example 1 was measured using a haze/transmittance/reflectometer HR-100 manufactured by Murakami Color Research Laboratory.
◯: Reflectivity is 80 to 100%
X: reflectance is less than 80%

[Examples 1 to 26, Comparative Examples 1 to 12]
A mixture having the composition shown in Table 1 and Table 2 and containing each component was supplied from the first supply port of the extruder. Such a mixture was obtained by mixing with a V type blender. For the extrusion, a bent type twin-screw extruder having a diameter of 30 mmφ (TEX30α-38.5BW-3V, Japan Steel Works, Ltd.) was used, and melt kneading was performed at a screw rotation speed of 230 rpm, a discharge rate of 25 kg/h, and a vent vacuum degree of 3 kPa. Pellets were obtained. When D-1 is further added, the third supply port (the first supply port and the first supply port) in the middle of the cylinder is used by using a liquid injection device (HYM-JS-08 manufactured by Fuji Techno Industry Co., Ltd.) while being heated to 80°C. From the position between the vent and the exhaust port), each was supplied to the extruder at a predetermined ratio. The liquid injection device was set to supply a fixed amount, and the amounts of the other raw materials supplied were precisely measured by a measuring instrument [CWF manufactured by Kubota Corporation]. The extrusion temperature was 260° C. from the first supply port to the die. Some of the obtained pellets were dried at 90 to 100° C. for 6 hours by a hot air circulation dryer, and then, using an injection molding machine, an ISO bending test piece was prepared at a cylinder temperature of 250° C. and a mold temperature of 50° C. (ISO179 compliant), ISO tensile test pieces (ISO527-1 and ISO527-2 compliant) and UL test pieces were molded.

  The components represented by symbols in Tables 1 and 2 are as follows.

(A component)
A-1: Aromatic polycarbonate resin (polycarbonate resin powder having a viscosity average molecular weight of 22,400 made from bisphenol A and phosgene by a conventional method, Panlite L-1225WP (product name) manufactured by Teijin Ltd.)
A-2: Aromatic polycarbonate resin (polycarbonate resin powder having a viscosity average molecular weight of 23,900 made from bisphenol A and phosgene by a conventional method, Panlite L-1250WP (product name) manufactured by Teijin Ltd.)

(B component)
B-1: Polyethylene terephthalate resin (intrinsic viscosity 0.77 dL/g, TRN-8550FF (product name) manufactured by Teijin Ltd.)
B-2: Polyethylene terephthalate resin (intrinsic viscosity 0.53 dL/g, TRN-MTJ (product name) manufactured by Teijin Ltd.)

(C component)
C-1: Silicone core-shell type graft polymer (a graft copolymer having a core-shell structure in which the core has a silicone-acrylic composite rubber as a main component at 70 wt% and the shell has methyl methacrylate as a main component at 30 wt %, Mitsubishi Rayon ( METABLEN S-2001 (product name))
C-2: butadiene-based core-shell type graft polymer (graft copolymer having a core-shell structure in which the core is 70 wt% with butadiene rubber as the main component, and the shell is 30 wt% with methyl methacrylate and styrene as the main components, Kaneka Corporation) Kane Ace M-701 (product name)
C-3: butadiene-based core-shell type graft polymer (graft copolymer having a core-shell structure in which the core is butadiene rubber as a main component at 60 wt% and the shell is methyl methacrylate as a main component at 40 wt %, Kaneka Co., Ltd. M-711 (product name))
C-4: Acrylic core-shell type graft polymer (graft copolymer having a core-shell structure in which the core is butadiene-acrylic composite rubber and butyl acrylate as main components 60 wt% and the shell is methyl methacrylate as main components 40 wt %, Mitsubishi Rayon Co., Ltd. Metablen W-600A (product name))

(D component)
D-1: Phosphate ester containing bisphenol A bis(diphenyl phosphate) as a main component (CR-741 (trade name) manufactured by Daihachi Chemical Industry Co., Ltd.)

(E component)
E-1: PTFE (Polyflon MPA FA500H (trade name) manufactured by Daikin Industries, Ltd.)
E-2: Coated PTFE (polytetrafluoroethylene coated with styrene-acrylonitrile copolymer (polytetrafluoroethylene content 50% by weight), SN3307 (trade name) manufactured by Shine polymer)
E-3: Coated PTFE (polytetrafluoroethylene coated with methyl methacrylate and butyl acrylate copolymer (polytetrafluoroethylene content 50% by weight), Mitsubishi Rayon Co., Ltd. METABLEN A3750 (trade name))
E-4: Coated branched PTFE (branched polytetrafluoroethylene coated with styrene-acrylonitrile copolymer (polytetrafluoroethylene content 50% by weight), SN3300B7 (trade name) manufactured by Shine polymer)

(F component)
F-1: Titanium dioxide (inorganic treatment agent: Al ₂ O ₃ , silicon, organic treatment agent: polysiloxane type, surface treatment amount: 5%, average particle diameter: 0.22 μm)
F-2: Titanium dioxide (inorganic treatment agent: Al ₂ O ₃ , organic treatment agent: polysiloxane type, surface treatment amount: 4%, average particle diameter: 0.20 μm)
F-3: Titanium dioxide (inorganic treatment agent: Al ₂ O ₃ , silicon, organic treatment agent: polysiloxane type, surface treatment amount: 9%, average particle diameter: 0.21 μm)
F-4: Titanium dioxide (inorganic treatment agent: Al ₂ O ₃ , silicon, organic treatment agent: polysiloxane type, surface treatment amount: 2%, average particle diameter: 0.21 μm)

(G component)
G: Talc (Hayashi Kasei Co., Ltd.; HST0.8 (trade name), average particle size 3.5 μm)

(Other ingredients)
STB-1: Phenolic heat stabilizer (octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, molecular weight 531, BASF Japan Ltd. Irganox 1076 (product name))
STB-2: Phosphorus-based heat stabilizer (tris(2,4-di-tert-butylphenyl)phosphite, BASF Japan KK Irgafos 168 (product name))
WAX-1: Fatty acid ester-based release agent (Rikemar SL900 (product name) manufactured by Riken Vitamin Co., Ltd.)
WAX-2: Olefin wax produced by copolymerization of α-olefin and maleic anhydride (manufactured by Mitsubishi Chemical Corporation; Diakarna 30M (trade name))

Claims (5)

  (C) Impact modifier (C component) with respect to 100 parts by weight of a resin component consisting of 30 to 95 parts by weight of (A) polycarbonate resin (component A) and 70 to 5 parts by weight of (B) polyester resin (component B). 1 to 10 parts by weight, (D) 1 to 30 parts by weight of a flame retardant containing a phosphoric acid ester (D component), (E) 0.05 to 2 parts by weight of anti-drip agent (E component) and (F) surface treatment amount Flame-retardant polycarbonate resin composition containing 0.1 to 30 parts by weight of a surface-treated titanium oxide pigment (F component) whose amount is 3.0 to 8.0% by weight based on all pigments. .   A graft polymer obtained by copolymerizing at least one rubber selected from the group consisting of butadiene rubber, acrylic rubber and silicone-acrylic composite rubber, with a monomer copolymerizable therewith. The flame-retardant polycarbonate resin composition according to claim 1, which is present.   The F component is surface-treated with a metal-containing hydroxide consisting of at least one selected from the group consisting of aluminum, silicon, titanium, zinc and zirconium, and at least one organic material selected from polyols, polysiloxanes and silane coupling agents. The flame-retardant polycarbonate resin composition according to claim 1 or 2, which is a titanium oxide pigment having an average particle diameter of 0.1 to 0.5 µm.   4. The composition according to claim 1, wherein 0.1 to 50 parts by weight of (G) silicate mineral (component G) is contained with respect to 100 parts by weight of the resin component consisting of the A component and the B component. The flame-retardant polycarbonate resin composition described. A molded article comprising the flame-retardant polycarbonate resin composition according to claim 1.