JPWO2019151497A1 - Flame-retardant polycarbonate resin composition - Google Patents

Abstract

The present invention provides a polycarbonate resin composition that satisfies mechanical properties, fluidity, flame retardancy, high light reflectivity, and appearance of a molded product at a high level. A single amount of (B) aromatic vinyl monomer, vinyl cyanide monomer and alkyl (meth) acrylate with respect to 100 parts by weight of the flame-retardant polycarbonate resin composition (A) polycarbonate resin (component A) of the present invention. 1 to 30 parts by weight of a polymer (B component) obtained by polymerizing one or more selected from the group consisting of bodies, (C) 1 to 10 parts by weight of an impact modifier (C component) excluding B component, (D) ) Phosphazen (D component) 1 to 20 parts by weight, (E) drip inhibitor (E component) 0.05 to 2 parts by weight, and (F) titanium oxide (F component) 0.05 to 30 parts by weight. It is characterized by.

Description

The present invention relates to a flame-retardant polycarbonate resin composition and a molded product thereof. More specifically, a graft polymer obtained by graft-polymerizing one or more selected from the group consisting of an aromatic vinyl monomer, a vinyl cyanide monomer and an alkyl (meth) acrylate monomer onto a polycarbonate resin. It relates to a polycarbonate resin composition in which mechanical properties, fluidity, flame retardancy, high light reflectivity, and appearance of a molded product are improved by adding an impact modifier, phosphazene, a drip inhibitor, and titanium oxide.

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

As a method for imparting high flame retardancy to an aromatic polycarbonate resin, a combined use of a halogen-based flame retardant such as a bromine compound and a flame retardant aid such as antimony trioxide has been generally used (Patent Document 1). reference).

However, in recent years, due to the problem of generation of harmful substances during combustion, studies on flame retardant use of organophosphorus flame retardants containing no halogen-based compound having brom have been actively conducted. For example, many compositions have been proposed in which a phosphoric acid ester flame retardant and polytetrafluoroethylene having a fibril forming ability are added to an aromatic polycarbonate resin, and related findings are widely known (see Patent Document 2).

Further, as a formulation for improving the toughness of the aromatic polycarbonate resin, a method of adding an impact modifier such as a graft polymer is known (see Patent Document 3).

In general, the addition of a flame retardant causes a decrease in mechanical properties, and the addition of an impact modifier also causes a decrease in flame retardancy. Therefore, depending on the balance between the amount of the flame retardant and the amount of the impact modifier, the mechanical properties and the difficulty are within a certain range. A flammable resin composition has been provided (see Patent Document 4). However, the current situation is that a resin composition that achieves UL94 V-0 in a thin wall and is excellent in both impact resistance and molded appearance has not been obtained.

Japanese Unexamined Patent Publication No. 2-199162 Japanese Unexamined Patent Publication No. 2-115262 JP-A-2009-203269 Japanese Unexamined Patent Publication No. 2001-123056

In view of the above, it is an object of the present invention to provide a polycarbonate resin composition that satisfies excellent mechanical properties, fluidity, flame retardancy, high light reflectivity, and appearance of a molded product at a high level.

As a result of diligent studies to solve the above problems, the present inventor has used a phosphoric acid ester system in a flame retardant polycarbonate resin composition containing an impact modifier, a drip inhibitor and titanium oxide. It has been found that the above problems can be solved by changing the flame retardant to phosphazene and further using a specific impact modifier. Without being bound by theory, this is because titanium oxide adheres to the impact modifier in the polycarbonate resin composition containing phosphazene and the impact modifier is properly dispersed during the extrusion molding process, resulting in high impact strength. It is thought that it was.

According to the present invention, the above object is achieved by the flame-retardant polycarbonate resin composition of the following aspects.
<< Aspect 1 >>
(A) With respect to 100 parts by weight of polycarbonate resin (component A)
(B) 1 to 30 parts by weight of a polymer (B component) obtained by polymerizing one or more selected from the group consisting of an aromatic vinyl monomer, a vinyl cyanide monomer and an alkyl (meth) acrylate monomer. ,
(C) Impact modifier (C component) excluding B component, 1 to 10 parts by weight,
(D) Phosphazene (D component) 1 to 20 parts by weight,
A flame-retardant polycarbonate resin composition containing 0.05 to 2 parts by weight of (E) drip inhibitor (E component) and 0.05 to 30 parts by weight of (F) titanium oxide (F component). ..
<< Aspect 2 >>
Component B consists of polystyrene resin, acrylonitrile-styrene copolymer, acrylonitrile-α-methylstyrene copolymer, methyl (meth) acrylate-styrene copolymer, and methyl (meth) acrylate-styrene-acrylonitrile copolymer. The composition according to aspect 1, which comprises a resin selected from the group.
<< Aspect 3 >>
The composition according to aspect 2, wherein the component B comprises an acrylonitrile-styrene copolymer.
<< Aspect 4 >>
The composition according to any one of aspects 1 to 3, wherein the component C is a polymer having a core-shell structure containing a rubber component in the core.
<< Aspect 5 >>
A graft in which at least one compound containing a (meth) acrylic acid ester compound is graft-polymerized with one rubber selected from the group consisting of a butadiene rubber, an acrylic rubber and a silicone / acrylic composite rubber as the C component. The composition according to aspect 4, wherein the composition is a polymer.
<< Aspect 6 >>
The composition according to any one of aspects 1 to 5, wherein the component E is a fluoropolymer.
<< Aspect 7 >>
The composition according to any one of aspects 1 to 6, wherein 0.1 to 50% by weight of (G) silicate mineral (G component) is further contained with respect to 100 parts by weight of the A component.
<< Aspect 8 >>
A molded product made of the flame-retardant polycarbonate resin composition according to any one of aspects 1 to 7.

Since the flame-retardant polycarbonate resin composition of the present invention has improved mechanical properties, fluidity, flame retardancy, high light reflectivity, and appearance of a molded product, the field of OA equipment, the field of electronic and electrical equipment, and various other fields Widely useful in. Therefore, the industrial effect of the present invention is extremely large.

The details of the present invention will be described below.

(Component A: Polycarbonate resin)
The polycarbonate resin used in the present invention is obtained by reacting a divalent phenol with a carbonate precursor. Examples of the reaction method include an interfacial polymerization method, a molten transesterification method, a solid phase 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 are hydroquinone, resorcinol, 4,4'-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl). ) Propane (commonly known as 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) Pentan, 4,4'-(p-phenylenediisopropyridene) diphenol, 4,4'-(m-phenylenediisopropyriden) 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) ketone 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. The preferred divalent phenol is bis (4-hydroxyphenyl) alkane, and among them, bisphenol A is particularly preferable from the viewpoint of impact resistance, and is widely used.

In the present invention, in addition to the bisphenol A-based polycarbonate, which is a general-purpose polycarbonate, a special polycarbonate produced by using other divalent phenols can be used as the A component.

For example, 4,4'-(m-phenylenediisopropyridene) diphenol (hereinafter sometimes abbreviated as "BPM"), 1,1-bis (4-hydroxy) as a part or all of the divalent phenol component. Phenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as "Bis-TMC"), 9,9-bis (4-hydroxyphenyl) Polycarbonates (monopolymers or copolymers) using fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as "BCF") have dimensions due to water absorption. Suitable for applications with particularly stringent requirements for change and morphological stability. It is preferable to use these divalent phenols other than BPA in an amount of 5 mol% or more, particularly 10 mol% or more, of the total divalent phenol components constituting the polycarbonate.

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

These special polycarbonates may be used alone or in admixture of two or more. Further, these can also be used by mixing them with a widely 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, JP-A-2002-117580 and the like. ing.

Among the various polycarbonates described above, those in which the water absorption rate and Tg (glass transition temperature) are 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 fields 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) Tg of 160 to 250 ° C. Polycarbonate preferably at 170 to 230 ° C. and having a water absorption rate of 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27%.

Here, the water absorption rate of polycarbonate is a value obtained by measuring the water content after immersing in water at 23 ° C. for 24 hours in accordance with ISO62-1980 using a disk-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm. is there. The Tg (glass transition temperature) is a value obtained by differential scanning calorimetry (DSC) measurement based on JIS K7121.

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

In producing an aromatic polycarbonate resin by interfacial polymerization of the divalent phenol and the carbonate precursor, if necessary, a catalyst, a terminal terminator, and an antioxidant for preventing the divalent phenol from being oxidized. 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, or a polyester obtained by copolymerizing an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid. It includes a carbonate resin, a copolymerized polycarbonate resin obtained by copolymerizing a bifunctional alcohol (including an alicyclic type), and a polyester carbonate resin obtained by copolymerizing both the bifunctional carboxylic acid and the bifunctional alcohol. Further, it may be a mixture of two or more of the obtained aromatic polycarbonate resins.

The branched polycarbonate resin can impart drip prevention performance and the like to the resin composition of the present invention. Examples of the trifunctional or higher polyfunctional aromatic compound used in such a branched polycarbonate resin include fluoroglusin, fluorogluside, or 4,6-dimethyl-2,4,6-tris (4-hydrokidiphenyl) hepten-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) Etan, 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, trisphenol such as α-dimethylbenzylphenol, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1, Examples thereof include 4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and their acid chlorides, among which 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 structural unit derived from the polyfunctional aromatic compound in the branched polycarbonate is preferably a total of 100 mol% of the structural unit derived from the divalent phenol and the structural unit derived from the polyfunctional aromatic compound. It is 0.01 to 1 mol%, more preferably 0.05 to 0.9 mol%, still more preferably 0.05 to 0.8 mol%.

Further, particularly in the case of the molten ester exchange method, branched structural units may be generated as a side reaction, and the amount of such branched structural units is preferably 100 mol% in total including the structural units derived from divalent phenol. It is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, still more preferably 0.01 to 0.8 mol%. The ratio of such a branched structure can be calculated by 1H-NMR measurement.

The aliphatic bifunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Examples of the aliphatic bifunctional carboxylic acid include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosandioic acid, and cyclohexanedicarboxylic acid. Such as alicyclic dicarboxylic acid is preferably mentioned. As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.

Reaction formats such as the interfacial polymerization method, the molten transesterification method, the carbonate prepolymer solid phase transesterification method, and the ring-opening polymerization method of the cyclic carbonate compound, which are the methods for producing the polycarbonate resin of the present invention, are described in various documents and patent publications. This 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. It is preferably 2.0 × 10 ^{4 to} 3.5 × 10 ⁴ , and more preferably 2.2 × 10 ^{4 to} 3.0 × 10 ⁴ . If the viscosity average molecular weight is in an appropriate range, good mechanical properties and good fluidity during injection molding tend to be obtained.

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 molding processability is exhibited in gas-assisted molding and foam molding, which may be used when molding a reinforced resin material into a structural member. Such improvement in molding processability is even better than that of the branched polycarbonate. In a more preferred embodiment, the A component is a polycarbonate resin A-1-1-1 component having a viscosity average molecular weight of 7 × 10 ^{4 to} 3 × 10 ⁵ ), and an aromatic having a viscosity average molecular weight of 1 × 10 ^{4 to} 3 × 10 ⁴ . A polycarbonate resin (A-1-1 component) composed of a group polycarbonate resin (A-1-1-2 component) having a viscosity average molecular weight of 1.6 × 10 ^{4 to} 3.5 × 10 ⁴ (hereinafter, “A-1-1 component)”. (Sometimes referred to as "polycarbonate resin containing a high molecular weight component") can 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, 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 ×. It is 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 A-1-1-1 component and the A-1-1-2 component in various proportions to satisfy a predetermined molecular weight range. Can be obtained. Preferably, the A-1-1-1 component is 2 to 40% by weight, and more preferably the A-1-1-1 component is 3 to 30% by weight, based on 100% by weight of the A-1-1 component. The A-1-1-1 component is more preferably 4 to 20% by weight, and particularly preferably the A-1-1-1 component is 5 to 20% by weight.

Further, as a 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). ) Such an aromatic polycarbonate resin using 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, as represented by the method shown in JP-A-5-306336. A method for producing so as to satisfy the conditions of the component A-1-1 of the present invention, and (3) an aromatic polycarbonate resin obtained by such a production method (the production method of (2)), and A separately produced. Examples thereof include a method of mixing the 1-1-1 component and / or the A-1-1-2 component.

The viscosity average molecular weight referred to in the present invention is first determined by using an Ostwald viscometer from a solution of 0.7 g of polycarbonate in 100 ml of methylene chloride at 20 ° C. for the specific viscosity (η _SP ) calculated by the following formula.
Specific viscosity (η _SP ) = (t-t ₀ ) / t ₀
[T ₀ is the number of seconds for methylene chloride to fall, t is the number of seconds for the sample solution to fall]
From the obtained specific viscosity (η _SP ), the viscosity average molecular weight M is calculated by the following formula.
η _SP / c = [η] + 0.45 × [η] ² c (where [η] is the ultimate 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 the weight of methylene chloride to dissolve the soluble component in the composition. Such soluble components are collected by Celite filtration. The solvent in the resulting solution is then removed. The solid after removing the solvent is sufficiently dried to obtain a solid having a component that dissolves in methylene chloride. From a solution prepared by dissolving 0.7 g of such a solid in 100 ml of methylene chloride, the specific viscosity at 20 ° C. is obtained in the same manner as described above, and the viscosity average molecular weight M is calculated from the specific viscosity in the same manner as described above.

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 above general formula (1), R ¹ and R ² are independently hydrogen atom, halogen atom, alkyl group having 1 to 18 carbon atoms, alkoxy group having 1 to 18 carbon atoms, and 6 to 18 carbon atoms, respectively. 20 cycloalkyl groups, cycloalkoxy groups with 6 to 20 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, aryl groups with 6 to 14 carbon atoms, aryloxy groups with 6 to 14 carbon atoms, carbon atoms Represents a group selected from the group consisting of an alkylyl group having a number of 7 to 20, an arylyloxy group having a carbon atom number of 7 to 20, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. E and f are each an integer of 1 to 4, and W is at least one group selected from the group consisting of a single bond or a group 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 above general formula (2), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are independently hydrogen atoms, alkyl groups having 1 to 18 carbon atoms, and carbon. 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, and R ¹⁹ and R ²⁰ are independent hydrogen atoms, halogen atoms, and carbon atoms 1 to 18 respectively. Alkyl group, alkoxy group with 1 to 10 carbon atoms, cycloalkyl group with 6 to 20 carbon atoms, cycloalkyl group with 6 to 20 carbon atoms, alkenyl group with 2 to 10 carbon atoms, 6 carbon atoms From an aryl group of ~ 14, 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. Represents a group selected from the group, and if there are a plurality of groups, they may be the same or different, and 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 above general formula (3), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently substituted with a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or 6 to 12 carbon atoms, respectively. Alternatively, it is an unsubstituted aryl group, and R ⁹ and R ¹⁰ are independently hydrogen atoms, halogen atoms, alkyl groups having 1 to 10 carbon atoms, and alkoxy groups 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 divalent phenol (I) represented by the general formula (1) include 4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and the like. 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'-dihydroxydiphenyl ether, 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'-dimethyldiphenylsulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfide, 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, 3-adamantandiyl) diphenol, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantan and the like can be mentioned.

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, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is preferred. Of these, 2,2-bis (4-hydroxyphenyl) propane, which has excellent strength and good durability, is most preferable. Moreover, these may be used individually or in combination of 2 or more types.

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

The hydroxyaryl-terminated polydiorganosiloxane (II) prescribes phenols having an olefinic unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, and 2-methoxy-4-allylphenol. It is easily produced by subjecting the terminal of a polysiloxane chain having the degree of polymerization of the above to a hydrosilylation reaction. Of these, (2-allylphenol) -terminated polydiorganosiloxane and (2-methoxy-4-allylphenol) -terminated polydiorganosiloxane are preferable, and (2-allylphenol) -terminated polydimethylsiloxane and (2-methoxy-4) are particularly preferable. -Allylphenol) -terminated polydimethylsiloxane is preferred. 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 low temperature impact property during high temperature molding. If the upper limit of such a suitable range is exceeded, the amount of outgas generated during high temperature molding is large, and the low temperature impact resistance may be inferior.

Further, in order to realize high impact resistance, the degree of polymerization (p + q) of the hydroxyaryl-terminated polydiorganosiloxane (II) is preferably 10 to 300. The degree of polymerization of diorganosiloxane (p + q) is preferably 10 to 200, more preferably 12 to 150, and even more preferably 14 to 100. Below the lower limit of the suitable range, the impact resistance characteristic of the polycarbonate-polydiorganosiloxane copolymer is not effectively exhibited, and when the upper limit of the suitable range is exceeded, poor appearance appears.

The content of polydiorganosiloxane in the total weight of the polycarbonate-polydiorganosiloxane copolymer resin used in 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, still more preferably 1 to 20% by weight. Above the lower limit of the suitable range, impact resistance and flame retardancy are excellent, and below the upper limit of the suitable range, a stable appearance that is not easily affected by molding conditions can be easily obtained. The degree of polymerization of polydiorganosiloxane and the content of polydiorganosiloxane can be calculated by 1H-NMR measurement.

In the present invention, only one type of hydroxyaryl-terminated polydiorganosiloxane (II) may be used, or two or more types may be used.

Further, as long as it does not interfere with the present invention, a comonomer other than the above divalent phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) may be added in a range 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 the reaction of divalent phenol (I) and a carbonic acid ester-forming compound in a mixed solution of an organic solvent insoluble in water and an alkaline aqueous solution. To do.

In producing the oligomer of divalent phenol (I), the entire amount of divalent phenol (I) used in the method of the present invention may be an oligomer at a time, or a part thereof may be used as a post-added monomer at the subsequent interface. It may be added as a reaction raw material to the polycondensation reaction. The post-added monomer is added to allow the polycondensation reaction in the subsequent stage to proceed rapidly, and it is not necessary to add it when it is not necessary.

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

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

As the acid binder, for example, 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 are used. Similarly to the above, the ratio of the acid binder used may be appropriately determined in consideration of the stoichiometric ratio (equivalent) of the reaction. Specifically, it is preferable to use 2 equivalents or a slightly excess amount of the acid binder with respect to the number of moles of divalent phenol (I) used for forming the oligomer (usually 1 mol corresponds to 2 equivalents). ..

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

The reaction pressure for forming the oligomer is not particularly limited and may be normal pressure, pressurization, 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 during polymerization, so it is desirable to cool with water or ice. The reaction time depends on other conditions and cannot be unconditionally defined, but is usually 0.2 to 10 hours. The pH range of the oligomer-forming reaction is the same as the known interfacial reaction conditions, and the pH is always adjusted to 10 or more.

In the present invention, after obtaining a mixed solution containing an oligomer of dihydric phenol (I) having a terminal chloroformate group, the molecular weight distribution (Mw / Mn) is up to 3 or less while stirring the mixed solution. 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 polycondensed. Thereby, 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 independently substituted with hydrogen atom, alkyl group having 1 to 12 carbon atoms or 6 to 12 carbon atoms, respectively. Alternatively, it is an unsubstituted aryl group, and R ⁹ and R ¹⁰ are independently hydrogen atoms, halogen atoms, alkyl groups having 1 to 10 carbon atoms, and alkoxy groups 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.)

In carrying out the interfacial polycondensation reaction, an acid binder may be added as appropriate in consideration of the chemical quantitative ratio (equivalent) of the reaction. As the acid binder, for example, 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 are used. Specifically, when a part of the hydroxyaryl-terminated polydiorganosiloxane (II) to be used or a part of the divalent phenol (I) as described above is added as a post-addition monomer to this reaction step, the post-addition amount is two. It is preferable to use 2 equivalents or an excess amount of alkali with respect to the total number of moles of the valent phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) (usually 1 mol corresponds to 2 equivalents).

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

In such a polymerization reaction, a terminal terminator or a molecular weight modifier is usually used. Examples of the terminal terminator include compounds having a monovalent phenolic hydroxyl group, and in addition to ordinary phenols, p-tert-butylphenols, p-cumylphenols, tribromophenols, etc., long-chain alkylphenols and aliphatic carboxylic acids Examples thereof include chloride, aliphatic carboxylic acid, hydroxybenzoic acid alkyl ester, hydroxyphenyl alkyl acid ester, and alkyl ether phenol. The amount used is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, with respect to 100 mol of all the divalent phenolic compounds used, and it is naturally possible to use two or more kinds of compounds in combination. is there.

A catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt may be added to promote the polycondensation reaction.
The reaction time of such a 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 divalent phenolic compound to obtain a branched polycarbonate-polydiorganosiloxane. Examples of the trifunctional or higher polyfunctional aromatic compound used in such a branched polycarbonate-polydiorganosiloxane copolymer resin include fluoroglusin, fluorogluside, or 4,6-dimethyl-2,4,6-tris (4-hydrokidiphenyl). ) Hepten-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, trisphenol such as α-dimethylbenzylphenol, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxy) Examples thereof include phenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and their acid chlorides, among which 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 ratio of the polyfunctional compound in the branched polycarbonate-polydiorganosiloxane copolymer resin is preferably 0.001 to 1 mol%, more preferably 0.005 to 0, based on the total amount of the aromatic polycarbonate-polydiorganosiloxane copolymer resin. It is 9.9 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 can be reduced pressure, normal pressure, or pressurized pressure, but usually, normal pressure or the self-pressure of the reaction system can be preferably used. The reaction temperature is selected from the range of -20 to 50 ° C., and in many cases, heat is generated during polymerization, so it is desirable to cool with water or ice. The reaction time varies depending on other conditions such as the reaction temperature and cannot be unconditionally specified, but 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, cross-linking treatment, partial decomposition treatment, etc.) to reduce the desired amount. 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 subjecting various post-treatments such as a known separation and purification method.

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

(Component B: Polymer obtained by polymerizing one or more selected from the group consisting of aromatic vinyl monomer, vinyl cyanide monomer and alkyl (meth) acrylate monomer)
The B component of the present invention is a polymer obtained by polymerizing one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers and alkyl (meth) acrylate monomers. Is. Aromatic vinyl monomers include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert-butylstyrene, vinylnaphthalene, and methoxystyrene. Styrene is particularly preferable. These can be used alone or in combination of two or more. Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile, and acrylonitrile is particularly preferable. These can be used alone or in combination of two or more. Specific examples of the alkyl (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and amyl (meth) acrylate. , Hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate And so on. The notation of (meth) acrylate indicates that both methacrylate and acrylate are included.

The component B is a polystyrene resin, specifically, an acrylonitrile-butadiene-styrene copolymer (ABS resin), a polystyrene resin (PS resin), an acrylonitrile-styrene copolymer (AS resin), and an acrylonitrile-α-methyl. Styrene copolymer (αMS-AN copolymer), methyl (meth) acrylate-styrene copolymer (MS copolymer), methyl (meth) acrylate-styrene-acrylonitrile copolymer (MAS copolymer), etc. Acrylonitrile-styrene copolymer (AS resin) is particularly preferable. The composition ratio of the AS resin is not particularly limited, but the ratio of styrene / acrylonitrile is preferably 95/5 to 50/50, more preferably 90/10 to 60/40.

The B component may be produced by any of bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. When the B component is a graft polymer, the copolymerization method is one-step grafting. However, it does not matter whether it is a multi-stage graft. Further, it may be a mixture with a copolymer containing only a graft component produced as a by-product during production.

The content of the B component is 1 to 30 parts by weight, preferably 5 to 20 parts by weight, and more preferably 10 to 15 parts by weight with respect to 100 parts by weight of the A component. If the content of component B is less than 1 part by weight, sufficient fluidity cannot be obtained, and if it exceeds 30 parts by weight, impact resistance, flame retardancy and appearance of the molded product are deteriorated.

(C component: impact modifier)
The flame-retardant polycarbonate resin composition of the present invention contains an impact modifier excluding the B component as the C component. The impact modifier is a polymer having a core-shell structure, preferably containing a rubber component, more preferably a rubber component in the core. Further, a graft polymer obtained by graft-polymerizing at least one compound containing a (meth) acrylic acid ester compound to one rubber selected from the group consisting of butadiene rubber, acrylic rubber and silicone / acrylic composite rubber. It is even more preferred that the graft polymer has a core-shell structure. The core-shell type graft polymer is one of the monomers selected from vinyl compounds copolymerizable with (meth) acrylic acid ester compounds, aromatic alkenyl compounds, etc., with a rubber component having a glass transition temperature of 10 ° C. or less as the core. It is a graft copolymer copolymerized with seeds or two or more kinds as a shell.

The rubber component of component C includes butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, silicone / acrylic composite rubber, isobutylene-silicone composite rubber, isoprene rubber, styrene-butadiene rubber, chloroprene rubber, and ethylene-propylene rubber. Nitrile rubber, ethylene-acrylic rubber, silicone rubber, epichlorohydrin rubber, fluororubber, and those in which hydrogen is added to these unsaturated bonds 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. The glass transition temperature of the rubber component is preferably −10 ° C. or lower, more preferably −30 ° C. or lower, and from these points, a butadiene rubber or an acrylic silicone / acrylic composite rubber is particularly preferable as the rubber component. The composite rubber refers to a rubber obtained by copolymerizing two kinds of rubber components or a rubber polymerized so as to have an IPN structure in which they are intertwined with each other so as not to be separated. In the core-shell type graft polymer, the particle size of the core is preferably 240 to 300 nm, more preferably 250 to 290 nm, still more preferably 260 to 280 nm in terms of weight average particle size. Better impact resistance is achieved in the range of 240-300 nm. Further, the particle size distribution is preferably a double dispersion type having two peaks, particularly preferably a double dispersion type having two peaks in the vicinity of 100 nm and 300 nm, and better impact resistance than the single peak single dispersion type is achieved. To.

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, and octyl acrylate, and examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, and butyl methacrylate. , Cyclohexyl methacrylate, octyl methacrylate and the like, 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 contain an aromatic vinyl component from the viewpoint of mechanical properties and flame retardancy. This is because the core-shell type graft polymer has an excellent affinity with the aromatic polycarbonate resin, so that more rubber components are present in the resin, and the good impact resistance of the aromatic polycarbonate resin is further improved. This is because it is 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 100% by weight of the shell in the case of a core-shell type polymer), preferably 10% by weight or more, and more preferably 15% by weight or more. Is preferable. 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, and the copolymerization method is as follows. It does not matter whether it is a one-stage graft or a multi-stage graft. Further, it may be a mixture with a copolymer containing only a graft component produced as a by-product during production. Further, 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 the aqueous phase and the monomer phase are individually held and both are accurately supplied to a continuous disperser, and the particle size 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 into an aqueous liquid having dispersibility by passing through a small-diameter orifice or a porous filter having a diameter of several to several tens of μm may be used. In the case of a core-shell type graft polymer, the reaction may be one-stage or multi-stage for both the core and the shell.

Such polymers are commercially available and easily available. For example, as a rubber component, those containing butadiene rubber as the main component are the Metabrene E series manufactured by Mitsubishi Chemical Corporation (for example, the shell component is E-875A whose main component is methyl methacrylate, and the shell component is mainly methyl methacrylate and styrene. E-870A and the like as a component) can be mentioned. 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 is mainly methyl methacrylate). Examples of those containing 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 shell component is mainly methyl methacrylate).

The content of the C component is 1 to 10 parts by weight, preferably 1.5 to 9 parts by weight, and more preferably 2 to 8 parts by weight with respect to 100 parts by weight of the A component. 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.

(D component: phosphazene)
The flame-retardant polycarbonate resin composition of the present invention contains a phosphazene compound as a D component. By containing a phosphorus atom and a nitrogen atom in the molecule, such a phosphazene compound can impart an effect of suppressing a decrease in flame retardancy and a decrease in impact strength to a flame-retardant polycarbonate resin composition. When a compound other than the phosphazene compound, for example, a phosphoric acid ester or a condensed phosphoric acid ester, is used as the phosphorus-based flame retardant, the impact strength and flame retardancy are reduced due to the plasticization of the polycarbonate resin. Occurs. The phosphazene compound is not particularly limited as long as it does not contain a halogen atom and has a phosphazene structure in the molecule. The phosphazene structure referred to here represents a structure represented by the formula: -P (R2) = N- [in the formula, R2 is an organic group]. The phosphazene compound is represented by the general formulas (5) and (6).

（式中、Ｘ_１、Ｘ_２、Ｘ_３、Ｘ_４は、水素、水酸基、アミノ基、またはハロゲン原子を含まない有機基を表す。また、ｎは３〜１０の整数を表す）。上記式（５）、（６）中、Ｘ_１、Ｘ_２、Ｘ_３、Ｘ_４で表されるハロゲン原子を含まない有機基としては、例えば、アルコキシ基、フェニル基、アミノ基、アリル基などが挙げられる。

(In the formula, X ₁ , X ₂ , X ₃ , and X ₄ represent organic groups that do not contain hydrogen, hydroxyl groups, amino groups, or halogen atoms, and n represents an integer of 3 to 10). Examples of the halogen atom-free organic group represented by X ₁ , X ₂ , X ₃ , and X ₄ in the above formulas (5) and (6) include an alkoxy group, a phenyl group, an amino group, and an allyl group. Can be mentioned.

Commercially available phosphazene compounds include SPS-100, SPE-100, SPR-100, SA-100, SPB-100, SPB-100L (all manufactured by Otsuka Chemical Co., Ltd.), FP-100, FP. -110 (above, manufactured by Fushimi Pharmaceutical Co., Ltd.) can be mentioned. In the present invention, it is allowed to contain other components within a range that does not interfere with the function of the phosphazene compound.

The content of the D component is 1 to 20 parts by weight, preferably 5 to 15 parts by weight, and more preferably 8 to 12 parts by weight with respect to 100 parts by weight of the resin component. If the content of the D component is less than 1 part by weight, the flame retardant effect is difficult to obtain, and if it exceeds 20 parts by weight, the impact resistance is lowered.

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

Examples of the drip inhibitor of the E component include a fluoropolymer having a fibril-forming ability, and examples of such a polymer include polytetrafluoroethylene and tetrafluoroethylene-based copolymers (for example, both tetrafluoroethylene and hexafluoropropylene). Polymers, etc.), partially fluorinated polymers as shown in US Pat. No. 4,379,910, polycarbonate resins made from fluorinated diphenols, and the like. Of these, polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is preferable.

The molecular weight of PTFE having the ability to form fibrils has an extremely high molecular weight, and exhibits a tendency to bond PTFE to each other to form fibers by an external action such as shearing force. Its molecular weight is 1 million to 10 million, more preferably 2 million to 9 million in the number average molecular weight obtained from the standard specific gravity. As the PTFE, not only a solid form but also an aqueous dispersion form can be used. Further, the PTFE having such a fibril-forming ability improves the dispersibility in the resin, and it is also possible to use a PTFE mixture in a mixed form with another resin in order to obtain better flame retardancy and mechanical properties. is there.

Examples of commercially available PTFE products having such a fibril-forming ability include Teflon (registered trademark) 6J of Mitsui-DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500 and F-201L of Daikin Industries, Ltd. and the like. Commercially available aqueous dispersions of PTFE include Fluon AD-1, AD-936 manufactured by Asahi Icy Fluoropolymers Co., Ltd., Fluon D-1 and D-2 manufactured by Daikin Industries, Ltd., and Mitsui Dupont Fluoro. Teflon (registered trademark) 30J manufactured by Chemical Co., Ltd. can be mentioned as a representative.

Examples of the mixed form of PTFE include (1) a method of mixing an aqueous dispersion of PTFE and an aqueous dispersion or solution of an organic polymer and co-precipitating to obtain a coaggregating mixture (Japanese Patent Laid-Open No. 60-258263). (Method described in JP-A-63-154744, etc.), (2) Method of mixing an aqueous dispersion of PTFE with dried organic polymer particles (method described in JP-A-4-272957). , (3) A method of uniformly mixing an aqueous dispersion of PTFE and an organic polymer particle solution and simultaneously removing each medium from such a mixture (Japanese Patent Laid-Open No. 06-220210, Japanese Patent Application Laid-Open No. 08-188653, etc.). The method described), (4) a method for 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 in which an aqueous dispersion and an organic polymer dispersion are uniformly mixed, and then a vinyl-based monomer is further polymerized in the mixed dispersion to obtain a mixture (method described in JP-A-11-29679). Can be used as obtained by. Examples of commercially available products of these mixed forms of PTFE include "Metabrene 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, 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 F component indicates the amount of the net anti-drip agent, and in the case of the mixed form of PTFE, it indicates the 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 0.2 to 1 part by weight with respect to 100 parts by weight of the A component. .. If the amount of the drip inhibitor exceeds the above range and is too small, the flame retardancy becomes insufficient. On the other hand, if the amount of the drip inhibitor exceeds the above range and is too large, PTFE is deposited on the surface of the molded product, which not only deteriorates the appearance but also leads to an increase in the cost of the resin composition.

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 which may be substituted with one or more groups selected from the group consisting of, eg, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, dimethylstyrene, ethyl-styrene, para-tert-butylstyrene. , Methoxystyrene, fluorostyrene, monobromostyrene, dibromostyrene, and tribromostyrene, vinylxylene, vinylnaphthalene, but are not limited thereto. The styrene-based monomer can be used alone or in combination of two or more types.

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 is composed of 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. May be substituted (meth) acrylate derivatives such as (meth) acrylonitril, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, hexyl. (Meta) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate and glycidyl (meth) ) Maleimides which may be substituted with an acrylate, an alkyl group having 1 to 6 carbon atoms, or an aryl group, for example, maleimide, N-methyl-maleimide and N-phenyl-maleimide, maleic acid, phthalic acid and itaconic acid are exemplified. However, it is not limited to these. The acrylic monomer can be used alone or in combination of two or more types. Of these, (meth) acrylonitrile is preferred.

The amount of the acrylic monomer-derived unit contained in the organic polymer used for 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 8-9 parts by weight. If the amount of the acrylic monomer-derived unit is less than 8 parts by weight, the coating strength may be lowered, 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, still more preferably 0.1 to 0%. 3% by weight. If the residual water content is more than 0.5% by weight, the flame retardancy may be adversely affected.

In the process of producing the polytetrafluoroethylene-based mixture of the present invention, a coating layer containing one or more monomers selected from the group consisting of styrene-based monomers and acrylic monomers in the presence of an initiator. Includes the step of forming the outer part of 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 steps. The drying step can be performed using methods known in the art, such as hot air drying or vacuum drying methods.

The initiator used in the polytetrafluoroethylene-based mixture of the present invention can be used without limitation as long as it is used for the polymerization reaction of styrene-based and / or acrylic-based monomers. Examples of the initiator include, but are not limited to, cumyl hydroperoxide, di-tert-butyl peroxide, benzoyl peroxide, hydrogen peroxide, and potassium peroxide. In the polytetrafluoroethylene-based mixture of the present invention, one or more of the initiators can be used 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 type / amount of the monomer, and is 0.15 to 0. Based on the amount of the total composition. It is preferable to use 25 parts by weight.

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

First, water and branched polytetrafluoroethylene dispersion (solid concentration: 60%, polytetrafluoroethylene particle size: 0.15 to 0.3 μm) are placed in the reactor, and then the acrylic monomer and styrene are 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 completion of the reaction, water was removed by centrifuging with a centrifuge for 30 minutes to obtain a paste-like product. Then, the paste of the product was dried in 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.

Since such a suspension polymerization method does not require a polymerization step by emulsion dispersion in the emulsion polymerization method exemplified in Japanese Patent No. 3469391, it does not require an emulsifier and electrolyte salts for coagulating and precipitating the latex after polymerization. Further, in the polytetrafluoroethylene mixture produced by the emulsion polymerization method, the emulsifier and the electrolyte salts in the mixture are easily mixed and difficult to remove, so that 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 a suspension polymerization method, sodium metal ions and potassium metal ions in the mixture are reduced because such emulsifiers and electrolyte salts are not used. It is possible to improve thermal stability and hydrolysis resistance.

Further, in the present invention, coated branched PTFE can be used as a drip inhibitor. 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 units and / or units 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-based monomer and an acrylic-based monomer.

The polytetrafluoroethylene contained in the coated branched PTFE is branched polytetrafluoroethylene. When the contained polytetrafluoroethylene is not branched polytetrafluoroethylene, the effect of preventing dropping becomes insufficient when the addition of polytetrafluoroethylene is small. The branched polytetrafluoroethylene is in the form of particles, preferably having a particle size of 0.1 to 0.6 μm, more preferably 0.3 to 0.5 μm, and even more 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 deteriorate. The number average molecular weight of the polytetrafluoroethylene used in the present invention is preferably 1 × 10 ⁴ to 1 × 10 ⁷ , more preferably 2 × 10 ^{6 to} 9 × 10 ⁶ , and generally has a high molecular weight of polytetra. Fluoroethylene is more preferred in terms of stability. Either powder or dispersion 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, still more preferably 47 to 47 to 100 parts by weight based on the total weight of the coated branched PTFE. It is 53 parts by weight, particularly preferably 48 to 52 parts by weight, and most preferably 49 to 51 parts by weight. When the ratio 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 an F component. (In the present invention, the titanium oxide component of the titanium oxide pigment is referred to as "Titanium ₂ ", and the entire pigment containing the surface treatment agent is referred to as "titanium oxide".) The crystal form of TiO ₂ in the F component is anatas type. , Rutile type, and they can be mixed and used as needed. The rutile type is more preferable in terms of initial mechanical properties and long-term weather resistance. In addition, the rutile type crystal may contain an anatas type crystal. Further, as the method for producing TiO ₂ , a product produced by a sulfuric acid method, a chlorine method, or 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 is more preferably in the form of particles. The average particle size of titanium oxide of the present invention is preferably 0.10 to 0.50 μm, more preferably 0.20 to 0.30 μm. If the average particle size is smaller than 0.10 μm, appearance defects such as silver are likely to occur when the particles are highly filled, and if the average particle size is larger than 0.5 μm, the appearance may be deteriorated or the mechanical properties may be deteriorated. The average particle size is calculated by measuring each single particle size from electron microscope observation and averaging the numbers.

The titanium oxide of the F component is preferably surface-treated with an organic compound. When titanium oxide that has not been organically treated is used, the appearance deteriorates due to yellowing, and the reflectance of the molded product is significantly reduced, so that sufficient solar reflectance may not be obtained. Therefore, it is used outdoors. May not be suitable for. As such a surface treatment agent, various treatment agents such as polyol-based, amine-based, and silicone-based can be used. Examples of the polyol-based surface treatment agent include pentaerythritol, trimethylolethane, and trimethylolpropane, and examples of the amine-based surface treatment agent include acetate of triethanolamine and acetate of trimethylolamine. Examples of the silicone-based surface treatment agent include alkylchlorosilane (trimethylchlorosilane and the like), alkylalkoxysilane (methyltrimethoxysilane and the like), and hydrogenpolysiloxane. Examples of the hydrogen polysiloxane include alkylhydrogenpolysiloxane and alkylphenylhydrogenpolysiloxane. As such an alkyl group, a methyl group and an ethyl group are suitable. Titanium oxide surface-treated with such alkylalkoxysilanes and / or hydrogenpolysiloxanes imparts better light reflectivity to the resin compositions of the present invention. The amount of the organic compound used for the surface treatment is preferably 0.05 to 5 parts by weight, more preferably 0.5 to 3 parts by weight, still more preferably 1.5 to 2.5 parts per 100 parts by weight of the F component. It is in the range of parts by weight. If the amount of surface treatment is less than 0.05 parts by weight, sufficient thermal stability may not be obtained, and if it exceeds 5 parts by weight, it is not preferable from the viewpoint of molding defects such as silver. The surface treatment agent for the organic compound is preferably titanium oxide (more preferably, titanium oxide coated with another metal oxide) in advance. However, a method may be used in which the surface treatment agent is separately added when the raw material of the resin composition is melt-kneaded, and the surface treatment of titanium oxide is performed in the melt-kneading step.

The content of the F component is 0.05 to 30 parts by weight, preferably 0.2 to 10 parts by weight, and more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the A component. If the content of the F component is less than 0.05 parts by weight, the impact modifying effect cannot be obtained, and if it exceeds 30 parts by weight, molding defects such as silver and physical properties are significantly 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 orthosilicates, disilicates, cyclic silicates, chain silicates, and the like are suitable. Silicate minerals take a crystalline state, and the crystal shape can take various shapes such as fibrous and plate-like.

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

The silicate mineral may be a hydrate. Those forms of crystal water in the hydrate is entering as a hydrogen silicate ion as Si-OH, which the metal cations into the ionically as hydroxide ion (OH @ -), and the H _{2 O} molecules in the gap of the structure It may be in any form of entering.

As the silicate mineral, an artificial compound corresponding to a natural product can also be used. As the artificial compound, silicate minerals obtained from 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 silicate minerals in each metal oxide component (MO) include the following. Here, the notation in parentheses is the name of a mineral or the like whose main component is such a silicate mineral, and means that the compound in parentheses can be used as an exemplified metal salt.

As those containing K ₂ O in the _{component, K 2 O · SiO 2,} K 2 O · 4SiO 2 · H 2 O, K 2 O · Al 2 O 3 · 2SiO 2 ( _{Karushiraito), K} 2 O · Al ₂ O ₃ · 4SiO ₂ (leucite), and _{K 2 O · Al 2 O 3} · 6SiO 2 ( orthoclase), and the like.

As comprising Na ₂ O in the _component, Na ₂ O · SiO _2, and its _{hydrates, Na 2 O · 2SiO 2,} 2Na 2 O · SiO 2, Na 2 O · 4SiO 2, Na 2 O · 3SiO _{2 · 3H 2 O, Na 2} O · Al 2 O 3 · 2SiO 2, Na 2 O · Al 2 O 3 · 4SiO 2 ( _{jadeite), 2Na 2 O · 3CaO ·} 5SiO 2, 3Na 2 O · 2CaO · 5SiO _2, and _{Na 2 O · Al 2 O 3} · 6SiO 2 ( albite), and the like.

Li ₂ O and as including the components _{thereof, Li 2 O · SiO 2,} 2Li 2 O · SiO 2, Li 2 O · SiO 2 · H 2 O, 3Li 2 O · 2SiO 2, Li 2 O · Al 2 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), and the like.

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 ochermanite and Guerenite (Merilite), CaO · SiO ₂ (Wollastonite (including both α-type and β-type)), CaO · MgO · 2SiO _{2 (Jiopusaido), CaO · MgO · SiO 2} ( ash magnesia _{olivine), 3CaO · MgO · 2SiO 2} ( _{Meruuinaito), CaO · Al 2 O 3} · 2SiO 2 ( anorthite), 5CaO · 6SiO ₂ · 5H ₂ O (tobermorite, other 5CaO · 6SiO ₂ · 9H ₂ O, etc.) tobamovirus light group hydrate, such as, wollastonite group hydrate, such as _{2CaO · SiO 2 · H 2 O} ( fin Blanc Daito), 6CaO · 6SiO Zono Toraito group hydrates such ₂ · _{H 2} O (xonotlite), the gyro light group hydrates such _{2CaO · SiO 2 · 2H 2 O} ( gyro _{light), 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.

Further, Portland cement can be mentioned as a silicate mineral containing CaO as a component thereof. The type of Portland cement is not particularly limited, and any type such as ordinary, early-strength, ultra-fast-strength, medium heat, sulfate-resistant, 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.
In addition, blast furnace slag, ferrite and the like can be mentioned as silicate minerals containing CaO as a component thereof.

Examples of those containing ZnO as its component include ZnO · SiO ₂ , ₂ ZnO · SiO ₂ (throstite), and 4 ZnO · 2SiO ₂ · H ₂ O (hemimorphite).

Examples of those containing MnO as its component include MnO · SiO ₂ , ₂ MnO · SiO ₂ , CaO · 4 MnO · 5SiO ₂ (rhodonite) and cause light.

As including FeO in its components, FeO · _SiO 2 (Feroshiraito), 2FeO · SiO _{2 (fayalite), 3FeO · Al 2 O 3} · 3SiO 2 ( Arumanjin), and 2CaO · 5FeO · 8SiO ₂ · H ₂ O (Tetsuakuchinosen stone), and the like.

Examples of those containing CoO as its component include CoO / SiO ₂ and 2CoO / SiO ₂ .

As those containing MgO to the component, MgO · _SiO 2 (steatite, enstatite), 2MgO · SiO _{2 (forsterite), 3MgO · Al 2 O 3} · 3SiO 2 ( Bairopu), 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 ( moisture sensor _{stone), 5MgO · Al 2 O 3} · 3SiO 2 · 4H 2 O ( chlorite) _{, K 2 O · 6MgO · Al} 2 O 3 · 6SiO 2 · 2H 2 O ( _{phlogopite), Na 2 O · 3MgO ·} 3Al 2 O 3 · 8SiO 2 · H 2 O ( melee stone), as well as magnesium tourmaline, straight Examples include sen stone, camington sen stone, vermiculite, and smectite.

Examples of those containing Fe ₂ O ₃ as its component include Fe ₂ O ₃ and SiO ₂ .

Examples of those containing ZrO ₂ as its component include ZrO ₂ · SiO ₂ (zircone) and AZS refractories.

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 O3 ·} 6SiO 2 · 2H 2 O ( phlogopite), and various zeolites, fluorine phlogopite, and biotite, and the like.

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

(talc)
Talc and the in the present invention, the chemical compositional a hydrated magnesium silicate, is generally represented by the chemical formula _{4SiO 2 · 3MgO · 2H 2 O} , a scaly particles having a regular layered structure, also the composition thereof include a SiO ₂ 56-65 wt%, the MgO 28 to 35 wt%, and a _{H 2} O about 5 wt%. Other small amounts of components include Fe ₂ O ₃ 0.03 to 1.2% by weight, Al ₂ O ₃ 0.05 to 1.5% by weight, Ca O 0.05 to 1.2% by weight, and K ₂ O. Contains 0.2% by weight or less, Na ₂ O contains 0.2% by weight or less, and the like. The particle size of talc has an average particle size of 0.1 to 15 μm (more preferably 0.2 to 12 μm, still more preferably 0.3 to 10 μm, particularly preferably 0.5 to 5 μm) measured by the sedimentation method. 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 size of talc refers to D50 (median diameter of particle size distribution) measured by the X-ray transmission method, which is one of the liquid phase sedimentation methods. Specific examples of the device for performing such measurement include Sedigrap 5100 manufactured by Micromeritix.

There are no particular restrictions on the manufacturing method for crushing talc from rough stones, and axial-flow milling methods, annual milling methods, roll milling methods, ball milling methods, jet milling methods, container rotary compression shear milling methods, etc. are used. can do. Further, the talc after crushing is preferably classified by various classifiers and has a uniform particle size distribution. There are no particular restrictions on the classifier, including impactor-type inertial force classifiers (variable impactors, etc.), Coanda effect-based inertial force classifiers (elbow jets, etc.), and centrifugal field classifiers (multi-stage cyclone, microplex, dispersion separator, etc.). , AccuCut, Turbo Classifier, Turboplex, Micron Separator, and Super Separator, etc.). Further, the talc is preferably in an aggregated state in terms of its handleability and the like, and as such a production method, there are a method by degassing compression, a method of compressing using a sizing agent and the like. In particular, the degassing compression method is preferable because it is simple and does not mix unnecessary sizing agent resin components 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 decrease in mechanical strength such as impact characteristics is extremely unfavorable. 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. As the aspect ratio, preferably 5 to 200, more preferably 10 to 100 can be used. The mica used is preferably muscovite mica, and its Mohs hardness is about 3. Muscovite mica can achieve higher rigidity and higher strength than other mica such as florobite, and solves the problem of the present invention at a better level. Further, the mica may be pulverized by either a dry pulverization method or a wet pulverization method. The dry pulverization method is more common at low cost, while the wet pulverization method is effective for pulverizing mica thinner and finer, and as a result, the effect of improving the rigidity of the resin composition is higher.

(Wallast Night)
The fiber diameter of wallastonite 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 determined by observing the reinforcing filler with an electron microscope, determining the individual fiber diameters, and calculating the number average fiber diameter from the measured values. An electron microscope is used because it is difficult for an optical microscope to accurately measure the size of a target level. For the fiber diameter, the filler to be measured for the fiber diameter is randomly extracted from the image obtained by observation with an electron microscope, the fiber diameter is measured near the center, and the number average fiber is obtained from the obtained measured value. Calculate the diameter. The observation magnification is about 1000 times, and the number of measurements 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 values. Observation with a light microscope begins with preparing a sample that is dispersed so that the fillers do not overlap very much. 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 by using an image analysis device for the obtained image data and using a program for obtaining the maximum distance between two points of the image data. Under such conditions, the size per pixel corresponds to a length of 1.25 μm, and the number of measurements is 500 or more (600 or less is suitable for work).

In order to fully reflect the original whiteness of the wallastnite of the present invention in the resin composition, the iron content mixed in the raw material ore and the iron content mixed in due to the wear of the equipment when the raw material ore is crushed are selected by a magnetic separator. It is preferable to remove as much as possible. By such magnetic separator treatment, the iron content in wallastnite is preferably 0.5% by weight or less in terms of Fe ₂ O ₃ .

Silicate minerals (more preferably mica, talc, wallastonite) are preferably not surface treated, but are surface treated with various surface treatment agents such as silane coupling agents, higher fatty acid esters, and waxes. May be. Further, it may be granulated with a sizing agent such as various resins, higher fatty acid esters, and waxes to form granules.

The content of the G component is preferably 0.1 to 50 parts by weight, more preferably 0.15 to 40 parts by weight, and further preferably 0.2 to 30 parts by weight with respect to 100 parts by weight of the A component. Is. With the addition of the G component, flame retardancy and rigidity can be improved, but if it exceeds 50 parts by weight, impact resistance may be 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, phosphonic acid, phosphonic acid and esters thereof, and tertiary phosphine.

Specifically, examples of the phosphite compound include triphenylphosphite, tris (nonylphenyl) phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite, and dioctylmonophenyl. Phosphite, diisopropylmonophenylphosphite, monobutyldiphenylphosphite, monodecyldiphenylphosphite, monooctyldiphenylphosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-iso-propylphenyl) -N-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, distearylpentaerythritol 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, dicyclohexylpentaerythritol diphosphite and the like.

Further, as another phosphite compound, a compound which reacts with divalent phenols and has a cyclic structure can also 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 thereof include butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite and 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphosphite.

Phosphate compounds 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 triphenyl phosphate and trimethyl phosphate are preferable.

Phenylnite compounds include tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite and tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylenedi. Phenylonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite , Tetrax (2,6-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, Tetrax (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-Phenylphenyl) -3-Phenyl-Phenylphosphonite, bis (2,6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) Examples thereof include -3-phenyl-phenylphosphonite, tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite and bis (di-tert-butylphenyl) -phenyl-phenylphosphonite are preferable, and tetrakis (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 a phosphite compound having an aryl group in which the alkyl group is substituted by 2 or more.

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

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

The phosphorus-based stabilizer can be used not only by one type but also by mixing two or more types. Among the above phosphorus-based stabilizers, a phosphonite compound or a phosphite compound represented by the following general formula (7) is preferable.

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

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

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

Further, more suitable phosphite compounds in the above formula (7) are distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, and bis (2,6-di). -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 Adecaster PEP-8 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and JPP681S (trademark, manufactured by Johoku Chemical Industry Co., Ltd.), and both can be used. Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite is Adecastab PEP-24G (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.), Alkanox P-24 (trademark, manufactured by Great Lakes), Ultranox. P626 (trademark, manufactured by GE Specialty Chemicals), Doverphos S-9432 (trademark, manufactured by Dover Chemicals), 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 Adecaster PEP-36 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and can be easily used. Bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite is Adecaster PEP-45 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and Doverphos S-9228 (trademark). , Made by Dover Chemical), and any of them can be used.

The phosphorus-based stabilizer 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, more preferably 0.03 to 0.8 parts by weight, still more preferably 0, with respect to 100 parts by weight of the component A. It is 05 to 0.5 parts by weight. If the content is less than 0.01 parts by weight, the effect of suppressing thermal decomposition during processing may not be exhibited, and the mechanical properties may not be deteriorated. If the content exceeds 1.0 parts by weight, the mechanical properties may be deteriorated. ..

(Ii) Phenolic Stabilizer The resin composition of the present invention can contain a phenolic stabilizer. Examples of the phenolic stabilizer include hindered phenol, semi-hindered phenol, and less hindered phenol compound, but the hindered phenol compound is particularly preferable from the viewpoint of applying a heat-stabilizing formulation to the polypropylene-based resin. Used for. Examples of such hindered phenol compounds include α-tocopherol, butylhydroxytoluene, cinapyl 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-methylphenylacrylate, 2,6-di-tert-butyl-4- (N, N-dimethylamino) Methyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl) -6-tert-butylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-dimethylene- Bis (6-α-methyl-benzyl-p-cresol), 2,2'-ethylidene-bis (4,6-di-tert-butylphenol), 2,2'-butylidene-bis (4-methyl-6-) tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate , 1,6-Hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- (3-tert-butyl) -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-butylpheno) , 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, triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, triethylene glycol-N-bis-3- (3-tert-Butyl-4-hydroxy-5-methylphenyl) acetate, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) acetyloxy} -1 , 1-Dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, tetrakis [methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane , 1,3,5-trimethyl-2,4,6-tris (3-tert-butyl-4-hydroxy-5-methylbenzyl) benzene, and tris (3-tert-butyl-4-hydroxy-5-methyl) Benzyl) isocyanurate and the like are exemplified. Among the above compounds, tetrakis [methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane and octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate is preferably used, and is represented by the following formula (8) (3,3', 3'', 5,5', 5 as being excellent in suppressing deterioration of mechanical properties due to thermal decomposition during processing. '' -Hexa-tert-butyl-a, a', a''-(mesitylen-2,4,6-triyl) tri-p-cresol, and 1,3,5 represented by the following formula (9). -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 phenolic stabilizers can be used alone or in combination of two or more. The content of the phenolic stabilizer is preferably 0.05 to 1.0 parts by weight, more preferably 0.07 to 0.8 parts by weight, and even more preferably 0. parts by weight with respect to 100 parts by weight of the A component. 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 the mechanical properties may be deteriorated, and if it exceeds 1.0 parts by weight, the mechanical properties may be deteriorated. ..

It is preferable that either a phosphorus-based stabilizer or a phenol-based stabilizer is blended, and the combined use of these is even more preferable. In the case of combined use, it is preferable that 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 blended with respect to 100 parts by weight of the component A.

(Iii) Ultraviolet absorber The flame-retardant polycarbonate resin composition of the present invention can contain an ultraviolet absorber. Examples of benzophenone-based UV absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, and 2-. Hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxitrihydrate 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 thereof include hydroxy-2-methoxyphenyl) methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

In the benzotriazole system, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazol, 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-benzotriazole-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazol, 2- (2- (2-) Hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5) -Tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2'- Methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis (1,3-benzoxazine-4-one), and 2- [2-hydroxy-3- (3,4) 5,6-Tetrahydrophthalimidemethyl) -5-methylphenyl] benzotriazol, and 2- (2'-hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole and vinyl-based monomers copolymerizable with 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. -A polymer having a benzotriazole skeleton is exemplified.

In the hydroxyphenyltriazine system, for example, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-hexyloxyphenol, 2- (4,6-diphenyl-1,3,5) -Triazine-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-ethyloxyphenol, 2- (4,6-diphenyl) -1,3,5-triazine-2-yl) -5-propyloxyphenol, and 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-butyloxyphenol, etc. Illustrated. Further, the phenyl group of the above-exemplified compound such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl) -5-hexyloxyphenol is 2,4-dimethyl. A compound that has become a phenyl group is exemplified.

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

In the cyanoacrylate system, 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 above-mentioned ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, so that such an ultraviolet-absorbing monomer and / or a photostable monomer and a single amount of an alkyl (meth) acrylate or the like are used. It may be a polymer-type ultraviolet absorber copolymerized with a body. Preferable examples of the ultraviolet-absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in an ester substituent of a (meth) acrylic acid ester. Ru.

Among the above compounds, in the present invention, the compound represented by any of the following formulas (10), (11) and (12) is more preferably used.

上記紫外線吸収剤は、単独でまたは２種以上を組合せて使用することができる。

The above-mentioned ultraviolet absorbers can be used alone or in combination of two or more.

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 further preferably 0.15 to 1 part by weight with respect to 100 parts by weight of the A component. Is. If the content of the ultraviolet absorber is less than 0.1 parts by weight, sufficient light resistance may not be exhibited, and if it is more than 3 parts by weight, it is not preferable from the viewpoint of poor appearance and deterioration of physical properties due to gas generation.

(Iv) Hindered Amine-based Light Stabilizer The flame-retardant polycarbonate resin composition of the present invention may contain a hindered amine-based light stabilizer. Hindered amine-based light stabilizers are generally called HALS (Hindered Amine Light Stabilizer) and are compounds having a 2,2,6,6-tetramethylpiperidine skeleton in their 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-) Piperidine) carbonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) oxalate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) malonate, bis (1,2, 2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) adipate, bis (1,2,2,6,6-pentamethyl-4-) Piperidine) terephthalate, N, N'-bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzenedicarboxyamide, 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-piperidyltrilen) -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-tetramethylpiperidine-4-yl) amino) -triazine-2-yl) -4,7-diazadecan-1,10-diamine, dibutylamine, 1,3,5-triazine, N, N' Polycondensate of −bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine , Poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-diyl} Piperidine) 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]- With 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- [2,4,5,10-tetraoxaspiro (5,5)) Undecane] Examples thereof include a condensate with diethanol.

Hindered amine-based photostabilizers are roughly classified according to the bond partner of the nitrogen atom in the piperidine skeleton, NH type (hydrogen is bonded to the nitrogen atom), NR type (alkyl group (R) is bonded to the nitrogen atom), There are three types, N-OR type (alkoxy group (OR) bonded to nitrogen atom), but when applied to polycarbonate resin, N-R is low basic from the viewpoint of basicity of hindered amine light stabilizer. It is more preferable to use a mold or N-OR mold.

Among the above compounds, the compounds represented by the following formulas (13) and (14) are more preferably used in the present invention.

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

(V) Release Agent It is preferable to further add a mold release agent to the flame-retardant polycarbonate resin composition of the present invention for the purpose of improving the productivity at the time of molding and reducing the distortion of the molded product. As such a release agent, a known one can be used. For example, saturated fatty acid esters, unsaturated fatty acid esters, polyolefin waxes (polyethylene wax, 1-alkene polymer, etc. those modified with functional group-containing compounds such as acid modification can also be used), silicone compounds, fluorine compounds ( Fluorooil represented by polyfluoroalkyl ether), paraffin wax, beeswax and the like can be mentioned. Among them, a fatty acid ester is mentioned as a preferable release agent. Such fatty acid esters are esters of fatty alcohols and aliphatic carboxylic acids. Such an aliphatic alcohol may be a monohydric alcohol or a divalent or higher polyhydric alcohol. The carbon number of the alcohol is in the range of 3 to 32, more preferably in the range of 5 to 30. Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, ceryl alcohol, triacontanol and the like. Examples of such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. In the fatty acid ester of the present invention, a polyhydric alcohol is more preferable.

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), nonadecanic acid, bechenic acid, and the like. Saturated aliphatic carboxylic acids such as icosanoic acid and docosanoic acid, and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and sethalic acid can be mentioned. .. Among the above, the aliphatic carboxylic acid preferably has 14 to 20 carbon atoms. Of these, saturated aliphatic carboxylic acids are preferable. Particularly stearic acid and palmitic acid are preferred.

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

The fatty acid ester of the present invention may be either a partial ester or a total ester (full ester). However, a partial ester usually has a high hydroxyl value and easily induces decomposition of the resin at a high temperature, so that it is more preferably a full ester. The acid value of the fatty acid ester of the present invention is preferably 20 or less, more preferably 4 to 20, and even more preferably 4 to 12 from the viewpoint of thermal stability. The acid value can be substantially 0. 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 0. These characteristics can be determined by the method specified in JIS K 0070.

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 further preferably 0.05 to 0.5 part by weight with respect to 100 parts by weight of the component A. Is. In such a range, the flame-retardant polycarbonate resin composition has good releasability and roll releasability. In particular, such an amount of fatty acid ester provides a flame-retardant polycarbonate resin composition having good releasability and roll releasability without impairing good hue.

(Vi) Dyeing Pigment The flame-retardant polycarbonate resin composition of the present invention can further provide a molded product containing various dyeing pigments and exhibiting various designs. By blending a fluorescent whitening agent or a fluorescent dye that emits light other than that, it is possible to impart a better design effect that makes the best use of the emitted color. It is also possible to provide a flame-retardant polycarbonate resin composition which is colored with a very small amount of dyeing pigment and has a vivid color development property.

Examples of the fluorescent dye (including the fluorescent whitening agent) used in the present invention include a coumarin-based fluorescent dye, a benzopyran-based fluorescent dye, a perylene-based fluorescent dye, an anthracinone-based fluorescent dye, a thioindigo-based fluorescent dye, and a xanthene-based fluorescent dye. , Xantone-based fluorescent dye, thioxanthene-based fluorescent dye, thioxanthone-based fluorescent dye, thiazine-based fluorescent dye, diaminostilben-based fluorescent dye, and the like. 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 the polycarbonate resin, are preferable.

Examples of dyes other than the above brewing agents and fluorescent dyes include perylene dyes, coumarin dyes, thioindigo dyes, anthracinone dyes, thioxanthone dyes, ferrocyanides such as navy blue, perinone dyes, quinoline dyes, and quinacridones. Examples thereof include dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Further, the resin composition of the present invention can also be blended with a metallic pigment to obtain a better metallic color. As the metallic pigment, those having a metal film or a metal oxide film on various plate-shaped fillers are preferable.

The content of the dye pigment is preferably 0.00001 to 1 part by weight, more preferably 0.00005 to 0.5 part by weight, based on 100 parts by weight of the A component.

(Vii) Other Heat Stabilizers The flame-retardant polycarbonate resin composition of the present invention may contain other heat stabilizers other than the above-mentioned phosphorus-based stabilizers and phenol-based stabilizers. Such other heat stabilizers are preferably used in combination with either of these stabilizers and antioxidants, and particularly preferably in combination with both. Examples of such other heat stabilizers include lactone-based stabilizers represented by reaction products of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene (such stabilizers). The details of the above are described in Japanese Patent Application Laid-Open No. 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. Also in the present invention, such a premixed stabilizer can be used. The blending amount of the lactone-based stabilizer is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight, based on 100 parts by weight of the A component.

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

(Viii) Filler The flame-retardant polycarbonate resin composition of the present invention can be blended with various fillers excluding silicate minerals, which are G components, as a reinforcing filler within the range in which the effects of the present invention are exhibited. .. For example, calcium carbonate, glass fiber, glass bead, glass balloon, glass milled fiber, glass flake, carbon fiber, carbon flake, carbon bead, carbon milled fiber, graphite, gas phase growth method ultrafine carbon fiber (fiber diameter 0.1 μm) Less than), carbon nanotubes (fiber diameter less than 0.1 μm, hollow), fullerene, 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 contained 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 A component.

(Ix) Other Resins and Elastomers In the resin composition of the present invention, other resins and elastomers can be used in a small proportion as long as the effects of the present invention are exhibited.
Examples of such other resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, and polymethacrylate resins. , Phenolic resin, epoxy resin and other resins.

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

(X) Other Additives In addition, the flame-retardant polycarbonate resin composition of the present invention contains a small proportion of additives known per se in order to impart various functions and improve properties to the molded product. Can be done. These additives are in the usual blending amount as long as the object of the present invention is not impaired.
Examples of such additives include sliding agents (for example, PTFE particles), colorants (for example, pigments and dyes such as carbon black), and light diffusers (for example, acrylic crosslinked particles, silicone crosslinked particles, ultrathin glass flakes, calcium carbonate particles). , Fluorescent dyes, inorganic phosphors (eg, phosphors whose mother crystal is aluminate), antistatic agents, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (eg, fine particle titanium oxide, fine particle oxidation) Zinc oxide), radical generators, infrared absorbers (heat ray absorbers), photochromic agents and the like.

The embodiment for carrying out the present invention is a collection of preferable ranges of each of the above requirements. For example, a representative example 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. Unless otherwise specified, the parts in the examples are parts by weight, and% is by weight%. 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 placed at a cylinder temperature of 250 ° C., a mold temperature of 60 ° C., and an injection speed of 30 mm / s. It was molded by injection molding under the conditions of (1), and its hue and the presence or absence of silver streaks were observed. For evaluation, the 10th shot from immediately after purging was discarded, the 11th shot was used for hue evaluation, and the molded product up to 20 shots was used for silver streak evaluation. The case where silver streak was not confirmed was indicated by "○", and the case where silver streak was confirmed was indicated by "x". (Ii) Charpy Impact Strength Using the ISO bending test piece obtained by the following method, the notched Charpy impact strength was measured according to ISO 179.
(Iii) Flame retardancy A V test and a 5V test were carried out according to UL94 using UL test pieces obtained by the following method. In addition, the case where the judgment could not meet any of the criteria of V-0, V-1, and V-2 was shown as "notV", and the case where the criteria of 5VB could not be met was shown as "not5V". ..
(Iv) Fluidity The Archimedes-type spiral flow length having a flow path thickness of 2 mm and a flow path width of 8 mm was measured by an injection molding machine [SG150U manufactured by Sumitomo Heavy Industries, Ltd.]. The measurement was performed at a cylinder temperature of 260 ° C., a mold temperature of 70 ° C., and an injection pressure of 98 MPa.

[Examples 1 to 26, Comparative Examples 1 to 11]
A mixture having the compositions shown in Tables 1 and 2 and consisting of components other than D-2 was supplied from the first supply port of the extruder. Such a mixture was obtained by mixing the following premix of (i) with other components with a V-type blender. That is, (i) a mixture of the drip inhibitor of the E component and the aromatic polycarbonate of the A component, and the entire bag is shaken uniformly in a polyethylene bag so that the E component is 2.5% by weight thereof. It is a mixed mixture. When further adding D-2, use a liquid injection device (HYM-JS-08 manufactured by Fuji Techno Industry Co., Ltd.) while heating to 80 ° C., and use a third supply port (with the first supply port) in the middle of the cylinder. It was supplied to the extruder in a predetermined ratio from the position between the vent and the exhaust port. The liquid injection device was set to supply a fixed amount, and the supply amount of other raw materials was precisely measured by a measuring instrument [CWF manufactured by Kubota Co., Ltd.]. For extrusion, a vent type twin-screw extruder with a diameter of 30 mmφ (Japan Steel Works, Ltd. TEX30α-38.5BW-3V) is used for melt-kneading 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. The extrusion temperature was 260 ° C. from the first supply port to the die portion. A part of the obtained pellets is dried at 90 to 100 ° C. for 6 hours in a hot air circulation type dryer, and then an ISO bending test piece is used at a cylinder temperature of 250 ° C. and a mold temperature of 70 ° C. using an injection molding machine. (ISO178 and ISO179) and UL test pieces were molded.

In addition, each component of the symbol notation in Table 1 and Table 2 is as follows.
(Component A)
A-1: Aromatic polycarbonate resin (polycarbonate resin powder with a viscosity average molecular weight of 20,900 made from bisphenol A and phosgene by a conventional method, Panlite L-1225WS (product name) manufactured by Teijin Limited)
A-2: Aromatic polycarbonate resin (polycarbonate resin powder with 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 Limited)
A-3: Aromatic polycarbonate resin (polycarbonate resin powder with 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 Limited)

(B component)
B-1: AS resin (Lightac-A BS218 (trade name) manufactured by Japan A & L Co., Ltd., weight average molecular weight converted to standard polystyrene by GPC measurement: 78,000)
B-2: AS resin (Lightac-A BS207 (trade name) manufactured by Japan A & L Co., Ltd .; weight average molecular weight converted to standard polystyrene by GPC measurement: 98,000)

(C component)
C-1: Silicone-based core-shell type graft polymer (Mitsubishi Rayon Co., Ltd., a graft copolymer having a core-shell structure in which the core is 70 wt% mainly composed of silicone / acrylic composite rubber and the shell is 30 wt% mainly composed of methyl methacrylate. ) Made polymer S-2001 (product name))
C-2: Butadiene-based core-shell type graft polymer (a graft copolymer having a core-shell structure in which the core is 70 wt% mainly composed of butadiene rubber and the shell is 30 wt% mainly composed of methyl methacrylate and styrene, manufactured by Kaneka Corporation. Kaneka M-701 (product name))
C-3: Butadiene-based core-shell type graft polymer (a graft copolymer having a core-shell structure in which the core is 60 wt% mainly composed of butadiene rubber and the shell is 40 wt% mainly composed of methyl methacrylate, Kaneka Corporation Kane Ace M -711 (product name))
C-4: Acrylic core-shell type graft polymer (a graft copolymer having a core-shell structure in which the core is 60 wt% mainly composed of butadiene-acrylic composite rubber and butyl acrylate and the shell is 40 wt% mainly composed of methyl methacrylate, Mitsubishi. Polymer W-600A (product name) manufactured by Rayon Co., Ltd.)

(D component)
D-1: Cyclic phenoxyphosphazene (manufactured by Fushimi Pharmaceutical Co., Ltd .: FP-110T (trade name))
D-2: Phosphate ester containing resorcinol bis (di-2,6-xylyl phosphate) as the main component (manufactured by Daihachi Chemical Industry Co., Ltd .: PX200 (trade name))

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

(F component)
F-1: Titanium dioxide (Typake PC-3 (trade name) manufactured by Ishihara Sangyo Co., Ltd.), the titanium dioxide is a rutile-type crystal produced by the chlorine method, and has a temperature of 23 ° C. to 100 by a thermoweight device (TGA). When the weight loss at ° C. is (a)% by weight and the weight loss at 23 ° C. to 300 ° C. is (b)% by weight, (b)-(a) is 0.57, and the Al element in the fluorescent X-ray measurement. Titanium dioxide pigment with a weight ratio of 0.014 / Ti element and 0.018 weight ratio of Si element / Ti element)
The weight ratio of each element in the fluorescent X-ray measurement was calculated by the basic parameter method using MESA-500 type manufactured by HORIBA, Ltd. Such a calculation method is the same for other titanium dioxide pigments.
F-2: Titanium dioxide (White DCF-T-17007 manufactured by Regino Color Industry Co., Ltd., the titanium dioxide is a rutile-type crystal produced by the chlorine method, and is used at 23 ° C to 100 ° C by a thermoweight device (TGA). When the weight loss is (a)% by weight and the weight loss at 23 ° C. to 300 ° C. is (b)% by weight, (b)-(a) is 0.28, and Al element / Ti element in fluorescent X-ray measurement. Titanium dioxide pigment with a weight ratio of 0.008 and a weight ratio of Si element / Ti element of 0.009)

(G component)
G: Talc (manufactured by 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 and Irganox 1076 (product name) manufactured by BASF Japan Ltd.)
STB-2: Phosphorus-based heat stabilizer (Tris (2,4-di-tert-butylphenyl) phosphite, Irgafos 168 (product name) manufactured by BASF Japan Ltd.)
WAX-1: Fatty acid ester-based release agent (Rikemar SL900 (product name) manufactured by RIKEN Vitamin Co., Ltd.)
WAX-2: Olefin wax by copolymerization of α-olefin and maleic anhydride (manufactured by Mitsubishi Chemical Corporation; Diacarna 30M (trade name))

Claims (8)

(A) With respect to 100 parts by weight of polycarbonate resin (component A)
(B) 1 to 30 parts by weight of a polymer (B component) obtained by polymerizing one or more selected from the group consisting of an aromatic vinyl monomer, a vinyl cyanide monomer and an alkyl (meth) acrylate monomer. ,
(C) Impact modifier (C component) excluding B component, 1 to 10 parts by weight,
(D) Phosphazene (D component) 1 to 20 parts by weight,
A flame-retardant polycarbonate resin composition containing 0.05 to 2 parts by weight of (E) drip inhibitor (E component) and 0.05 to 30 parts by weight of (F) titanium oxide (F component). .. Component B is polystyrene resin, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-α-methylstyrene copolymer, methyl (meth) acrylate-styrene copolymer, and methyl (meth) acrylate. The composition according to claim 1, which comprises a resin selected from the group consisting of a polystyrene-acrylonitrile copolymer. The composition according to claim 2, wherein the component B contains an acrylonitrile-styrene copolymer. The composition according to any one of claims 1 to 3, wherein the component C is a polymer having a core-shell structure containing a rubber component in the core. A graft in which at least one compound including a (meth) acrylic acid ester compound is graft-polymerized with one rubber selected from the group consisting of a butadiene rubber, an acrylic rubber and a silicone / acrylic composite rubber as the C component. The composition according to claim 4, which is a polymer. The composition according to any one of claims 1 to 5, wherein the component E is a fluoropolymer. The composition according to any one of claims 1 to 6, further containing 0.1 to 50 weight by weight of (G) silicate mineral (G component) with respect to 100 parts by weight of component A. A molded product made of the flame-retardant polycarbonate resin composition according to any one of claims 1 to 7.