JP6673638B2 - Flame retardant polycarbonate resin composition - Google Patents

Description

  The present invention relates to a flame-retardant polycarbonate resin composition and a molded product thereof. More specifically, by adding an inorganic filler to a resin composition containing a polycarbonate resin, a polypropylene resin, a styrene thermoplastic elastomer and a flame retardant, mechanical properties, chemical resistance, flame retardancy, surface hardness and The present invention relates to a polycarbonate resin composition having an improved appearance.

  Polycarbonate resins have excellent mechanical and thermal properties, and are therefore widely used in various fields such as OA equipment, electronic and electrical equipment, and automobiles. However, polycarbonate resins have poor meltability due to their high melt viscosity, and because they are amorphous resins, they have difficulty in chemical resistance especially to household or commercial detergents. Therefore, it is known to add a polyolefin-based resin to compensate for these drawbacks.However, with simple addition, the compatibility between the polycarbonate resin and the polyolefin-based resin is low, delamination occurs, and sufficient mechanical properties are obtained. Since it is difficult to obtain, it is in a state of poor practical use.

Therefore, various resin compositions have been proposed in order to increase the compatibility between the polycarbonate resin and the polyolefin-based resin and to impart practical mechanical properties.
For example, a method in which an elastomer graft-modified with a hydroxyl group-containing vinyl monomer is added as a compatibilizer (see Patent Documents 1 and 2), a method in which polypropylene modified with a hydroxyl group-containing vinyl monomer is used as a compatibilizer, and ethylene and carbon atoms 4 A method using an ethylene-α-olefin copolymer comprising the above α-olefin as an impact modifier (see Patent Documents 3 and 4) and a method using a terminal carboxylated polycarbonate resin and an epoxidized polypropylene resin (see Patent Document 5). ), A method using a terminal carboxylated polycarbonate resin and a maleic anhydride-modified polypropylene resin (see Patent Document 6), and a method of adding a styrene-ethylene / butylene-styrene block copolymer as a compatibilizer (see Patent Document 7). Styrene-ethylene-propylene-styrene copolymer There is a method of adding polycarbonate (see Patent Document 8) and the like, but none of them has achieved both chemical resistance so as to exceed the practical range of polycarbonate and mechanical properties that can withstand practical use comparable to PC / ABS.

  In addition, various methods for imparting flame retardancy to a resin composition containing polycarbonate have been reported, but a method for simultaneously imparting high rigidity and flame retardancy to a resin composition containing both polycarbonate and polypropylene. At present, there are almost no reports (see Patent Document 9).

JP-A-7-330972 JP-A-8-134277 JP 2005-132937 A JP-A-54-53162 JP-A-63-215750 JP-A-63-215752 JP-A-5-17633 JP 2000-17120 A JP-A-54-106557

  In view of the above, an object of the present invention is to provide a polycarbonate resin composition having excellent mechanical properties, chemical resistance, flame retardancy, surface hardness, and appearance.

  The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, by adding an inorganic filler to a resin composition containing a polycarbonate-based resin, a polypropylene-based resin, a styrene-based thermoplastic elastomer and a flame retardant, the mechanical properties were improved. The present inventors have found a method for obtaining a polycarbonate resin composition that satisfies chemical resistance, flame retardancy, surface hardness and appearance at a high level, and have completed the present invention.

According to the present invention, the above-mentioned problem is solved by (C) a styrene-based thermoplastic elastomer (C component) with respect to 100 parts by weight of a total of (A) a polycarbonate resin (A component) and (B) a polypropylene resin (B component). ) 1 to 15 parts by weight, (D) 0.01 to 30 parts by weight of a flame retardant (component D) and (E) 1 to 80 parts by weight of an inorganic filler (component E) This is achieved by a resin composition.
Hereinafter, details of the present invention will be described.

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

  Representative examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl). ) Propane (commonly 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) Pentane, 4,4 ′-(p-phenylenediisopropylidene) diphenol, 4,4 ′-(m-phenylenediisoprop Pyridene) diphenol, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ester, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) Fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. Preferred dihydric phenols are bis (4-hydroxyphenyl) alkanes. Among them, bisphenol A is particularly preferred from the viewpoint of impact resistance, and is widely used.

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

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

These special polycarbonates may be used alone, or two or more of them may be appropriately mixed and used. These can also be used by mixing with a commonly used bisphenol A type polycarbonate.
The production methods and properties of these special polycarbonates are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580. ing.

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

Here, the water absorption of polycarbonate is a value obtained by measuring the water content after immersion in 23 ° C water 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. Further, Tg (glass transition temperature) is a value determined by a differential scanning calorimeter (DSC) measurement based on JIS K7121.
As the carbonate precursor, carbonyl halide, carbonic acid diester, haloformate and the like are used, and specific examples include phosgene, diphenyl carbonate and dihaloformate of dihydric phenol.

  In producing the aromatic polycarbonate resin by the interfacial polymerization method of the dihydric phenol and the carbonate precursor, a catalyst, a terminal stopper, and an antioxidant for preventing the dihydric phenol from being oxidized as necessary. May be used. The aromatic polycarbonate resin of the present invention may be 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) difunctional carboxylic acid. Includes carbonate resins, copolymerized polycarbonate resins copolymerized with difunctional alcohols (including alicyclics), and polyester carbonate resins copolymerized with such difunctional carboxylic acids and difunctional alcohols. Also, a mixture of two or more of the obtained aromatic polycarbonate resins may be used.

  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 phloroglucin, phloroglucid, and 4,6-dimethyl-2,4,6-tris (4-hydrokidiphenyl) heptene-2,2. , 4,6-Trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) Ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4- [ 1,1-bis (4-hydroxyphenyl) ethyl] benzene {-α, α-dimethylbenzylphenol, etc. Loxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acids Chloride and the like, among which 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable, and in particular, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane is preferable. 1-Tris (4-hydroxyphenyl) ethane is preferred.

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

  In addition, particularly in the case of the melt transesterification method, a branched structural unit may be generated as a side reaction, and the amount of such a branched structural unit is preferably in a total of 100 mol% with a structural unit derived from a dihydric phenol. It is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, and still more preferably 0.01 to 0.8 mol%. The ratio of the branched structure can be calculated by 1H-NMR measurement.

  The aliphatic difunctional carboxylic acid is preferably an α, ω-dicarboxylic acid. Examples of the aliphatic difunctional carboxylic acid include straight-chain saturated aliphatic dicarboxylic acids such as sebacic acid (decandioic acid), dodecandioic acid, tetradecandioic acid, icosandioic acid, and cyclohexanedicarboxylic acid. And alicyclic dicarboxylic acids. As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.

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

In producing the resin composition of the present invention, the viscosity average molecular weight (M) of the polycarbonate resin is not particularly limited, but is preferably 1 × 10 ^{4 to} 5 × 10 ⁴ , and more preferably 1.4 × 10 4. ^{It is 4 to} 3 × 10 ⁴ , more preferably 1.4 × 10 ^{4 to} 2.4 × 10 ⁴ . In the case of a polycarbonate resin having a viscosity average molecular weight of less than 1 × 10 ⁴ , good mechanical properties may not be obtained. On the other hand, a resin composition obtained from an aromatic polycarbonate resin having a viscosity average molecular weight exceeding 5 × 10 ⁴ may be inferior in versatility in that it is inferior in fluidity during injection molding.

In addition, 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 ) has improved entropic elasticity of the resin. As a result, good moldability is exhibited in gas-assist molding and foam molding that are sometimes used when molding a reinforced resin material into a structural member. Such improvement in moldability is even better than the above-mentioned branched polycarbonate. More preferably, the A component has a viscosity-average molecular weight of 7 × 10 ^{4 to} 3 × 10 ^{5 and} a polycarbonate resin A-1-1-1 component) and a viscosity-average molecular weight of 1 × 10 ^{4 to} 3 × 10 ⁴ . A polycarbonate resin (A-1-1 component) comprising an aromatic polycarbonate resin (A-1-1-2 component) and having a viscosity average molecular weight of 1.6 × 10 ^{4 to} 3.5 × 10 ⁴ (hereinafter referred to as “A-1-1 component”) , "Polycarbonate resin containing high molecular weight component").

In such a polycarbonate resin containing a high molecular weight component (A-1-1 component), the molecular weight of the A-1-1-1 component is preferably from 7 × 10 ⁴ to 2 × 10 ⁵ , more preferably from 8 × 10 ⁴ to 2 × 10 ^4. × 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 A-1-1-2 component is preferably from 1 × 10 ^{4 to} 2.5 × 10 ⁴ , more preferably from 1.1 × 10 ^{4 to} 2.4 × 10 ⁴ , and even more preferably 1.2 × 10 ⁴ . 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 obtained by mixing the above A-1-1-1 component and A-1-1-2 component in various ratios so as to satisfy a predetermined molecular weight range. It can be obtained by adjusting. Preferably, the A-1-1-1 component is 2 to 40% by weight based on 100% by weight of the A-1-1 component, and more preferably, the A-1-1-1 component is 3 to 30% by weight. And more preferably the A-1-1-1 component is 4 to 20% by weight, and particularly preferably the A-1-1-1 component is 5 to 20% by weight.

  As the method for preparing the A-1-1 component, (1) a method in which the A-1-1-1 component and the A-1-1-2 component are independently polymerized and mixed, and (2) A method for producing an aromatic polycarbonate resin having a plurality of polymer peaks in a molecular weight distribution chart by the GPC method, which is represented by the method disclosed in JP-A-5-306336, in the same system, And (3) an aromatic polycarbonate resin obtained by such a production method (the production method of (2)), and A prepared separately. A method of mixing the -1-1-1 component and / or the A-1-1-2 component can be exemplified.

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

  The calculation of the viscosity average molecular weight of the polycarbonate resin in the polycarbonate resin composition of the present invention is performed in the following manner. That is, the composition is mixed with 20 to 30 times the weight of methylene chloride to dissolve soluble components in the composition. The soluble matter is collected by Celite filtration. Thereafter, the solvent in the obtained solution is removed. The solid after removing the solvent is sufficiently dried to obtain a solid of a component soluble in methylene chloride. From a solution in which 0.7 g of the solid is dissolved in 100 ml of methylene chloride, the specific viscosity at 20 ° C. is determined in the same manner as above, and the viscosity average molecular weight M is calculated from the specific viscosity in the same manner as above.

  As the polycarbonate resin (A component) of the present invention, a polycarbonate-polydiorganosiloxane copolymer resin can also be used. 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 a polymer resin.

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

[In the general formula (2), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, Represents a group selected from the group consisting of an aryl group having 3 to 14 atoms and an aralkyl group having 7 to 20 carbon atoms, and R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, a carbon atom having 1 to 18 carbon atoms. Alkyl group, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and 3 carbon atoms To 14 aryl groups, C6 to C10 aryloxy groups, C7 to C20 aralkyl groups, C7 to C20 aralkyloxy groups, nitro groups, aldehyde groups, cyano groups and Represents a group selected from the group consisting of a carboxyl group, and when there are a plurality of groups, they may be the same or different; g is an integer of 1 to 10; h is an integer of 4 to 7; ]

[In the above general formula (3), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a substitution having 6 to 12 carbon atoms. R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and p is a natural number. And q is 0 or a natural number, and p + q is a natural number of 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms. ]

  Examples of the dihydric phenol (I) represented by the general formula (1) include 4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1 -Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxy-3,3'-biphenyl) propane, 2,2-bis (4-hydroxy-3-isopropyl) Phenyl) propane, 2,2-bis (3-t-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2, -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'-dimethyldi Phenyl ether, 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-adamantanediyl) diphenol, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane and the like.

  Among them, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4′-sulfonyldiphenol, 2,2′-dimethyl- 4,4'-sulfonyldiphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis} 2- (4-Hydroxyphenyl) propyl} benzene is preferred, especially 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4 Hydroxyphenyl) cyclohexane (BPZ), 4,4'-sulfonyl diphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is preferred. Among them, 2,2-bis (4-hydroxyphenyl) propane, which has excellent strength and good durability, is most preferable. These may be used alone or in combination of two or more.

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

  The hydroxyaryl-terminated polydiorganosiloxane (II) is a phenol having an olefinic unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, or 2-methoxy-4-allylphenol. Can be easily produced by subjecting a polysiloxane chain terminal having a degree of polymerization to a hydrosilylation reaction. Among them, (2-allylphenol) -terminated polydiorganosiloxane and (2-methoxy-4-allylphenol) -terminated polydiorganosiloxane are preferable, and particularly, (2-allylphenol) -terminated polydimethylsiloxane, (2-methoxy-4) -(Allylphenol) -terminated polydimethylsiloxane is preferred. The hydroxyaryl-terminated polydiorganosiloxane (II) preferably has a molecular weight distribution (Mw / Mn) of 3 or less. Such 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 the preferred range is exceeded, the amount of outgas generated during high-temperature molding is large, and the low-temperature impact resistance may be poor.

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

  The content of the polydiorganosiloxane based on 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, and still more preferably 1 to 20% by weight. Above the lower limit of such a preferred range, excellent impact resistance and flame retardancy are obtained, and below the upper limit of such a preferred range, a stable appearance that is less affected by molding conditions is likely to be obtained. Such polydiorganosiloxane polymerization degree and polydiorganosiloxane content can be calculated by 1H-NMR measurement.

In the present invention, one kind of hydroxyaryl-terminated polydiorganosiloxane (II) may be used alone, or two or more kinds may be used.
Further, within a range that does not hinder the present invention, comonomers other than the dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) are used in an amount of 10% by weight or less based on the total weight of the copolymer. They can be used together.

In the present invention, a mixed solution containing an oligomer having a terminal chloroformate group is prepared by reacting a dihydric phenol (I) with a carbonate-forming compound in a mixed solution of an organic solvent insoluble in water and an aqueous alkali solution in advance. I do.
In producing the oligomer of the dihydric phenol (I), the whole amount of the dihydric phenol (I) used in the method of the present invention may be converted into the oligomer at one time, or a part of the oligomer may be used as a post-addition monomer in the subsequent interface. You may add as a reaction raw material to a polycondensation reaction. The post-addition monomer is added for promptly proceeding the subsequent polycondensation reaction, and it is not necessary to add it when unnecessary.

The method of the oligomer formation reaction is not particularly limited, but a method in which the reaction is usually carried out in a solvent in the presence of an acid binder is preferable.
The proportion of the carbonate-forming compound used may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. When a gaseous carbonate-forming compound such as phosgene is used, a method of blowing the compound into the reaction system can be suitably employed.

  Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. 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 preferred to use 2 equivalents or a slight excess of the acid binder relative to the number of moles of the dihydric phenol (I) used for forming the oligomer (usually 1 mole corresponds to 2 equivalents). .

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

  The reaction pressure for forming the oligomer is not particularly limited, and may be any of normal pressure, increased pressure, and reduced pressure. However, 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 the polymerization. The reaction time depends on other conditions and cannot be specified unconditionally, but is usually 0.2 to 10 hours. The pH range of the oligomer formation reaction is the same as known interface reaction conditions, and the pH is always adjusted to 10 or more.

  The present invention thus obtains a mixed solution containing an oligomer of dihydric phenol (I) having a terminal chloroformate group and then stirs the mixed solution until the molecular weight distribution (Mw / Mn) becomes 3 or less. Highly purified hydroxyaryl-terminated polydiorganosiloxane (II) represented by formula (4) is added to dihydric phenol (I), and the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer are interfacially polycondensed. Thereby, a polycarbonate-polydiorganosiloxane copolymer is obtained.

(In the above general formula (4), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a substitution having 6 to 12 carbon atoms. R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and p is a natural number. And 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.)

In performing the interfacial polycondensation reaction, an acid binder may be appropriately added in consideration of the stoichiometric ratio (equivalent) of the reaction. Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. Specifically, when a part of the hydroxyaryl-terminated polydiorganosiloxane (II) or the dihydric phenol (I) used as a post-addition monomer is added to this reaction step as described above, the post-addition It is preferable to use 2 equivalents or more of an alkali in excess of the total number of moles of the dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) (1 mole usually corresponds to 2 equivalents).
The polycondensation of the oligomer of the dihydric phenol (I) with the hydroxyaryl-terminated polydiorganosiloxane (II) by the interfacial polycondensation reaction is carried out by vigorously stirring the mixture.

  In such a polymerization reaction, a terminal terminator or a molecular weight regulator is usually used. Examples of the terminal stopper include compounds having a monovalent phenolic hydroxyl group. In addition to ordinary phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, and the like, long-chain alkylphenol, aliphatic carboxylic acid Examples thereof include chloride, aliphatic carboxylic acid, hydroxybenzoic acid alkyl ester, hydroxyphenylalkyl acid ester, and alkyl ether phenol. The amount used is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, based on 100 mol of all the dihydric phenol compounds used, and it is naturally possible to use two or more compounds in combination. is there.

A catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt may be added to accelerate the polycondensation reaction.
The reaction time of 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-mentioned dihydric phenol compound to obtain a branched polycarbonate-polydiorganosiloxane. Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate-polydiorganosiloxane copolymer resin include phloroglucin, phloroglucid, and 4,6-dimethyl-2,4,6-tris (4-hydrodiphenyl). ) Heptene-2,2,4,6-trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol Lisphenol, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenone Examples thereof include tetracarboxylic acids and acid chlorides thereof. Among them, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are exemplified. Preferred is 1,1,1-tris (4-hydroxyphenyl) ethane. The proportion of the polyfunctional compound in the branched polycarbonate-polydiorganosiloxane copolymer resin is preferably from 0.001 to 1 mol%, more preferably from 0.005 to 0 mol%, based on the total amount of the aromatic polycarbonate-polydiorganosiloxane copolymer resin. 9.9 mol%, more preferably 0.01 to 0.8 mol%, 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 any of reduced pressure, normal pressure and pressurized pressure, but usually, it can be suitably performed at normal pressure or about the self-pressure of the reaction system. The reaction temperature is selected from the range of −20 to 50 ° C., and in many cases, heat is generated during the polymerization. Since the reaction time varies depending on other conditions such as the reaction temperature, it cannot be unconditionally specified, but is usually 0.5 to 10 hours.

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

  The average size of the polydiorganosiloxane domains in the polycarbonate-polydiorganosiloxane copolymer resin molded product is preferably in the range of 1 to 40 nm. Such an average size is more preferably 1 to 30 nm, even more preferably 5 to 25 nm. If the amount is less than the lower limit of the preferable range, impact resistance and flame retardancy may not be sufficiently exhibited, and if the value exceeds the upper limit of the preferable range, the impact resistance may not be stably exhibited. This provides a polycarbonate resin composition having excellent impact resistance and appearance.

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

In the above formula (1), δ is the standard deviation of the polydiorganosiloxane domain size, and Dav is the average domain size.
The terms "average domain size" and "normalized variance" used in connection with the present invention refer to the measurement of a 1.0-mm-thick portion of a three-stage plate manufactured by the method described in the examples by such a small-angle X-ray scattering method. Shows the measured values obtained by The analysis was performed using an isolated particle model that did not consider the interaction between particles (inter-particle interference).

(B component: polypropylene resin)
The resin composition of the present invention contains a polypropylene resin as the B component. The polypropylene resin is a polymer of propylene, but in the present invention, includes a copolymer with another monomer. Examples of the polypropylene resin of the present invention include a homopolypropylene resin, a block copolymer of propylene with ethylene and an α-olefin having 4 to 10 carbon atoms (also referred to as “block polypropylene”), propylene with ethylene and 4 to 4 carbon atoms. 10 random copolymers with α-olefins (also referred to as “random polypropylene”). In addition, "block polypropylene" and "random polypropylene" are collectively referred to as "polypropylene copolymer".

In the present invention, one or more of the above-mentioned homopolypropylene resin, block polypropylene, and random polypropylene may be used as the polypropylene resin, and among them, homopolypropylene and block polypropylene are preferable.
Examples of the α-olefin having 4 to 10 carbon atoms used in the polypropylene copolymer include 1-butene, 1-pentene, isobutylene, 3-methyl-1-butene, 1-hexene, and 3,4-dimethyl-1. -Butene, 1-heptene, 3-methyl-1-hexene.
The content of ethylene in the polypropylene copolymer is preferably 5% by mass or less based on all monomers. The content of the α-olefin having 4 to 10 carbon atoms in the polypropylene copolymer is preferably 20% by mass or less based on all the monomers.
The polypropylene copolymer is preferably a copolymer of propylene and ethylene or a copolymer of propylene and 1-butene, and particularly preferably a copolymer of propylene and ethylene.

  The melt flow rate (230 ° C., 2.16 kg) of the polypropylene resin in the present invention is preferably 0.1 to 5 g / 10 min, more preferably 0.2 to 4 g / 10 min, and 0.3 to 10 g / 10 min. Particularly preferred is 3 g / 10 min. If the melt flow rate of the polypropylene resin is less than 0.1 g / 10 min, the moldability is inferior due to high viscosity, and if it exceeds 5 g / 10 min, sufficient toughness may not be exhibited. The melt flow rate is also called “MFR”. In addition, MFR was measured based on ISO1133.

  The composition ratio of the polycarbonate resin (component A) and the polypropylene resin (component B) in the resin composition of the present invention is preferably 100 to 90 parts by weight, and more preferably 60 to 90 parts by weight, and more preferably 100 parts by weight. 62.5 to 75 parts by weight, more preferably 65 to 70 parts by weight, component B is preferably 10 to 40 parts by weight, more preferably 25.0 to 37.5 parts by weight, further preferably 30 to 35 parts by weight. is there. If the component A is less than 60 parts by weight, strength and flame retardancy may not be sufficiently exhibited, and if it exceeds 90 parts by weight, chemical resistance may be deteriorated and density may be increased.

(Component C: styrene-based thermoplastic elastomer)
The resin composition of the present invention contains a styrene-based thermoplastic elastomer as the C component. The styrene-based thermoplastic elastomer used in the present invention is preferably a block copolymer represented by the following formula (I) or (II).
X- (YX) n ... (I)
(XY) n ... (II)

  X in the general formulas (I) and (II) is an aromatic vinyl polymer block. In the formula (I), the degree of polymerization may be the same or different at both molecular chain terminals. Y is a butadiene polymer block, an isoprene polymer block, a butadiene / isoprene copolymer block, a hydrogenated butadiene polymer block, a hydrogenated isoprene polymer block, a hydrogenated butadiene / isoprene copolymer block. It is at least one selected from a coalesced block, a partially hydrogenated butadiene polymer block, a partially hydrogenated isoprene polymer block, and a partially hydrogenated butadiene / isoprene copolymer block. N is an integer of 1 or more.

  Specific examples include styrene-ethylene-butylene-styrene copolymer, styrene-ethylene-propylene-styrene copolymer, styrene-ethylene-ethylene-propylene-styrene copolymer, styrene-butadiene-butene-styrene copolymer Styrene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-hydrogenated butadiene diblock copolymer, styrene-hydrogenated isoprene diblock copolymer, styrene-butadiene diblock copolymer, Styrene-isoprene diblock copolymers and the like, among which styrene-ethylene-butylene-styrene copolymer, styrene-ethylene-propylene-styrene copolymer, styrene-ethylene-ethylene-propylene-styrene copolymer, Styrene-butadi Down - butene - styrene copolymer it is most preferred.

  It is desirable that the content of the X component in the block copolymer is in the range of 20 to 80% by weight, preferably 30 to 75% by weight, and more preferably 40 to 70% by weight. When the amount is less than 20% by weight, the rigidity and impact strength of the resin composition are reduced, and when the amount is more than 80% by weight, the impact strength is sometimes reduced.

  The weight average molecular weight of the styrene-based thermoplastic elastomer is preferably 250,000 or less, more preferably 200,000 or less, and still more preferably 150,000 or less. When the weight average molecular weight exceeds 250,000, the moldability is reduced, and the dispersibility in the polycarbonate resin composition may be deteriorated. The lower limit of the weight average molecular weight is not particularly limited, but is preferably 40,000 or more, more preferably 50,000 or more. The weight average molecular weight was measured by the following method. That is, the molecular weight was measured in terms of polystyrene by gel permeation chromatography, and the weight average molecular weight was calculated. The melt flow rate (230 ° C., 2.16 kg) of the styrenic thermoplastic elastomer in the present invention is preferably 0.1 to 10 g / 10 min, more preferably 0.15 to 9 g / 10 min, and 0 to 10 g / 10 min. It is particularly preferred that the pressure be 0.2 to 8 g / 10 min. If the melt flow rate of the styrene-based thermoplastic elastomer is less than 0.1 g / 10 min and exceeds 10 g / 10 min, sufficient toughness may not be exhibited. The MFR was measured at 230 ° C. under a load of 2.16 kg in accordance with ISO1133.

  The content of the component C is 1 to 15 parts by weight, preferably 2 to 14 parts by weight, more preferably 3 to 13 parts by weight based on 100 parts by weight of the total of the component A and the component B. If the content is less than 1 part by weight, impact strength and chemical resistance are reduced, and the appearance of a molded article is poor. If the content is more than 15 parts by weight, rigidity, surface hardness and flame retardancy are reduced.

(D component: flame retardant)
As the D component of the present invention, various compounds conventionally known as a flame retardant of a thermoplastic resin, particularly a polycarbonate resin, can be applied. More preferably, (i) a halogen-based flame retardant (for example, brominated polycarbonate) is used. Compounds, etc.) (ii) phosphorus-based flame retardants (e.g., monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, phosphonic amide compounds, phosphazene compounds, etc.), (iii) metal salt-based flame retardants ( Examples thereof include alkali (earth) metal salts of organic sulfonates, metal borate-based flame retardants, and metal stannate-based flame retardants), and (iv) a silicone-based flame retardant comprising a silicone compound. The compounding of the compound used as a flame retardant not only improves the flame retardancy, but also provides, for example, an improvement in antistatic properties, fluidity, rigidity, and thermal stability based on the properties of each compound.

  The content of the component D is 0.01 to 30 parts by weight, preferably 0.05 to 28 parts by weight, more preferably 0.08 to 25 parts by weight based on 100 parts by weight of the total of the component A and the component B. Department. When the content of the D component is less than 0.01 part by weight, sufficient flame retardancy cannot be obtained, and when it exceeds 30 parts by weight, the impact strength and the chemical resistance are greatly reduced.

(D-1 component: halogen-based flame retardant)
As the halogen-based flame retardant, brominated polycarbonate (including oligomer) is particularly suitable. Brominated polycarbonate is excellent in heat resistance and can greatly improve flame retardancy. In the brominated polycarbonate used in the present invention, the constitutional unit represented by the following formula (5) is preferably at least 60 mol%, more preferably at least 80 mol% of all the constitutional units, and particularly preferably substantially the following constitutional units. It is a brominated polycarbonate compound comprising a structural unit represented by the formula (5).

In the formula (5), X is a bromine atom, R is an alkylene group having 1 to 4 carbon atoms, an alkylidene group having 1 to 4 carbon atoms, or —SO ₂ —.
Further, in such formula (5), preferably R is a methylene group, an ethylene group, an isopropylidene group, -SO 2 - shows a _particularly preferably isopropylidene group.

  The brominated polycarbonate has few residual chloroformate group terminals, and the terminal chlorine content is preferably 0.3 ppm or less, more preferably 0.2 ppm or less. The amount of terminal chlorine can be determined by dissolving the sample in methylene chloride, adding 4- (p-nitrobenzyl) pyridine and reacting with terminal chlorine (terminal chloroformate), and using an ultraviolet-visible spectrophotometer (U-manufactured by Hitachi, Ltd.). -3200). When the amount of terminal chlorine is 0.3 ppm or less, the thermal stability of the polycarbonate resin composition becomes better, and molding at a higher temperature becomes possible. As a result, a resin composition having more excellent moldability is provided.

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

The specific viscosity of the brominated polycarbonate is preferably in the range of 0.015 to 0.1, more preferably in the range of 0.015 to 0.08. The specific viscosity of the brominated polycarbonate is calculated according to the above-described formula for calculating the specific viscosity used in calculating the viscosity average molecular weight of the polycarbonate resin as the component A of the present invention.
When such a halogen-based flame retardant is blended as a flame retardant, the content is 1 to 30 parts by weight, preferably 2 to 27 parts by weight, more preferably 2 to 27 parts by weight, based on 100 parts by weight of the total of the component A and the component B. It is 3 to 25 parts by weight.

Further, the halogen-based flame retardant can further enhance the flame retardancy of the resin composition when used in combination with the antimony oxide compound. Examples of the antimony oxide compound include antimony trioxide, antimony tetroxide, antimony pentoxide represented by (NaO) p · (Sb ₂ O ₅ ) · qH ₂ O (p = 0 to 1, q = 0 to 4) and Sodium antimonate can be used. The antimony oxide compound is preferably used as particles having a particle size of 0.02 to 5 μm. The compounding amount of the antimony oxide compound is 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the total of the component A and the component B. If the amount is less than 0.5 part by weight, the flame retarding effect of the composition due to the synergistic action with the halogen-based flame retardant is small, and if it exceeds 10 parts by weight, the mechanical properties of the composition deteriorate.

(D-2 component: phosphorus-based flame retardant)
The phosphorus-based flame retardant of the present invention is not particularly limited as long as it contains a phosphorus atom in the molecule. And the like. The phosphate ester refers to an ester compound of phosphoric acid and an alcohol compound or a phenol compound.

  Specific examples of the phosphoric acid ester include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, and tris (isopropylphenyl). Phosphate, tris (phenylphenyl) phosphate, trinaphthylphosphate, cresyldiphenylphosphate, xylenyldiphenylphosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenylphosphate, monoisodecylphosphate, 2-acryloyloxyethyl Acid phosphate, 2-methacryloyloxyethyl acid phosphate, diphenyl 2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, diethyl phenylphosphonate, resorcinol poly Examples include phenyl phosphate, resorcinol poly (di-2,6-xylyl) phosphate, bisphenol A polycresyl phosphate, hydroquinone poly (2,6-xylyl) phosphate, and condensed phosphates such as condensates thereof. Examples of the condensed phosphate include resorcinol bis (di-2,6-xylyl) phosphate, resorcinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate) and the like. Commercial products of resorcinol bis (di-2,6-xylyl) phosphate include PX-200 (manufactured by Daihachi Chemical Industry Co., Ltd.). Commercial products of resorcinol bis (diphenyl phosphate) include CR-733S (manufactured by Daihachi Chemical Industry Co., Ltd.). As a commercial product of bisphenol A bis (diphenyl phosphate), CR-741 (manufactured by Daihachi Chemical Industry Co., Ltd.) can be mentioned. Among them, resorcinol bis (di-2,6-xylyl) phosphate is preferably used because of its excellent heat resistance.

  The phosphazene compound can impart flame retardancy to the resin composition by containing a phosphorus atom and a nitrogen atom in the molecule. The phosphazene compound is not particularly limited as long as it does not contain a halogen atom and has a phosphazene structure in the molecule. Here, the phosphazene structure represents a structure represented by the formula: -P (R2) = N- [wherein, R2 is an organic group]. The phosphazene compound is represented by the general formulas (6) and (7).

(In the formula, X ₁ , X ₂ , X ₃ , and X _{4 each} represent hydrogen, a hydroxyl group, an amino group, or an organic group containing no halogen atom; and n represents an integer of 3 to 10.).

In the above formulas (6) and (7), examples of the organic group containing no halogen atom represented by X ₁ , X ₂ , X ₃ and X ₄ include, for example, an alkoxy group, a phenyl group, an amino group, an allyl group and the like. Is mentioned.
Commercially available phosphazene compounds include SPS-100, SPR-100, SA-100, SPB-100, SPB-100L (all manufactured by Otsuka Chemical Co., Ltd.), FP-100, FP-110 (all manufactured by Fushimi Pharmaceutical Co., Ltd.) Manufactured).

  Further, as the red phosphorus, not only untreated red phosphorus but also one whose surface is coated with a metal hydrate and a resin to enhance stability is used. Examples of the metal hydrate include aluminum hydroxide, magnesium hydroxide, zinc hydroxide, and titanium hydroxide. There is no particular limitation on the type of the resin and the amount of the coating, but the resin is preferably a phenol resin or an epoxy resin having a high affinity for the polycarbonate resin used in the present invention.

Further, the coating amount is preferably 1% by weight or more based on red phosphorus. If the amount is less than 1% by weight, the coating effect is not sufficient, and phosphine gas may be generated during high-temperature kneading. The greater the amount of the coating, the more preferable in terms of stability, but preferably not more than 20% by weight from the viewpoint of flame retardancy.
When such a phosphorus-based flame retardant is blended as a flame retardant, its content is 1 to 30 parts by weight, preferably 2 to 27 parts by weight, more preferably 2 to 27 parts by weight, based on 100 parts by weight of the total of the component A and the component B. It is 3 to 25 parts by weight.

(D-3 component: organometallic salt-based flame retardant)
The organic metal salt-based flame retardant is advantageous in that heat resistance is substantially maintained. The organometallic salt-based flame retardants most advantageously used in the present invention are alkali (earth) metal sulfonates. Among them, preferred are alkali (earth) metal salts of fluorine-substituted organic sulfonic acids, and particularly preferred are alkali (earth) metal salts of sulfonic acids having a perfluoroalkyl group. Here, the carbon number of the perfluoroalkyl group is preferably in the range of 1 to 18, more preferably in the range of 1 to 10, and still more preferably in the range of 1 to 8.

  The metal constituting the metal ion of the fluorine-substituted organic sulfonic acid alkali (earth) metal salt is an alkali metal or an alkaline earth metal. Examples of the alkali metal include lithium, sodium, potassium, rubidium, and cesium. Like metals include beryllium, magnesium, calcium, strontium and barium. More preferably, it is an alkali metal. Accordingly, a preferred organic metal salt-based flame retardant is an alkali metal perfluoroalkylsulfonic acid. Among such alkali metals, if the requirement for transparency is higher, rubidium and cesium are preferred, but since they are not versatile and difficult to purify, they may be disadvantageous in terms of cost. is there. On the other hand, while lithium and sodium are advantageous in terms of cost and flame retardancy, they may be disadvantageous in terms of transparency. In consideration of these, the alkali metal in the perfluoroalkylsulfonic acid alkali metal salt can be properly used, and in all respects, potassium perfluoroalkylsulfonic acid salt having an excellent balance of properties is most preferable. Such a potassium salt and a perfluoroalkylsulfonic acid alkali metal salt comprising another alkali metal can be used in combination.

  Such perfluoroalkylsulfonic acid alkali metal salts include potassium trifluoromethanesulfonate, potassium perfluorobutanesulfonate, potassium perfluorohexanesulfonate, potassium perfluorooctanesulfonate, sodium pentafluoroethanesulfonate, perfluorobutanesulfonate Sodium acid, sodium perfluorooctanesulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutanesulfonate, lithium perfluoroheptanesulfonate, cesium trifluoromethanesulfonate, cesium perfluorobutanesulfonate, cesium perfluorooctanesulfonate, Cesium perfluorohexanesulfonate, rubidium perfluorobutanesulfonate, and perflu B hexane sulfonate rubidium, and these may be used in combination of at least one or two. Of these, potassium perfluorobutanesulfonate is particularly preferred.

  The content of the fluoride ion of the above-mentioned organometallic salt-based flame retardant is preferably 50 ppm or less, more preferably 20 ppm or less, further preferably 10 ppm or less, as measured by ion chromatography. The lower the fluoride ion content, the better the flame retardancy and light resistance. Although the lower limit of the fluoride ion content can be set to substantially 0, it is practically preferably about 0.2 ppm from the viewpoint of the number of purification steps and the effect. The alkali metal perfluoroalkylsulfonate having such a fluoride ion content is purified, for example, as follows. The perfluoroalkylsulfonic acid alkali metal salt is dissolved in ion-exchanged water 2 to 10 times the weight of the metal salt in the range of 40 to 90 ° C (more preferably 60 to 85 ° C). The perfluoroalkylsulfonic acid alkali metal salt is prepared by neutralizing perfluoroalkylsulfonic acid with an alkali metal carbonate or hydroxide, or perfluoroalkylsulfonyl fluoride with an alkali metal carbonate or hydroxide. It is produced by a method of neutralization (more preferably by the latter method). The ion-exchanged water is particularly preferably water having an electric resistance value of 18 MΩ · cm or more. The solution in which the metal salt is dissolved is stirred at the above temperature for 0.1 to 3 hours, more preferably 0.5 to 2.5 hours. Thereafter, the liquid is cooled to a range of 0 to 40C, more preferably 10 to 35C. Crystals precipitate upon cooling. The precipitated crystals are taken out by filtration. This produces a suitable purified perfluoroalkylsulfonic acid alkali metal salt.

  When an alkali (earth) metal salt of a fluorine-substituted organic sulfonic acid is used as a flame retardant, the compounding amount is preferably 0.01 to 1.0 part by weight, preferably 100 parts by weight of the total of the component A and the component B Is 0.05 to 0.8 part by weight, more preferably 0.08 to 0.6 part by weight. The flame retardancy is exhibited by the addition of the alkali (earth) metal salt of the fluorine-substituted organic sulfonate as the content is within such a preferable range.

  As the organic metal salt-based flame retardant other than the alkali (earth) metal salt of the fluorine-substituted organic sulfonic acid, a metal salt of an organic sulfonic acid containing no fluorine atom is suitable. Examples of the metal salt include alkali metal salts of aliphatic sulfonic acids, alkaline earth metal salts of aliphatic sulfonic acids, alkali metal salts of aromatic sulfonic acids, and alkaline earth metal salts of aromatic sulfonic acids. Also does not contain a fluorine atom).

  Preferred examples of the aliphatic sulfonic acid metal salt include an alkali (earth) metal alkyl sulfonic acid salt, and these can be used alone or in combination of two or more. The notation of (earth) metal salt is used to include both alkali metal salts and alkaline earth metal salts. Preferred examples of the alkanesulfonic acid used for such an alkali (earth) metal salt of an alkylsulfonic acid include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, methylbutanesulfonic acid, hexanesulfonic acid, and heptane. Sulfonic acid, octanesulfonic acid and the like can be mentioned, and these can be used alone or in combination of two or more.

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

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

  Among the metal salts of organic sulfonic acids not containing a fluorine atom, alkali (earth) metal salts of aromatic sulfonic acids are preferred, and potassium salts are particularly preferred. When such an alkali (earth) metal salt of an aromatic sulfonate is blended as a flame retardant, the content thereof is preferably 0.01 to 1 part by weight, based on 100 parts by weight of the total of the A component and the B component. Is 0.05 to 0.8 part by weight, more preferably 0.08 to 0.6 part by weight.

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

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

Specifically, the structure of the silicone compound used for the silicone-based flame retardant is represented by D _n , T _p , M _m D _n , M _m T _p , M _m Q _q , and M _m D _n T _p as descriptive formulas. _{, M m D n Q q,} M m T p Q q, M m D n T p Q q, D n T p, D n Q q, include _{D n} T p _{Q q.} Structure of preferred silicone compounds in this _is the _{M m D n, M m T} p, M m D n T p, M m D n Q q, more preferably _structures, M m _{D n} or _M m _{D n} T _p .

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

  The silicone compound may be linear or have a branched structure. Further, the organic residue bonded to the silicon atom is preferably an organic residue having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. Specific examples of the organic residue include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a decyl group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group; And aralkyl groups such as tolyl groups. More preferably, it is an alkyl group, alkenyl group or aryl group having 1 to 8 carbon atoms. As the alkyl group, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, and a propyl group is particularly preferable.

  Further, the silicone compound used as the silicone-based flame retardant preferably contains an aryl group. More preferably, the ratio of the aromatic group represented by the following general formula (8) (the amount of the aromatic group) is 10 to 70% by weight (more preferably, 15 to 60% by weight).

(In Formula (8), X independently represents an OH group or a monovalent organic residue having 1 to 20 carbon atoms. N represents an integer of 0 to 5. In Formula (8), n represents 2 In the above cases, different types of X can be taken.)

The silicone compound used as the silicone-based flame retardant may contain a reactive group in addition to the Si—H group and the alkoxy group. Examples of the reactive group include an amino group, a carboxyl group, an epoxy group, and a vinyl group. Groups, mercapto groups, and methacryloxy groups.
As the silicone compound having a Si—H group, a silicone compound containing at least one of the structural units represented by the following general formulas (9) and (10) is preferably exemplified.

(In the formulas (9) and (10), Z ^{1 to} Z ³ each independently represent a hydrogen atom, a monovalent organic residue having 1 to 20 carbon atoms, or a compound represented by the following general formula (11). Α ^{1 to} α ³ each independently represent 0 or 1. m1 represents an integer of 0 or 1 or more. In the formula (9), when m1 is 2 or more, the repeating unit is a plurality of different repeating units. You can take units.)

(In Formula (11), Z ^{4 to} Z ⁸ each independently represent a hydrogen atom or a monovalent organic residue having 1 to 20 carbon atoms. Α ^{4 to} α ⁸ each independently represent 0 or 1. m2 Represents 0 or an integer of 1 or more. Further, in the formula (11), when m2 is 2 or more, the repeating unit may have a plurality of different repeating units.

  In the silicone compound used for the silicone-based flame retardant, examples of the silicone compound having an alkoxy group include at least one compound selected from the compounds represented by the general formulas (12) and (13).

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

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

When a silicone-based flame retardant is used as the flame retardant, the amount thereof is 0.1 to 5 parts by weight, preferably 0.2 to 4 parts by weight, based on 100 parts by weight of the total of the component A and the component B. And more preferably 0.3 to 3 parts by weight.
The flame retardants D-1, D-2, D-3 and D-4 may be used alone or in combination of two or more.

(E component: inorganic filler)
The resin composition of the present invention contains an inorganic filler as the E component. Inorganic fillers are generally known such as glass fiber, flat glass fiber, milled fiber, carbon fiber, glass flake, wollastonite, kaolin clay, mica, talc and various whiskers (potassium titanate whisker, aluminum borate whisker, etc.). Various fillers can be used. The shape of the inorganic filler can be freely selected from fibrous, flake, spherical, and hollow shapes. In order to improve the strength and impact resistance of the resin composition, in particular, fibrous and plate-like materials are suitably used. . Further, a glass-based inorganic filler such as glass fiber or glass flake has a problem that a mold is easily worn during molding. Therefore, a silicate mineral is more preferably used as the E component. The silicate mineral used as the E component of the present invention is a mineral composed of at least a metal oxide component and a SiO ₂ component, and is preferably an orthosilicate, a disilicate, a cyclic silicate, a chain silicate, or the like. The silicate mineral takes a crystalline state, and the crystal can take various shapes such as a fibrous shape and a plate shape.

The silicate mineral may be any compound of a complex oxide, an oxyacid salt (consisting of an ionic lattice) and a solid solution. Further, the complex 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 may be a solid solution of any one of a solid solution of two or more metal oxides and a solid solution of two or more oxyacid salts. The silicate mineral may be a hydrate. The form of the water of crystallization in the hydrate includes those entering as hydrogen silicate ions as Si-OH, those entering ionicly as hydroxide ions (OH ⁻ ) to metal cations, and H ₂ O molecules in the gaps of the structure. Any of the forms that can be entered may be used.

  As the silicate mineral, an artificial synthetic product corresponding to a natural product can also be used. As the artificially synthesized product, silicate minerals obtained from various conventionally known methods, for example, various synthetic methods utilizing a solid reaction, a hydrothermal reaction, an ultra-high pressure reaction, and the like can be used.

Specific examples of the silicate mineral in each metal oxide component (MO) include the following. Here, the notation in parentheses is the name of a mineral or the like containing such a silicate mineral as a main component, and means that the compound in parenthesis can be used as the exemplified metal salt.
Examples of those containing K ₂ O in its components include K ₂ O · SiO ₂ , K ₂ O · 4SiO ₂ · H ₂ O, K ₂ O · Al ₂ O ₃ · 2SiO ₂ (calcilite), 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 (gehlenite), a solid solution of O Keruma Knight and gehlenite (melilite), CaO · SiO ₂ (wollastonite (alpha-type, including any of the 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, etc.), Zono Toraito group hydrate, such as _{2CaO · SiO 2 · H 2 O} ( fin Blanc Daito) wollastonite group hydrate, such _{as, 6CaO · 6SiO 2 · H 2} O ( xonotlite) _{, 2CaO · SiO 2 · 2H 2} O gyro light group hydrates such (gyro _{lights), CaO · Al 2 O 3} · 2SiO 2 · H 2 O ( _{Rosonaito), CaO · FeO · 2SiO 2} ( Hedenki stone), 3CaO · 2SiO _{2 (Chirukoanaito), 3CaO · Al 2 O 3} · 3SiO 2 ( _{Guroshura), 3CaO · Fe 2 O 3} · 3SiO 2 ( Andhra _{Daito), 6CaO · 4Al 2 O 3} · FeO · SiO 2 ( pleo black Ait ), And clinozoisite, rhodolite, bryanite, vesuvite, onostone, Koutite, augite and the like.

Portland cement can also be mentioned as a silicate mineral containing CaO in its component. The type of Portland cement is not particularly limited, and any type such as ordinary, fast, super fast, medium heat, sulfate resistant, and white can be used. Further, various mixed cements such as blast furnace cement, silica cement, fly ash cement and the like can be used as the E component.
Blast furnace slag, ferrite and the like can also be mentioned as other silicate minerals containing CaO as a component.

Examples of those containing ZnO in its component include ZnO.SiO ₂ , 2ZnO.SiO ₂ (troostite), and 4ZnO.2SiO ₂ .H ₂ O (hematite).
As including MnO into its _components, such as _{MnO · SiO 2, 2MnO · SiO} 2, CaO · 4MnO · 5SiO 2 ( rhodonite) and Coe write the like.
FeO.SiO ₂ (ferrosilite), 2FeO.SiO ₂ (iron olivine), 3FeO.Al ₂ O ₃ .3SiO ₂ (almandine), and 2CaO.5FeO.8SiO _2. H ₂ O (Tetactinocene stone) and the like.
Examples of those containing CoO in 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 · _{MgO · 3Al 2 O 3 · 8SiO} 2 · H 2 O ( melee stone), as well as magnesium tourmaline, linearity stone, Kamintonsen stone, vermiculite, etc. smectite and the like.

As containing Fe ₂ O ₃ on the _component, and a Fe ₂ O 3 · SiO _2.
As those containing ZrO ₂ into its _components, ZrO 2 · SiO ₂ (zircon) and AZS refractory and the like.
Examples of those containing Al ₂ O ₃ in its component include Al ₂ O ₃ .SiO ₂ (sillimanite, andalusite, kyanite), 2Al ₂ O ₃ .SiO ₂ , Al ₂ O ₃ .3SiO ₂ , and 3Al ₂ O _3. .2SiO ₂ (mullite), Al ₂ O ₃ .2SiO ₂ .2H ₂ O (kaolinite), Al ₂ O ₃ .4SiO ₂ .H ₂ O (pyrophyllite), Al ₂ O ₃ .4SiO ₂ .H ₂ O _{(bentonite), K 2 O · 3Na 2} O · 4Al 2 O 3 · 8SiO 2 ( _{nepheline), K 2 O · 3Al 2} O 3 · 6SiO 2 · 2H 2 O ( muscovite, sericite), _{K 2} O.6MgO.Al ₂ O ₃ .6SiO ₂ .2H ₂ O (phlogovite), various zeolites, fluorophlogopite, biotite and the like can be mentioned.
Among the above silicate minerals, particularly preferred are mica, talc and wollastonite, and more preferably one or more silicate minerals containing talc.

(talc)
The talc in the present invention is a hydrated magnesium silicate in chemical composition, is generally represented by the chemical formula 4SiO ₂ · 3MgO · 2H ₂ O, and is usually a flaky particle having a layered structure. thereof include a SiO ₂ fifty-six to sixty-five wt%, the MgO 28 to 35 wt%, and a _{H 2} O about 5 wt%. Other minor _Fe 2 _{O 3} as a component from 0.03 to 1.2 wt%, _Al 2 _{O 3} is 0.05 to 1.5 wt%, CaO is 0.05 to 1.2 _{wt%, K} 2 O Contains 0.2% by weight or less, and Na ₂ O contains 0.2% by weight or less. The particle size of talc is such that the average particle size measured by the sedimentation method is 0.1 to 15 μm (more preferably 0.2 to 12 μm, further preferably 0.3 to 10 μm, particularly preferably 0.5 to 5 μm). It is preferably within the range. It is particularly preferable to use talc having a bulk density of 0.5 (g / cm ³ ) or more as a raw material. The average particle diameter of talc refers to D50 (median diameter of particle diameter distribution) measured by an X-ray transmission method which is one of the liquid phase sedimentation methods. As a specific example of an apparatus for performing such a measurement, Sedigraph 5100 manufactured by Micromeritics Co., Ltd. can be mentioned.

There is no particular limitation on the production method for crushing talc from rough stone, and an axial flow mill method, an annular mill method, a roll mill method, a ball mill method, a jet mill method, a container rotating compression shearing mill method, and the like are used. can do. Further, the talc after the pulverization is subjected to a classification treatment by various classifiers, and one having a uniform particle size distribution is preferable. There are no particular restrictions on classifiers. Impactor-type inertial classifiers (variable impactors, etc.), Coanda effect-type inertial classifiers (elbow jet, etc.), centrifugal classifiers (multistage cyclones, microplexes, dispersion separators) , AccuCut, Turbo Classifier, Turboplex, Micron Separator, Super Separator and the like).
Further, talc is preferably in an agglomerated state in terms of handling properties and the like. Examples of such a production method include a method by degassing and compression, and a method of compressing using a sizing agent. In particular, the degassing compression method is preferred because it is simple and does not mix unnecessary sizing agent resin components into the resin composition of the present invention.

(Mica)
Mica having an average particle diameter of 10 to 100 μm measured by a microtrack laser diffraction method can be preferably used. More preferably, the average particle diameter is 20 to 50 μm. If the average particle size of mica is less than 10 μm, the effect of improving rigidity may not be sufficient, and if it exceeds 100 μm, the rigidity may not be sufficiently improved, and mechanical strength such as impact characteristics may be significantly reduced. . Mica having a thickness actually measured by observation with an electron microscope of 0.01 to 1 μm can be preferably used. More preferably, the thickness is from 0.03 to 0.3 μm. The aspect ratio is preferably from 5 to 200, and more preferably from 10 to 100. The mica used is preferably muscovite mica, and its Mohs hardness is about 3. Muscobite mica can achieve higher rigidity and higher strength than other mica such as phlogovite, and solves the problems of the present invention at a better level. Further, as a method for pulverizing mica, any one produced by a dry pulverization method or a wet pulverization method may be used. The dry grinding method is generally more inexpensive at low cost, while the wet grinding method is effective for grinding the mica thinner and finer, and as a result, the effect of improving the rigidity of the resin composition is higher.

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

The wollastonite of the present invention is a magnetic separator that reflects the iron content mixed in the raw material ore and the iron content mixed due to wear of the equipment when the raw material ore is crushed in order to sufficiently reflect the whiteness inherent in the resin composition. Is preferably removed as much as possible. It is preferable that the iron content in wollastonite is 0.5% by weight or less in terms of Fe ₂ O ₃ by the magnetic separator treatment.
Although silicate minerals (more preferably, mica, talc, wollastonite) are preferably not surface-treated, they are surface-treated with various surface treatment agents such as silane coupling agents, higher fatty acid esters, and waxes. May be. Further, the mixture may be granulated with a sizing agent such as various resins, higher fatty acid esters, and wax to form granules.
The content of the component E is 1 to 80 parts by weight, preferably 2 to 70 parts by weight, and more preferably 3 to 60 parts by weight based on 100 parts by weight of the total of the components A and B. If the content of the E component is less than 1 part by weight, sufficient rigidity and surface hardness cannot be obtained, and if it exceeds 80 parts by weight, impact resistance is largely lost, appearance defects such as silver occur, and filler Flame retardancy is reduced by promoting the candle effect.

(F component: rubbery elastic body other than C component)
The resin composition of the present invention may contain a rubbery elastic body other than the C component as the F component. The rubber-like elastic body contains 40% by weight or more of a rubber component having a glass transition temperature of 10 ° C or lower, preferably -10 ° C or lower, more preferably -30 ° C or lower. For example, a graft obtained by copolymerizing one or more monomers selected from aromatic vinyl, vinyl cyanide, acrylic acid ester, methacrylic acid ester, and a vinyl compound copolymerizable therewith with such a rubber component. Copolymers can be mentioned. On the other hand, it is also possible to use various types of thermoplastic elastomers having no crosslinked structure other than the component C, such as polyurethane elastomers, polyester elastomers, and polyetheramide elastomers. As the rubber component having a glass transition temperature of 10 ° C. or less, butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, acrylic-silicone composite rubber, isobutylene-silicone composite rubber, isoprene rubber, styrene-butadiene rubber, chloroprene rubber , Ethylene-propylene rubber, nitrile rubber, ethylene-acryl rubber, silicone rubber, epichlorohydrin rubber, fluororubber, and those obtained by adding hydrogen to unsaturated bond portions thereof.

  Among these, a core-schul type graft polymer is preferred. The core-shell type graft polymer referred to here is selected from aromatic vinyl, vinyl cyanide, acrylic acid ester, methacrylic acid ester, and a vinyl compound copolymerizable therewith, with a rubber component having a glass transition temperature of 10 ° C. or less as a core. Is a graft copolymer obtained by copolymerizing one or more of the above monomers as a shell. As the rubber component of the core-shell type graft polymer, butadiene rubber, butadiene-acryl composite rubber, acrylic rubber, acrylic-silicone composite rubber, isobutylene-silicone composite rubber, isoprene rubber, styrene-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, Nitrile rubber, ethylene-acryl rubber, silicone rubber, epichlorohydrin rubber, fluoro rubber and those in which hydrogen is added to the unsaturated bond thereof can be mentioned, but from the viewpoint of generating harmful substances during combustion. A rubber component containing no halogen atom is preferable from the viewpoint of environmental load. The glass transition temperature of the rubber component is preferably −10 ° C. or lower, more preferably −30 ° C. or lower. As the rubber component, butadiene rubber, butadiene-acryl composite rubber, acrylic rubber, and acrylic-silicone composite rubber are particularly preferable. The composite rubber refers to a rubber obtained by copolymerizing two types of rubber components or a rubber obtained by polymerizing so as to have an IPN structure entangled with each other so as not to be separated. In the core-shell type graft polymer, the particle diameter of the core is preferably 0.05 to 0.8 μm, more preferably 0.1 to 0.6 μm, and still more preferably 0.15 to 0.5 μm in terms of weight average particle diameter. In the range of 0.05 to 0.8 μm, better impact resistance is achieved.

  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 include methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, octyl acrylate, and the like. Examples of the methacrylate include methyl methacrylate, ethyl methacrylate, and butyl methacrylate. And cyclohexyl methacrylate, octyl methacrylate and the like, with methyl methacrylate being particularly preferred. Among these, it is particularly preferable to contain a methacrylate 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 thermal stability. This is because the core-shell type graft polymer has 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 more improved. This is because the resin composition 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 the case of a core-shell type polymer, in 100% by weight of the shell), preferably 10% by weight or more, more preferably 15% by weight or more. The elastic polymer containing a rubber component having a glass transition temperature of 10 ° C. or lower may be produced by any polymerization method of bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. A single-stage graft or a multi-stage graft may be used. Further, it may be a mixture with a copolymer of only a graft component produced as a by-product at the time of production. Examples of the polymerization method include a general emulsion polymerization method, a soap-free polymerization method using an initiator such as potassium persulfate, a seed polymerization method, and a two-step swelling polymerization method. In the suspension polymerization method, a method in which an aqueous phase and a monomer phase are separately held, and both are accurately supplied to a continuous disperser, and the particle diameter is controlled by the number of revolutions of the disperser. In the method, a method in which the monomer phase is supplied into an aqueous liquid having dispersibility by passing it through a small-diameter orifice having a diameter of several to several tens of μm or a porous filter to control the particle size may be performed. 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 can be easily obtained. For example, as a rubber component, one having a butadiene rubber as a main component is a Kaneace M series manufactured by Kaneka Corporation (for example, M-711 having a shell component of methyl methacrylate as a main component, and a shell component of methyl methacrylate / styrene as a main component). M-701), METABLEN C series manufactured by Mitsubishi Rayon Co., Ltd. (for example, C-223A having a shell component of methyl methacrylate / styrene as a main component), E series (eg, a shell component of methyl methacrylate / styrene). E-860A as a main component, etc.) and Paraloid EXL series of DOW Chemical Co., Ltd. (eg, EXL-2690 as a shell component containing methyl methacrylate as a main component), and acrylic rubber or butadiene-acryl composite rubber as a main component. W series (For example, W-600A whose shell component is mainly composed of methyl methacrylate) and Paraloid EXL series of DOW Chemical Co., Ltd. (for example, EXL-2390 whose shell component is mainly composed of methyl methacrylate). As a component having an acrylic-silicone composite rubber as a main component, Mitsubishi Rayon Co., Ltd. has a shell component of methbrene S-2001 whose main component is methyl methacrylate or a shell component of SRK- whose main component is acrylonitrile / styrene. The one marketed under the trade name of 200 can be mentioned. Among these, those containing no styrene, which is an aromatic vinyl component, are particularly preferably used in terms of mechanical properties and chemical resistance.

  The content of the component F is preferably from 1 to 10 parts by weight, more preferably from 1.5 to 7.5 parts by weight, and still more preferably from 2 to 100 parts by weight based on 100 parts by weight of the total of the components A and B. 6 parts by weight. If the content is less than 1 part by weight, impact strength and chemical resistance may decrease, and if it exceeds 10 parts by weight, rigidity and surface hardness may decrease.

(G component: anti-drip agent)
The resin composition of the present invention can contain an anti-drip agent (G component). By containing the anti-drip agent, good flame retardancy can be achieved without impairing the physical properties of the molded article.
Examples of the anti-drip agent include a fluorine-containing polymer having a fibril-forming ability. Examples of such a polymer include polytetrafluoroethylene and a tetrafluoroethylene-based copolymer (for example, a tetrafluoroethylene / hexafluoropropylene copolymer, And the like, and partially fluorinated polymers as disclosed in U.S. Pat. No. 4,379,910, polycarbonate resins produced from fluorinated diphenols, and the like. Among them, polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is preferable.

PTFE having a fibril-forming ability has an extremely high molecular weight, and tends to combine with each other by an external action such as shearing force to form a fibrous form. Its molecular weight is 1,000,000 to 10,000,000, more preferably 2,000,000 to 9,000,000 in terms of the number average molecular weight determined from the standard specific gravity. Such PTFE may be in the form of an aqueous dispersion in addition to the solid form. In addition, PTFE having such fibril-forming ability can improve the dispersibility in a resin, and a PTFE mixture in a mixed form with another resin can be used to obtain better flame retardancy and mechanical properties. is there.
Examples of commercially available PTFE having a fibril-forming ability include Teflon (registered trademark) 6J of Mitsui-DuPont Fluorochemicals Co., Ltd., and Polyflon MPA FA500 and F-201L of Daikin Industries, Ltd. Commercially available PTFE aqueous dispersions include Fluon AD-1, AD-936 manufactured by Asahi ICI 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. may 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 performing coprecipitation to obtain a coaggregated mixture (Japanese Patent Laid-Open No. 60-258263, (2) a method of mixing an aqueous dispersion of PTFE and dried organic polymer particles (a 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 the respective media from the mixture (described in JP-A-06-220210, JP-A-08-188655, and the like) (4) a method of polymerizing a monomer forming an organic polymer in an aqueous dispersion of PTFE (a method described in JP-A-9-95583), and (5) A method of uniformly mixing an aqueous dispersion of TFE and an organic polymer dispersion, further polymerizing a vinyl monomer in the mixed dispersion, and then obtaining a mixture (described in JP-A-11-29679 and the like). Method) can be used. Examples of commercially available PTFE in the mixed form include “METABLEN A3800” (trade name) manufactured by Mitsubishi Rayon Co., Ltd. and “BLENDEX B449” (trade name) manufactured by GE Specialty Chemicals.

The ratio 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 content of the component G is preferably 0.1 to 3 parts by weight, more preferably 0.15 to 2 parts by weight, and still more preferably 0.2 to 2 parts by weight, based on 100 parts by weight of the total of the components A and B. 1 part by weight. If the amount of the anti-drip agent is less than the above range, the flame retardancy may be insufficient. On the other hand, when the amount of the anti-drip agent exceeds the above range, the PTFE precipitates on the surface of the molded article, resulting in poor appearance and also leads to an increase in the cost of the resin composition. The content of the G component indicates the net amount of the anti-drip agent, and in the case of PTFE in a mixed form, indicates the net amount of PTFE.

  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, for example, 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 monomers may be used alone or in combination of two or more.

  The acrylic monomer used in the organic polymer used in the polytetrafluoroethylene-based mixture of the present invention contains a (meth) acrylate derivative which may be substituted. Specifically, the acrylic monomer includes one or more groups selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group, and a glycidyl group. Optionally substituted (meth) acrylate derivatives, such as (meth) acrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, hexyl (Meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, and glycidyl (meth) acrylate ) Acrylate, alkyl having 1 to 6 carbon atoms Group, or maleimide which may be substituted by an aryl group, for example, maleimide, N- methyl - maleimide and N- phenyl - maleimide, maleic acid, phthalic acid and itaconic acid are exemplified, but are not limited thereto. The acrylic monomers may be used alone or in combination of two or more. Among 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 to 9 parts by weight. If the unit derived from the acrylic monomer is less than 8 parts by weight, the coating strength may be reduced, and if it is more than 11 parts by weight, the surface appearance of the molded article may be deteriorated.
The polytetrafluoroethylene-based mixture of the present invention preferably has a residual moisture content of 0.5% by weight or less, more preferably 0.2 to 0.4% by weight, still more preferably 0.1 to 0.4% by weight. 3% by weight. If the residual water content is more than 0.5% by weight, the flame retardancy may be adversely affected.

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

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

The polytetrafluoroethylene-based mixture of the present invention was produced by a suspension polymerization method according to the following procedure.
First, water and a branched polytetrafluoroethylene dispersion (solid concentration: 60%, polytetrafluoroethylene particle diameter: 0.15 to 0.3 μm) are put into a reactor, and then the acrylic monomer and styrene are stirred. Cumene hydroperoxide was added as a monomer and a water-soluble initiator, and the mixture was reacted at 80 to 90 ° C. for 9 hours. After the completion of the reaction, water was removed by centrifugation for 30 minutes using a centrifuge to obtain a paste-like product. Thereafter, the product paste was dried at 80 to 100 ° C. for 8 hours using a hot air drier. Thereafter, the dried product was pulverized to obtain a polytetrafluoroethylene-based mixture of the present invention.

  Such a suspension polymerization method does not require a polymerization step by emulsification and dispersion in an emulsion polymerization method exemplified in Japanese Patent No. 3469391, and thus does not require an emulsifier and electrolyte salts for coagulating and precipitating a 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 such emulsifier, sodium metal ions and potassium metal ions derived from the electrolyte salts are reduced. It is difficult. Since the polytetrafluoroethylene-based mixture (component B) used in the present invention is manufactured by a suspension polymerization method, sodium metal ions and potassium metal ions in the mixture are used because such an emulsifier and electrolyte salts are not used. Can be reduced, and heat stability and hydrolysis resistance can be improved.

  In the present invention, a coated branched PTFE can be used as an anti-drip agent. The coated branched PTFE is a polytetrafluoroethylene-based mixture composed of branched polytetrafluoroethylene particles and an organic polymer, and an organic polymer, preferably a styrene-based monomer, is provided 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 the branched polytetrafluoroethylene. The coating layer preferably contains a copolymer of a styrene monomer and an acrylic monomer.

The polytetrafluoroethylene contained in the coated branched PTFE is a branched polytetrafluoroethylene. If the polytetrafluoroethylene contained is not a branched polytetrafluoroethylene, the effect of preventing dripping when the addition of polytetrafluoroethylene is small is insufficient. The branched polytetrafluoroethylene is in the form of particles, and preferably has a particle diameter of 0.1 to 0.6 μm, more preferably 0.3 to 0.5 μm, and still more preferably 0.3 to 0.4 μm. When the particle size is smaller than 0.1 μm, the surface appearance of the molded article is excellent, but it is difficult to commercially obtain polytetrafluoroethylene having a particle size smaller than 0.1 μm. When the particle diameter is larger than 0.6 μm, the surface appearance of the molded product may be deteriorated. 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 polytetrafluoroethylene having a high molecular weight. Fluoroethylene is more preferred in terms of stability. Either in powder or dispersion form can be used.

  The content of the 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 100 parts by weight based on the total weight of the coated branched PTFE of 100 parts by weight. 53 parts by weight, particularly preferably 48 to 52 parts by weight, most preferably 49 to 51 parts by weight. When the proportion of the branched polytetrafluoroethylene is in such a range, good dispersibility of the branched polytetrafluoroethylene can be achieved.

(H component: phenolic heat stabilizer)
The resin composition of the present invention can contain a phenolic heat stabilizer as the H component. Phenolic heat stabilizers generally include hindered phenols, semi-hindered phenols, and re-hindered phenol compounds, but in particular, hindered phenol compounds are more preferable in terms of applying a heat stabilizing formulation to a polypropylene resin. It is preferably used. Examples of such hindered phenol compounds include α-tocopherol, butylhydroxytoluene, sinapyr 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-hexanediolbis [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] -1,1,1. -Dimethylethyl {-2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4'-thiobis (6-tert-butyl-m-cresol), 4,4'-thiobis (3- Methyl-6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4 ′ -Di-thiobis (2,6-di-tert-butylphenol), 4,4'-tri-thiobis (2,6-di-tert-butylphenol), 2,2-thiodie Lenbis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-tert- (Butylanilino) -1,3,5-triazine, N, N′-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N′-bis [3- (3 , 5-Di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl -2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) iso Cyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris 2 [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-methylbenzyl) isocyanurate. Among the above compounds, in the present invention, tetrakis [methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, octadecyl-3- (3,5-di-tert-butyl-) 4-Hydroxyphenyl) propionate is preferably used. Further, as a material excellent in suppressing a decrease in mechanical properties due to thermal decomposition during processing, (3,3 ′, 3 ″, 5, 5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesitylene-2,4,6-triyl) tri-p-cresol, and 1 represented by the following formula (15) , 3,5-Tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione is more preferred. Used.

The phenolic heat stabilizers may be used alone or in combination of two or more.
The content of the H component is preferably 0.05 to 1.0 part by weight, more preferably 0.07 to 0.8 part by weight, and still more preferably 100 parts by weight of the total of the A component and the B component. Is 0.1 to 0.5 parts by weight. If the content is less than 0.05 part by weight, the effect of suppressing thermal decomposition during processing is not exhibited, and mechanical properties may be reduced. Even if the content exceeds 1.0 part by weight, mechanical properties may be reduced. .

(I component: phosphorus-based heat stabilizer)
The resin composition of the present invention can contain a phosphorus-based heat stabilizer as an I component. Examples of the phosphorus-based stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphine.

  Specifically, examples of the phosphite compound include triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, and dioctyl monophenyl. Phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, tris (diethyl phenyl) phosphite, tris (di-iso-propyl phenyl) phosphite, tris (di -N-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, disis Allyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite, phenylbisphenol A Examples include pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, and dicyclohexylpentaerythritol diphosphite.

  Further, other phosphite compounds having a cyclic structure by reacting with a dihydric phenol 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-butyl-phenyl) Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite and 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite.

  Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenylcresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, and dioctyl phosphate. Examples thereof include diisopropyl phosphate, and preferred are triphenyl phosphate and trimethyl phosphate.

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

Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.
As the tertiary phosphine, triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolyl Examples include phosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine.
The phosphorus-based stabilizers can be used alone or in combination of two or more. Among the phosphorus stabilizers, a phosphonite compound or a phosphite compound represented by the following general formula (16) is preferable.

(In the formula (16), 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 phosphonite as a main component is Sandostab P-EPQ (trademark, manufactured by Clariant). ) And Irgafos P-EPQ (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and both can be used.
Among the above-mentioned formulas (16), more preferred phosphite compounds include distearylpentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, and bis (2,6-diphosphite). -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 ADK STAB PEP-8 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and JPP681S (trademark, manufactured by Johoku Chemical Co., Ltd.), and any of them can be used. Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite is manufactured by ADK STAB 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 Chemical Company), and Irgaofos 126 and 126FF (trademark, manufactured by CIBA SPELICY CHEMICALS) are commercially available. Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is commercially available as ADK STAB PEP-36 (trademark, manufactured by Asahi Denka Kogyo KK) and can be easily used. Bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite is manufactured by ADK STAB PEP-45 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and Doverphos S-9228 (trademark). , And Dover Chemical Co., Ltd.).

  The phosphorus-based heat stabilizer is more preferably used in combination with a phenol-based heat stabilizer (H component), and the blending amount of the phosphorus-based heat stabilizer is preferably based on 100 parts by weight of the total of the A component and the B component. The amount is 0.05 to 1.0 part by weight, more preferably 0.07 to 0.8 part by weight, and still more preferably 0.1 to 0.5 part by weight. When used in combination with the phenolic heat stabilizer (H component), 0.05 to 1.0 part by weight of the phosphorus stabilizer and 0.05 to 1.0 part by weight are added to the total of 100 parts by weight of the component A and the component B. More preferably, the phenolic heat stabilizer is added in parts by weight.

(J component: titanium oxide)
The resin composition of the present invention can contain titanium oxide as a J component. As the titanium oxide to be used, titanium oxide having an average particle diameter of 0.1 to 5.0 μm, which is surface-treated with an organic substance, is preferable. (In the present invention, the titanium oxide component of the titanium oxide pigment is described as "TiO2", and the entire pigment including the surface treatment agent is described as "titanium oxide.") Any of the types may be used, and they may be mixed and used as needed. The rutile type is more preferable in terms of initial mechanical properties and long-term weather resistance. The rutile-type crystal may contain an anatase-type crystal. Further, as a method for producing TiO2, products produced by various methods such as a sulfuric acid method and a chlorine method can be used, but the chlorine method is more preferable. The titanium oxide of the present invention is not particularly limited in its shape, but is preferably in the form of particles. Titanium oxide is generally used for various coloring purposes, and the average particle diameter of titanium oxide used as the H component of the present invention is preferably 0.10 to 5.0 μm, and 0.15 to 2.0 μm. 0 μm is more preferred, and 0.18 to 1.5 μm is even more preferred. When the average particle diameter is smaller than 0.10 μm, poor appearance such as silver is likely to occur when the filling is high, and when the average particle diameter is larger than 5.0 μm, the appearance may be deteriorated and the mechanical properties may be deteriorated. The average particle diameter is calculated from the number average of individual single particle diameters measured by electron microscope observation.

  The titanium oxide as the component J is preferably surface-treated with an organic compound. When using titanium oxide that has not been subjected to organic treatment, the appearance is deteriorated due to yellowing, and the reflectance of the molded product is significantly reduced, so that sufficient solar reflectance may not be obtained. May not be suitable for As such a surface treating agent, various treating 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.Examples of the amine-based surface treatment agent include triethanolamine acetate and trimethylolamine acetate. Examples of the silicone-based surface treating agent include alkyl chlorosilane (such as trimethylchlorosilane), alkylalkoxysilane (such as methyltrimethoxysilane), and hydrogenpolysiloxane. Examples of the hydrogen polysiloxane include an alkyl hydrogen polysiloxane and an alkylphenyl hydrogen polysiloxane. As such an alkyl group, a methyl group and an ethyl group are preferable. The titanium oxide surface-treated with such an alkylalkoxysilane and / or hydrogenpolysiloxane gives the resin composition of the present invention better light reflectivity. 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, and still more preferably 1.5 to 2.5 parts by weight per 100 parts by weight of the J component. It is in the range of parts by weight. If the surface treatment amount 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 in terms of molding defects such as silver. It is preferable that the surface treatment agent of the organic compound is previously formed on titanium oxide (more preferably, titanium oxide coated with another metal oxide). However, a method may be used in which the surface treatment agent is separately added when the raw materials of the resin composition are melt-kneaded, and the surface treatment of the titanium oxide is performed in the melt-kneading step.

  The content of the component J is preferably 0.1 to 10 parts by weight, more preferably 0.15 to 7.5 parts by weight, and still more preferably 100 parts by weight of the total of the components A and B. 0.15 to 5 parts by weight. When the content of the J component is less than 0.1 part by weight, a sufficient white appearance or light-shielding property may not be obtained, and when it exceeds 10 parts by weight, molding defects such as silver and physical properties may be significantly reduced. There is not preferred.

(Other additives)
(I) Release Agent The polycarbonate resin composition of the present invention preferably further contains a release agent for the purpose of improving productivity during molding and reducing distortion of a molded product. Known release agents can be used. For example, saturated fatty acid esters, unsaturated fatty acid esters, polyolefin-based waxes (polyethylene wax, 1-alkene polymer, etc .; those modified with a functional group-containing compound such as acid modification can also be used), silicone compounds, fluorine compounds ( Fluorine oil represented by polyfluoroalkyl ether), paraffin wax, beeswax and the like. Among them, preferred release agents include fatty acid esters. Such a fatty acid ester is an ester of an aliphatic alcohol and an aliphatic carboxylic acid. Such an aliphatic alcohol may be a monohydric alcohol or a dihydric or higher polyhydric alcohol. The alcohol has a carbon number of 3 to 32, more preferably 5 to 30. Examples of such a monohydric alcohol include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, seryl alcohol, and triacontanol. Such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, mannitol, and the like. Polyhydric alcohols are more preferred in the fatty acid ester of the present invention.

  On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, particularly preferably an aliphatic carboxylic acid having 10 to 22 carbon atoms. Examples of the aliphatic carboxylic acid include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, behenic acid, Mention may be made of saturated aliphatic carboxylic acids such as 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 setrenic acid. . Among the above, the aliphatic carboxylic acid preferably has 14 to 20 carbon atoms. Among them, saturated aliphatic carboxylic acids are preferred. 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 natural fats and oils such as animal fats and fats such as beef tallow and lard, and vegetable fats and fats such as palm oil and sunflower oil. Therefore, these aliphatic carboxylic acids are usually mixtures containing other carboxylic acid components having different numbers of carbon atoms. Therefore, in the production of the fatty acid ester of the present invention, an aliphatic carboxylic acid, particularly stearic acid or palmitic acid, which is produced from such natural fats and oils and is in the form of a mixture containing other carboxylic acid components, is preferably used.

  The fatty acid ester of the present invention may be either a partial ester or a whole ester (full ester). However, a partial ester is more preferably a full ester, since the hydroxyl value usually increases and the resin is easily decomposed at a high temperature. The acid value of the fatty acid ester of the present invention is preferably 20 or less, more preferably 4 to 20, and still more preferably 4 to 12, from the viewpoint of thermal stability. Incidentally, the acid value can take substantially zero. Further, the hydroxyl value of the fatty acid ester is more preferably in the range of 0.1 to 30. Further, the iodine value is preferably 10 or less. Incidentally, the iodine value can take substantially zero. These characteristics can be determined by a method specified in JIS K0070.

  The content of the release agent is preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight, and further preferably 0.05 to 100 parts by weight of the total of the component A and the component B. 0.5 part by weight. Within such a range, the polycarbonate resin composition has good release properties and roll release properties. In particular, such an amount of the fatty acid ester provides a polycarbonate resin composition having a good releasing property and a good roll releasing property without impairing a good hue.

(Ii) Ultraviolet absorber The polycarbonate resin composition of the present invention can contain an ultraviolet absorber. In the benzophenone system, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy- 5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydrate benzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, , 2'-Dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl ) Methane, 2-hydroxy Examples thereof include -4-n-dodecyloxybensophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like.

  In the benzotriazole type, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2′-methylenebis [4- (1,1,3 , 3-Tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole, 2- (2- Hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5 Di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole, 2- ( 2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2'-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis (1,3-benzoxazine-4 -One), and 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, and 2- (2'-hydroxy-5-methacryloxy) Copolymerization of (ethylphenyl) -2H-benzotriazole and a vinyl monomer copolymerizable with the monomer -Hydroxyphenyl-2H-benzotriazole skeleton such as a copolymer or a copolymer of 2- (2'-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole and a vinyl monomer copolymerizable with the monomer And the like.

  In the hydroxyphenyltriazine type, for example, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol, 2- (4,6-diphenyl-1,3,5 -Triazin-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxyphenol, 2- (4,6-diphenyl -1,3,5-triazin-2-yl) -5-propyloxyphenol and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-butyloxyphenol Is exemplified. Furthermore, the phenyl group of the exemplified compound such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol is 2,4-dimethyl A compound having a phenyl group is exemplified.

  In the cyclic imino ester system, for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) bis (3,1-benzoxazine -4-one) and 2,2 '-(2,6-naphthalene) bis (3,1-benzoxazin-4-one).

  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, and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene.

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

Among them, benzotriazole-based and hydroxyphenyltriazine-based resins are preferred from the viewpoint of ultraviolet absorbing ability, and cyclic iminoester-based and cyanoacrylate-based resins are preferred from the viewpoint of heat resistance and hue (transparency). The ultraviolet absorbers may be used alone or as a mixture of two or more.
The content of the ultraviolet absorber is preferably 0.01 to 2 parts by weight, more preferably 0.02 to 2 parts by weight, and still more preferably 0.03 to 100 parts by weight of the total of the component A and the component B. To 1 part by weight, more preferably 0.05 to 0.5 part by weight.

(Iii) Hindered amine light stabilizer The polycarbonate resin composition of the present invention can contain a hindered amine light stabilizer. The hindered amine light stabilizer is generally called HALS (Hindered Amine Light Stabilizer), and is a compound having a 2,2,6,6-tetramethylpiperidine skeleton in the 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- Tramethylpiperidine, 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-tetramethyl-4-piperidyl) oxalate, bis (2,2,6,6-tetramethyl-4-) Piperidyl) malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl) 4-piperidyl) adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) carbonate, bis (1,2 , 2,6,6-pentamethyl-4-piperidyl) oxalate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) malonate, bis (1,2,2,6,6-pentamethyl-4) -Piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) adipate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) terephthalate, N, N'- Bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzenedicarboxamide, 1,2-bis (2,2,6,6-tetramethyl-4-piperid Loxy) ethane, α, α'-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2,6,6-tetramethyl-4-piperidyltolylene -2,4-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene-1,6-dicarbamate, tris (2,2,6,6-tetramethyl-4 -Piperidyl) -benzene-1,3,5-tricarboxylate, N, N ', N ", N"'-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2 , 6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine-1,3,5-triazine.N, N ' -Bis (2,2,6,6-tetramethyl-4-pi Polycondensate of N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [{6- (1,1,3,3-tetra Methylbutyl) amino-1,3,5-triazine-2,4-diyl {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene} (2,2,6,6- Tetramethyl-4-piperidyl) imino}], tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2) 6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene-1,3,4- Tricarboxylate 1- [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} butyl] -4- [3- (3,5-di-t-butyl-4-hydroxyphenyl ) Propionyloxy] 2,2,6,6-tetramethylpiperidine, and 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, and condensates with β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethanol.

Hindered amine light stabilizers are roughly classified according to the bonding partner of the nitrogen atom in the piperidine skeleton, such as NH (hydrogen is bonded to a nitrogen atom), NR (alkyl group (R) is bonded to a nitrogen atom), There are three types of N-OR type (alkoxy group (OR) is bonded to a nitrogen atom), but when applied to a polycarbonate resin, from the viewpoint of basicity of the hindered amine light stabilizer, low basicity N-R And N-OR type are more preferable.
Among the above compounds, compounds represented by the following formulas (17) and (18) are more preferably used in the present invention.

The hindered amine light stabilizers can be used alone or in combination of two or more.
The content of the hindered amine-based light stabilizer is preferably from 0 to 1 part by weight, more preferably from 0.05 to 1 part by weight, even more preferably from 0.1 to 1 part by weight, based on 100 parts by weight of the total of the component A and the component B. 08 to 0.7 part by weight, particularly preferably 0.1 to 0.5 part by weight. If the content of the hindered amine-based light stabilizer is more than 1 part by weight, appearance may be poor due to generation of gas, or physical properties may be deteriorated due to decomposition of the polycarbonate resin. If the amount is less than 0.05 parts by weight, sufficient light resistance may not be exhibited.

(Iv) Dye / Pig The polycarbonate resin composition of the present invention can further contain various dye / pigments to provide molded articles exhibiting various design properties. By blending a fluorescent whitening agent or other fluorescent dye that emits light, a better design effect utilizing the emitted color can be provided. It is also possible to provide a polycarbonate resin composition which is colored by a trace amount of dye and pigment and has vivid coloration.

  Examples of the fluorescent dye (including a fluorescent whitening agent) used in the present invention include a coumarin fluorescent dye, a benzopyran fluorescent dye, a perylene fluorescent dye, an anthraquinone fluorescent dye, a thioindigo fluorescent dye, and a xanthene fluorescent dye. And xanthone fluorescent dyes, thioxanthene fluorescent dyes, thioxanthone fluorescent dyes, thiazine fluorescent dyes, and diaminostilbene fluorescent dyes. Of these, coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, and perylene-based fluorescent dyes, which have good heat resistance and are less likely to deteriorate during molding of the polycarbonate resin, are preferred.

Dyes other than the bluing agents and fluorescent dyes include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as navy blue, perinone dyes, quinoline dyes, quinacridone Dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Further, the resin composition of the present invention can obtain a better metallic color by blending a metallic pigment. As the metallic pigment, those having a metal coating or a metal oxide coating on various plate-like 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 total of the component A and the component B.

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

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

(Vi) White Pigment for High Light Reflection The polycarbonate resin composition of the present invention can be imparted with a light reflection effect by blending a white pigment for high light reflection separately from the H component. Such white pigments include zinc sulfide, zinc oxide, barium sulfate, calcium carbonate, calcined kaolin and the like. The content of the white pigment for high light reflection is preferably 3 to 30 parts by weight, more preferably 8 to 25 parts by weight, based on 100 parts by weight of the total of the component A and the component B. In addition, two or more kinds of white pigments for high light reflection can be used in combination.

(Vii) Other Resins In the resin composition of the present invention, other resins may be used in a small proportion as long as the effects of the present invention are exhibited.
As such other resins, for example, polyethylene terephthalate, polyester resins such as polybutylene terephthalate, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polyethylene, polypropylene And polyolefin resins, polymethacrylate resins, phenol resins, and epoxy resins.

(Viii) Other additives In addition, the aromatic polycarbonate resin composition of the present invention may contain a small amount of additives known per se for imparting various functions to the molded article and improving the properties. it can. These additives are used in usual amounts unless the object of the present invention is impaired.
Examples of such additives include a sliding agent (eg, PTFE particles), a coloring agent other than the H component (eg, a pigment or dye such as carbon black), a light diffusing agent (eg, cross-linked acrylic particles, cross-linked silicon particles, ultra-thin glass flakes, Calcium carbonate particles), fluorescent dyes, inorganic phosphors (for example, phosphors using aluminate as a mother crystal), antistatic agents, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (for example, fine particle oxidation) Titanium, particulate zinc oxide), radical generators, infrared absorbers (heat ray absorbers), photochromic agents, and the like.

(Production of polycarbonate resin composition)
To produce the polycarbonate resin composition of the present invention, any method is employed. For example, after thoroughly mixing the components A to E and optionally other additives using a pre-mixing means such as a V-type blender, a Henschel mixer, a mechanochemical device, and an extrusion mixer, if necessary, extrusion granulation is performed. Such a premix is granulated by an apparatus or a briquetting machine, melt-kneaded by a melt kneader represented by a vented twin-screw extruder, and then pelletized by a pelletizer.

  Alternatively, each component may be independently supplied to a melt kneader represented by a vented twin-screw extruder, or a part of each component may be premixed and then supplied to the melt kneader independently of the remaining components. And the like. As a method of premixing a part of each component, for example, there is a method in which components other than the component A are premixed in advance and then mixed with the polycarbonate resin of the component A or directly supplied to an extruder.

  As a method of pre-mixing, for example, in the case where a component having the form of powder as the A component is included, a master batch of an additive diluted with powder is produced by blending a part of the powder and an additive to be blended, and There is a method using a master batch. Further, a method in which one component is independently supplied from the middle of the melt extruder may be used. When there is a liquid component to be blended, a so-called liquid injection device or liquid addition device can be used for supply to the melt extruder.

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

  The resin extruded as described above is directly cut into pellets, or after forming a strand, the strand is cut with a pelletizer and pelletized. When it is necessary to reduce the influence of external dust and the like during pelletization, it is preferable to clean the atmosphere around the extruder. Furthermore, in the production of such pellets, using various methods already proposed for polycarbonate resins for optical discs, narrowing of the shape distribution of pellets, reduction of miscuts, reduction of fine powder generated during transportation or transportation. In addition, air bubbles (vacuum air bubbles) generated inside the strands and pellets can be appropriately reduced. By these prescriptions, it is possible to increase the cycle of molding and to reduce the rate of occurrence of defects such as silver. The shape of the pellet may be a general shape such as a cylinder, a prism, and a sphere, but is more preferably a cylinder. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and still more preferably 2 to 3.3 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and further preferably 2.5 to 3.5 mm.

(About the molded article comprising the resin composition of the present invention)
The resin composition of the present invention can be used to produce various products by injection molding the pellets obtained by the above-described method. In such injection molding, not only ordinary molding methods, but also injection compression molding, injection press molding, gas assist injection molding, foam molding (including injection by supercritical fluid), insert molding, A molded product can be obtained by using an injection molding method such as in-mold coating molding, heat-insulating mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultra-high-speed injection molding. The advantages of these various molding methods are already widely known. For the molding, either a cold runner method or a hot runner method can be selected.

  Further, the resin composition of the present invention can be used in the form of various shaped extruded products, sheets, films and the like by extrusion molding. For forming a sheet or film, an inflation method, a calendar method, a casting method, or the like can be used. Furthermore, it is also possible to form a heat-shrinkable tube by performing a specific stretching operation. Further, the resin composition of the present invention can be formed into a molded product by rotational molding or blow molding.

  Specific examples of molded articles in which the resin composition of the present invention is used are those suitable for application to living materials, building materials, interior goods, internal parts of OA equipment and home electric appliances, housings, and the like. These products include, for example, personal computers, notebook computers, CRT displays, printers, mobile terminals, mobile phones, copiers, faxes, recording media (CD, CD-ROM, DVD, PD, FDD, etc.) drives, parabolic antennas, Tools, VTRs, TVs, irons, hair dryers, rice cookers, microwave ovens, audio equipment, audio equipment such as audio, laser disks (registered trademark) and compact disks, lighting equipment, refrigerators, air conditioners, typewriters, word processors, suitcases And living materials such as cleaning tools. Resin products formed from the thermoplastic resin composition of the present invention can be used for various components such as housings. Other resin products include vehicle parts such as deflector parts, car navigation parts, and car stereo parts.

  Since the polycarbonate resin composition of the present invention has a high level of compatibility in mechanical properties, chemical resistance, flame retardancy, surface hardness, and appearance, it is not limited to outdoor / indoor use, but also for housing equipment use, building material use, and daily life. It is widely useful in material applications, infrastructure equipment applications, automotive applications, OA / EE applications, outdoor equipment applications, and other various fields. Therefore, the industrial effects of the present invention are extremely large.

  The mode of the present invention that the present inventor considers the best is a collection of the preferred ranges of the above-mentioned requirements. For example, representative examples are described in the following Examples. Of course, the present invention is not limited to these embodiments.

  Hereinafter, the present invention will be further described with reference to examples. Unless otherwise specified, parts in Examples are parts by weight and% is% by weight. The evaluation was performed by the following method.

(Evaluation of polycarbonate resin composition)
(I) Appearance The appearance of an ISO tensile test piece produced by the following method was visually evaluated. The evaluation was performed according to the following criteria.
◎: Particularly excellent appearance ○: Almost no poor appearance △: Some appearance defects such as flow mark and silver from the gate side ×: Flow mark and silver from the gate side Those with strong appearance defects such as

(Ii) Chemical resistance After applying 1% strain by a three-point bending test method using an ISO tensile test piece obtained by the following method, magic phosphorus, bath magic phosphorus, and toilet magic phosphorus (all, After a cloth impregnated with (Kao Corporation) was impregnated and allowed to stand at 23 ° C. for 96 hours, the presence or absence of an appearance change was confirmed. The evaluation was performed according to the following criteria.
：: No change in appearance is observed △: Fine cracks are observed X: Large cracks leading to fracture are observed

(Iii) Flexural Modulus The flexural modulus was measured according to ISO 178 using an ISO flexural test piece obtained by the following method.

(Iv) Charpy impact strength Notched Charpy impact strength was measured in accordance with ISO 179 using an ISO bending test piece obtained by the following method.

(V) Flame retardancy Using a UL test piece obtained by the following method, a V test was performed at a thickness of 1.5 mm and 2.5 mm according to UL94.

(Vi) Surface hardness The pencil hardness was determined using the square plate obtained by the following method in accordance with JIS K5600-5-4 under the following conditions.
[Used equipment]
Tester: Pencil hardness tester No. 553-M (manufactured by Yasuda Seiki Co., Ltd.)
Pencils used: Mitsubishi pencil uni (HB-5B)
* Pencil is exposed about 5-6mm in core and polished with # 400 sandpaper so that the tip is flat and the corners are sharp [Test conditions]
Load: 750g
Test speed: about 30mm / min
[Criteria]
The test site was visually observed, and the pencil hardness that was evaluated as ○ (no damage) was determined.

[Examples 1 to 45, Comparative Examples 1 to 6]
Mixtures having the compositions shown in Tables 1 to 4 and excluding the B-component polypropylene resin were supplied from the first supply port of the extruder. Such a mixture was obtained by mixing with a V-type blender. The B-component polypropylene-based resin was supplied from the second supply port using a side feeder. Extrusion was carried out using a vent-type twin-screw extruder with a diameter of 30 mmφ (Nippon Steel Works TEX30α-38.5BW-3V) at a screw rotation speed of 230 rpm, a discharge rate of 25 kg / h, and a degree of vacuum of the vent of 3 kPa. A pellet was obtained. The extrusion temperature was 270 ° C. from the first supply port to the die.
After a part of the obtained pellets was dried at 90 to 100 ° C. for 6 hours using a hot air circulating drier, a test for evaluation was performed using an injection molding machine at a cylinder temperature of 260 ° C. and a mold temperature of 70 ° C. Specimens (ISO tensile test pieces (based on ISO527-1 and ISO527-2), ISO bending test pieces (based on ISO178 and ISO179)), UL test pieces, and square plates (150 mm x 150 mm x 2 mmt) were formed.

In addition, each component of the symbol notation in Tables 1-4 is as follows.
(A component)
A-1: Aromatic polycarbonate resin (polycarbonate resin powder having a viscosity average molecular weight of 25,100, manufactured by bisphenol A and phosgene by a conventional method, Panlite L-1250WQ (product name) manufactured by Teijin Limited)
A-2: Aromatic polycarbonate resin (Polycarbonate resin powder having a viscosity average molecular weight of 22,400, made from bisphenol A and phosgene by a conventional method, Panlite L-1225WP (product name) manufactured by Teijin Limited)
A-3: Aromatic polycarbonate resin (polycarbonate resin powder made from bisphenol A and phosgene by a conventional method and having a viscosity average molecular weight of 19,800, Panlite L-1225WX (product name) manufactured by Teijin Limited)
A-4: Polycarbonate-polydiorganosiloxane copolymer resin (viscosity average molecular weight 19,800, PDMS amount 8.4%, PDMS polymerization degree 37)

(B component)
B-1: Polypropylene resin (homopolymer, MFR: 2.0 g / 10 min, Sun Allomer PL400A (product name) manufactured by Sun Allomer Co., Ltd.)
B-2: Polypropylene resin (homopolymer, MFR: 0.5 g / 10 min, Sun Allomer VS200A (product name) manufactured by Sun Allomer Co., Ltd.)
B-3: Polypropylene resin (homopolymer, MFR: 10 g / 10 min, Sun Allomer VS700A (product name) manufactured by Sun Allomer Co., Ltd.)
B-4: Polypropylene resin (block polymer, MFR: 1.5 g / 10 min, Sun Allomer VB370BA (product name) manufactured by Sun Allomer Co., Ltd.)

(C component)
C-1: Styrene-ethylene propylene-styrene block copolymer (styrene content: 65 wt%, MFR: 0.4 g / 10 min, Septon 2104 (product name) manufactured by Kuraray Co., Ltd.)
C-2: Styrene-ethylene propylene-styrene block copolymer (styrene content: 30 wt%, MFR: 70 g / 10 min, Septon 2002 (product name) manufactured by Kuraray Co., Ltd.)
C-3: Styrene-ethylene / butylene-styrene block copolymer (styrene content: 67 wt%, MFR: 2.0 g / 10 min, Tuftec H1043 (product name) manufactured by Asahi Kasei Chemicals Corporation)
C-4: Styrene-butadiene-butylene-styrene block copolymer (styrene content: 67 wt%, MFR: 28 g / 10 min, Asahi Kasei Chemicals Corporation, Tuftec P2000 (product name))

(D component)
D-1: Halogen flame retardant (brominated carbonate oligomer having bisphenol A skeleton, FG-7000 (product name) manufactured by Teijin Limited)
D-2: Antimony compound (antimony trioxide, PATOX-K (product name) manufactured by Nippon Seiko Co., Ltd.)
D-3: Cyclic phenoxyphosphazene (manufactured by Fushimi Pharmaceutical Co., Ltd .: FP-110 (trade name))
D-4: Phosphate ester mainly composed of bisphenol A bis (diphenyl phosphate) (CR-741 (trade name) manufactured by Daihachi Chemical Industry Co., Ltd.)

(E component)
E-1: Talc (manufactured by Hayashi Kasei Co., Ltd .; HST 0.8 (trade name), average particle size 3.5 μm)
E-2: Talc (manufactured by IMI Fabi SpA; HTP ultra 5c (trade name), average particle size 0.5 μm)
E-3: talc (manufactured by Katsumitsu Mine Co., Ltd .; Victorylite SG-A (trade name), average particle size 15.2 μm)
E-4: Wollastonite (NYCOS: NYGLOS4 (trade name))
E-5: Mica (manufactured by Kinsei Matech Co., Ltd .: mica powder MT-200B (trade name))

(F component)
F-1: Butadiene-based core-shell type graft polymer (a graft copolymer having a core-shell structure in which the core is 70 wt% with butadiene rubber as a main component and the shell is 30 wt% with methyl methacrylate and styrene as main components, manufactured by Kaneka Corporation) Kane Ace M-701 (product name)
F-2: butadiene-based core-shell type graft polymer (graft copolymer having a core-shell structure in which the core is butadiene rubber as a main component and the shell is methyl methacrylate as a main component and the weight is 40 wt%, Kaneace M manufactured by Kaneka Corporation) -711 (product name))
F-3: an acrylic core-shell type graft polymer (a graft copolymer having a core-shell structure in which the core is a butadiene-acryl composite rubber and butyl acrylate as main components and the shell is 40 wt% and methyl methacrylate as a main component, Mitsubishi METABLEN W-600A (product name) manufactured by Rayon Co., Ltd.)
F-4: Silicone-based core-shell type graft polymer (a graft copolymer having a core-shell structure in which the core is 70% by weight based on an acryl-silicone composite rubber as a main component and the shell is 30% by weight based on methyl methacrylate, Mitsubishi Rayon Co., Ltd. ) METABLEN S-2001 (product name))
F-5: Silicone-based core-shell type graft polymer (a graft copolymer having a core-shell structure having a core of 70% by weight based on an acrylic-silicone composite rubber as a main component and a shell of 30% by weight based on acrylonitrile and styrene, Mitsubishi Rayon ( METABLEN SRK-200A (product name)
F-6: ethylene-ethyl acrylate copolymer (copolymer of ethylene and ethyl acrylate, Nippon Polyethylene Co., Ltd., Lexpearl EEA A4250 (product name))

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

(H component)
H-1: phenolic heat stabilizer (octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, molecular weight 531, Irganox 1076 (product name) manufactured by BASF Japan Ltd.)
H-2: phenolic heat stabilizer (3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesitylene-2,4, 6-triyl) tri-p-cresol, molecular weight 775, Irganox 1330 (product name) manufactured by BASF Japan K.K.
H-3: phenolic heat stabilizer (1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H , 3H, 5H) -trione, molecular weight 784, Irganox 3114 (product name) manufactured by BASF Japan Ltd.)

(I component)
I-1: Phosphorus-based heat stabilizer (trimethyl phosphate, TMP (product name) manufactured by Daihachi Chemical Industry Co., Ltd.)
I-2: phosphorus-based heat stabilizer (tris (2,4-di-tert-butylphenyl) phosphite, manufactured by Ciba Specialty Chemicals Co., Ltd .; Irgafos 168 (trade name))
(J component)
J: Titanium oxide (titanium oxide, 0.2 to 0.3 μm, RTC-30 (product name), manufactured by Taioxide)
(Other components)
WAX: fatty acid ester release agent (Rikemar SL900 (product name) manufactured by Riken Vitamin Co., Ltd.)

  From the above Tables 1 to 4, it can be seen that the formulation of the present invention can provide a polycarbonate resin composition that satisfies mechanical properties, chemical resistance, flame retardancy, surface hardness and appearance in a high dimension.

Claims (15)

(C) 1 to 15 parts by weight of (C) a styrene-based thermoplastic elastomer (component (C)) based on 100 parts by weight of the total of the polycarbonate resin (component (A)) and (B) the polypropylene resin (component (B)); At least one flame retardant (D component ) selected from the group consisting of 0.01 to 30 parts by weight of a halogen-based flame retardant, 0.01 to 30 parts by weight of a phosphorus-based flame retardant, and 0.5 to 10 parts by weight of an antimony oxide compound; And (E) 1 to 80 parts by weight of an inorganic filler (component E) (excluding the inorganic filler having flame retardancy) and 0.1 to 3 parts by weight of (G) an anti-drip agent (component G). A flame-retardant polycarbonate resin composition, comprising: (However, the case where the content of the polycarbonate resin is 0 parts by weight is excluded.)   The flame-retardant polycarbonate resin composition according to claim 1, wherein the resin composition contains 1 to 10 parts by weight of a rubbery elastic body (F component) other than the (F) C component based on 100 parts by weight of the resin component.   The flame-retardant polycarbonate resin composition according to claim 1 or 2, wherein the E component is a silicate mineral.   The flame-retardant polycarbonate resin composition according to claim 2 or 3, wherein the F component is a core-shell type graft polymer.   The flame-retardant polycarbonate resin composition according to any one of claims 1 to 4, wherein the content of the styrene unit of the C component is 40 to 70% by weight.   The flame-retardant polycarbonate resin according to any one of claims 1 to 5, wherein the hydrogenated polydiene unit in the component C is a hydrogenated isoprene unit, and is a block copolymer having an ethylene / propylene block unit. Composition.   The flame-retardant polycarbonate resin according to any one of claims 1 to 5, wherein the hydrogenated polydiene unit in the component C is a hydrogenated butadiene unit, and is a block copolymer having an ethylene / butylene block unit. Composition.   The flame-retardant polycarbonate according to any one of claims 1 to 5, wherein the hydrogenated polydiene unit in the component C is a partially hydrogenated butadiene unit, and is a block copolymer having a butadiene / butylene block unit. Resin composition.   The flame retardant polycarbonate resin composition according to any one of claims 1 to 8, wherein the MFR of the component C at 230 ° C under a load of 2.16 kg is 0.1 to 10 g / 10 min.   The flame-retardant polycarbonate resin composition according to any one of claims 5 to 9, wherein the F component is a core-shell type graft polymer containing no styrene component.   The flame retardant polycarbonate resin composition according to any one of claims 1 to 10, wherein the MFR of the component B at 230 ° C under a load of 2.16 kg is 0.1 to 5 g / 10 min.   The ratio (weight ratio) (A / B) of (A) the polycarbonate resin (A component) and (B) the polypropylene resin (B component) is 90/10 to 60/40. 12. The flame-retardant polycarbonate resin composition according to any one of items 1 to 11.   The flame retardant according to any one of claims 1 to 12, wherein (H) a phenolic heat stabilizer (H component) is contained in an amount of 0.05 to 1.0 part by weight based on 100 parts by weight of the resin component. Polycarbonate resin composition. The flame-retardant polycarbonate resin composition according to claim 13, wherein the H component is a compound having a structure represented by the following formula (14) or (15).

  The flame retardancy according to any one of claims 1 to 14, wherein the resin component contains 0.05 to 1.0 parts by weight of the phosphorus-based heat stabilizer (I component) based on 100 parts by weight of the resin component. Polycarbonate resin composition.