JP6622100B2 - 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 a polyolefin resin having a MFR (230 ° C., 2.16 kg load) of 40 g / min or more, a styrene thermoplastic elastomer, a flame retardant, and an inorganic filler to a polycarbonate resin, mechanical properties are obtained. The present invention relates to a polycarbonate resin composition having improved flame retardancy, chemical resistance, appearance, tape peel resistance and surface hardness.

Polycarbonate resins have excellent mechanical and thermal properties, and are therefore widely used in various fields such as the OA equipment field, the electronic and electrical equipment field, and the automobile field. However, polycarbonate resins have poor workability due to their high melt viscosity, and because they are amorphous resins, they have difficulties in chemical resistance, particularly to detergents. Therefore, it is known to add a polyolefin resin to make up for these drawbacks, but the simple addition causes poor appearance and delamination due to the low compatibility between the polycarbonate resin and the polyolefin resin. Since it is difficult to obtain sufficient mechanical properties, it is in a state of poor practical application.
Accordingly, various resin compositions have been proposed in order to enhance the compatibility of the polycarbonate resin and the polyolefin resin and to provide practical mechanical properties.

  For example, a method in which an elastomer graft-modified with a hydroxyl group-containing vinyl monomer is added as a compatibilizing agent (see Patent Documents 1 and 2), or a polypropylene modified with a hydroxyl group-containing vinyl monomer is used as a compatibilizing agent. A method using an ethylene-α-olefin copolymer composed of the above α-olefin as an impact resistance agent (see Patent Documents 3 and 4), 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), a method of adding a styrene-ethylene-butylene-styrene block copolymer as a compatibilizing agent (see Patent Document 7) Styrene-ethylene / propylene-styrene copolymer Although there is a method of adding (see Patent Document 8) and the like, none of them has developed excellent chemical resistance and mechanical properties, appearance and tape peel resistance exceeding the practical range of polycarbonate. In addition, since polycarbonate and polyolefin have a large difference in melt viscosity, which is a cause of low compatibility, polyolefins having a relatively low MFR are often used in these application examples. However, resin compositions using low MFR polyolefin have not been obtained with improved appearance and tape peel resistance, and application examples of resin compositions using high MFR have been reported. The current situation is not. In addition, many methods for imparting mechanical properties such as rigidity and flame retardancy to resin compositions containing polycarbonate have been reported, but the formulation for resin compositions containing both polycarbonate and polypropylene is There are almost no reports (see Patent Document 9).

JP-A-7-330972 JP-A-8-134277 JP 2005-132937 A JP 54-53162 A JP-A-63-215750 Japanese Unexamined Patent Publication No. 63-215752 Japanese Patent Laid-Open No. 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 flame retardant polycarbonate resin composition having excellent mechanical properties, flame retardancy, chemical resistance, appearance, tape peel resistance and surface hardness.

  As a result of intensive studies to solve the above problems, the present inventor has found that a polycarbonate resin having a MFR (230 ° C., 2.16 kg load) of 40 g / min or more, a polyolefin resin, a styrene thermoplastic elastomer, a flame retardant And a method for obtaining a flame retardant polycarbonate resin composition with improved mechanical properties, flame resistance, chemical resistance, appearance, tape peel resistance and surface hardness by adding an inorganic filler. It came to be completed.

According to the present invention, the above problem is the sum of (A) polycarbonate resin (component A) and (B) polyolefin resin (component B) having an MFR of 40 g / min or more at 230 ° C. and a load of 2.16 kg. (C) Styrenic thermoplastic elastomer (C component) 1-20 parts by weight, (D) Flame retardant (D component) 0.01-30 parts by weight, and (E) Inorganic filler (E component) And 1) to 100 parts by weight of the flame retardant polycarbonate resin composition.
Details of the present invention will be described below.

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

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

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

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

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

Among the various polycarbonates described above, those having a water absorption and Tg (glass transition temperature) adjusted within the following ranges by adjusting the copolymer composition and the like have good hydrolysis resistance of the polymer itself, and Since it is remarkably excellent also in the low curvature property after shaping | molding, it is especially suitable in the field | area where form stability is requested | required.
(I) polycarbonate having a water absorption of 0.05 to 0.15%, preferably 0.06 to 0.13% and Tg of 120 to 180 ° C, or (ii) Tg of 160 to 250 ° C, Polycarbonate which is preferably 170 to 230 ° C. and has a water absorption of 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27%.

Here, the water absorption rate of the polycarbonate is a value obtained by measuring the moisture content after being immersed in water at 23 ° C. for 24 hours in accordance with ISO 62-1980 using a disc-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm. is there. Moreover, Tg (glass transition temperature) is a value calculated | required by the differential scanning calorimeter (DSC) measurement based on JISK7121.
As the carbonate precursor, carbonyl halide, carbonic acid diester, haloformate or the like is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.

  In producing the aromatic polycarbonate resin by the interfacial polymerization method using the dihydric phenol and the carbonate precursor, a catalyst, a terminal terminator, and an antioxidant for preventing the dihydric phenol from being oxidized as necessary. Etc. may be used. The aromatic polycarbonate resin of the present invention is a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, a polyester copolymerized with an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. Carbonate resin, copolymer polycarbonate resin copolymerized with bifunctional alcohol (including alicyclic), and polyester carbonate resin copolymerized with such bifunctional carboxylic acid and bifunctional alcohol are included. Moreover, the mixture which mixed 2 or more types of the obtained aromatic polycarbonate resin may be sufficient.

  The branched polycarbonate resin can impart anti-drip performance and the like to the resin composition of the present invention. Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin include phloroglucin, phloroglucid, or 4,6-dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2, 2 , 4,6-trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) Ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4- [ Trisphenol such as 1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol, tetra (4-hydride) Loxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acids Among them, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable. 1-Tris (4-hydroxyphenyl) ethane is preferred.

  The structural unit derived from the polyfunctional aromatic compound in the branched polycarbonate is preferably a total of 100 mol% of the structural unit derived from the dihydric phenol and the structural unit derived from the polyfunctional aromatic compound. It is 0.01-1 mol%, More preferably, it is 0.05-0.9 mol%, More preferably, it is 0.05-0.8 mol%.

  In particular, in the case of the melt transesterification method, a branched structural unit may be generated as a side reaction, and the amount of the branched structural unit is preferably 100% by mole in total with the structural unit derived from dihydric phenol. The content 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%. In addition, about the ratio of this branched structure, it is possible to calculate by 1H-NMR measurement.

  The aliphatic bifunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Examples of the aliphatic difunctional carboxylic acid include sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, icosanedioic acid and other straight-chain saturated aliphatic dicarboxylic acids, and cyclohexanedicarboxylic acid. Preferred are alicyclic dicarboxylic acids such as As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecane dimethanol.

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

In producing the flame retardant polycarbonate resin composition of the present invention, the viscosity average molecular weight (M) of the polycarbonate-based resin is not particularly limited, but is preferably 1.8 × 10 ^{4 to} 4.0 × 10 ⁴ , more preferably ^{2.0 × 10 4 ~3.5 × 10 4} , more preferably from ^{2.2 × 10 4 ~3.0 × 10 4} . With polycarbonate resins having a viscosity average molecular weight of less than 1.8 × 10 ⁴ , good mechanical properties may not be obtained, and the difference in melt viscosity with polyolefin resins is small, so the appearance and tape peel resistance May decrease. On the other hand, a resin composition obtained from a polycarbonate-based resin having a viscosity average molecular weight exceeding 4.0 × 10 ⁴ is inferior in versatility in that it is inferior in fluidity during injection molding.

In addition, the said polycarbonate-type resin may be obtained by mixing that whose viscosity average molecular weight is outside the said range. In particular, a polycarbonate resin having a viscosity average molecular weight exceeding the above range (5 × 10 ⁴ ) improves the entropy elasticity of the resin. As a result, good moldability is exhibited in gas assist molding and foam molding which may be used when molding a reinforced resin material into a structural member. Such improvement in moldability is even better than that of the branched polycarbonate. As a more preferable aspect, the A component has a viscosity average molecular weight of 7 × 10 ^{4 to} 3 × 10 ⁵ polycarbonate resin A-1-1-1 component), and the viscosity average molecular weight of 1 × 10 ^{4 to} 3 × 10 ⁴ . Polycarbonate resin (A-1-1 component) consisting of 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 (below) , Sometimes referred to as “high molecular weight component-containing polycarbonate resin”).

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

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

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

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

  In addition, calculation of the viscosity average molecular weight of polycarbonate-type resin in the flame-retardant polycarbonate resin composition of this invention is performed in the following way. That is, the composition is mixed with 20 to 30 times its weight of methylene chloride to dissolve the soluble component in the composition. Such soluble matter is collected by Celite filtration. Thereafter, the solvent in the obtained solution is removed. The solid after removal of the solvent is sufficiently dried to obtain a solid component that dissolves in methylene chloride. A specific viscosity at 20 ° C. is determined from a solution obtained by dissolving 0.7 g of the solid in 100 ml of methylene chloride in the same manner as described above, and the viscosity average molecular weight M is calculated from the specific viscosity in the same manner as described above.

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

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

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

[In the general formula (3), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substitution having 6 to 12 carbon atoms. Or an unsubstituted aryl group, R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and p is a natural number Q is 0 or a natural number, and p + q is a natural number of 10-300. X is a C2-C8 divalent aliphatic group. ]

  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-tert-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 Enyl ether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 4,4 '-Dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 4,4'- Dihydroxy-3,3′-diphenyldiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-diphenyldiphenyl sulfide, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis (4-hydro Xylphenyl) cyclohexane, 1,3-bis (4-hydroxyphenyl) cyclohexane, 4,8-bis (4-hydroxyphenyl) tricyclo [5.2.1.02,6] decane, 4,4 ′-(1, 3-adamantanediyl) diphenol, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, and the like.

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

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

  The hydroxyaryl-terminated polydiorganosiloxane (II) is a phenol having an olefinically unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, 2-methoxy-4-allylphenol. It is easily produced by hydrosilylation reaction at the end of a polysiloxane chain having a degree of polymerization of. Of these, (2-allylphenol) -terminated polydiorganosiloxane and (2-methoxy-4-allylphenol) -terminated polydiorganosiloxane are preferred, and (2-allylphenol) -terminated polydimethylsiloxane, especially (2-methoxy-4) -Allylphenol) -terminated polydimethylsiloxane is preferred. The hydroxyaryl-terminated polydiorganosiloxane (II) preferably has a molecular weight distribution (Mw / Mn) of 3 or less. The molecular weight distribution (Mw / Mn) is more preferably 2.5 or less, and even more preferably 2 or less, in order to develop further excellent low outgassing properties and low temperature impact properties during high temperature molding. When the upper limit of such a suitable range is exceeded, the amount of outgas generated during high temperature molding is large, and the low temperature impact property may be inferior.

  In order to achieve high impact resistance, the diorganosiloxane polymerization degree (p + q) of the hydroxyaryl-terminated polydiorganosiloxane (II) is suitably 10 to 300. The degree of diorganosiloxane polymerization (p + q) is preferably 10 to 200, more preferably 12 to 150, and still more preferably 14 to 100. If the amount is less than the lower limit of the preferable range, the impact resistance characteristic of the polycarbonate-polydiorganosiloxane copolymer is not effectively exhibited. If the upper limit of the preferable range is exceeded, poor appearance appears.

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

In the present invention, the hydroxyaryl-terminated polydiorganosiloxane (II) may be used alone or in combination of two or more.
Further, within the range not hindering the present invention, other comonomer other than the dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) is within a range of 10% by weight or less based on the total weight of the copolymer. It can also be used together.
In the present invention, a mixed solution containing an oligomer having a terminal chloroformate group is prepared in advance by the reaction of a dihydric phenol (I) and a carbonate-forming compound in a mixed solution of an organic solvent insoluble in water and an aqueous alkaline solution. To 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 made into an oligomer at one time, or a part of the dihydric phenol (I) is used as a post-added monomer at the latter stage interface. You may add to a polycondensation reaction as a reaction raw material. The post-added monomer is added to allow the subsequent polycondensation reaction to proceed rapidly, and it is not necessary to add it when it is not necessary.
Although the method of this oligomer production | generation reaction is not specifically limited, Usually, the method performed in a solvent in presence of an acid binder is suitable.
The use ratio of the carbonate-forming compound may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. Moreover, when using gaseous carbonate ester-forming compounds, such as phosgene, the method of blowing this into a reaction system can be employ | adopted suitably.

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

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

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

  In the present invention, after obtaining a mixed solution containing an oligomer of dihydric phenol (I) having a terminal chloroformate group in this way, the molecular weight distribution (Mw / Mn) is up to 3 while stirring the mixed solution. A highly purified hydroxyaryl-terminated polydiorganosiloxane (II) represented by the general formula (4) is added to the dihydric phenol (I), and the polyhydroxyorganosiloxane (II) and the oligomer are interfacially polycondensed. As a result, a polycarbonate-polydiorganosiloxane copolymer is obtained.

In (the general formula ^{(4), R 3, R} 4, R 5, R 6, R 7 and ^{R 8} are each independently a hydrogen atom, substituted 6-12 alkyl group carbon atoms or from 1 to 12 carbon atoms Or an unsubstituted aryl group, R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and p is a natural number Q is 0 or a natural number, 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 the hydroxyaryl-terminated polydiorganosiloxane (II) to be used or a part of the dihydric phenol (I) is added as a post-added monomer to the reaction stage as described above, It is preferable to use 2 equivalents or an excess amount of alkali with respect to the total number of moles of monovalent phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) (usually 1 mole corresponds to 2 equivalents).
The polycondensation by the interfacial polycondensation reaction between the dihydric phenol (I) oligomer and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the above mixed solution.

In such a polymerization reaction, a terminal terminator or a molecular weight modifier is usually used. Examples of the terminal terminator include compounds having a monovalent phenolic hydroxyl group. In addition to ordinary phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, etc., long-chain alkylphenols, aliphatic carboxylic acids Examples include chloride, aliphatic carboxylic acid, hydroxybenzoic acid alkyl ester, hydroxyphenylalkyl acid ester, alkyl ether phenol and the like. The amount used is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, with respect to 100 mol of all dihydric phenol compounds used, and it is naturally possible to use two or more compounds in combination. is there.
In order to accelerate the polycondensation reaction, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt may be added.
The reaction time of such a polymerization reaction is preferably 30 minutes or more, more preferably 50 minutes or more. If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added.

  A branching agent can be used in combination with the above dihydric phenol compound to form a branched polycarbonate-polydiorganosiloxane. Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate-polydiorganosiloxane copolymer resin include phloroglucin, phloroglucid, or 4,6-dimethyl-2,4,6-tris (4-hydroxydiphenyl). ) Heptene-2,2,4,6-trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol and the like 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 acid and acid chlorides thereof, among which 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are included. 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferable. The ratio of the polyfunctional compound in the branched polycarbonate-polydiorganosiloxane copolymer resin is preferably 0.001 to 1 mol%, more preferably 0.005 to 0 in the total amount of the aromatic polycarbonate-polydiorganosiloxane copolymer resin. 0.9 mol%, more preferably 0.01 to 0.8 mol%, particularly preferably 0.05 to 0.4 mol%. Such a branched structure amount can be calculated by 1H-NMR measurement.

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

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

  The average size of the polydiorganosiloxane domain in the polycarbonate-polydiorganosiloxane copolymer resin molded article is preferably in the range of 1 to 40 nm. The average size is more preferably 1 to 30 nm, still more preferably 5 to 25 nm. If it is less than the lower limit of such a suitable range, the impact resistance and flame retardancy are not sufficiently exhibited, and if it exceeds the upper limit of such a suitable range, the impact resistance may not be stably exhibited. Thereby, a flame retardant polycarbonate resin composition excellent in impact resistance and appearance is provided.

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

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

(B component: polyolefin resin)
The resin composition of the present invention contains a polyolefin resin as the B component. The polyolefin resin is a synthetic resin obtained by polymerizing or copolymerizing an olefin monomer having a radical polymerizable double bond. The olefin monomer is not particularly limited, and examples thereof include α- such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and 4-methyl-1-pentene. Examples thereof include olefins and conjugated dienes such as butadiene and isoprene. Olefinic monomers may be used alone or in combination of two or more. The polyolefin-based resin is not particularly limited. For example, a homopolymer of ethylene, a copolymer of ethylene and an α-olefin other than ethylene, a homopolymer of propylene, and a copolymer of propylene and an α-olefin other than propylene. Examples include polymers, butene homopolymers, homopolymers or copolymers of conjugated dienes such as butadiene and isoprene, and propylene homopolymers and copolymers of propylene and α-olefins other than propylene are preferred. . More preferably, it is a homopolymer of propylene. Polyolefin resin may be used independently or 2 or more types may be used together.

  In the present invention, a polypropylene resin is more preferably used from the viewpoint of versatility and rigidity. Polypropylene resin is a polymer of propylene, but in the present invention, it also includes copolymers with other monomers. Examples of the polypropylene resin of the present invention include a homopolypropylene resin, a block copolymer of propylene, ethylene, and an α-olefin having 4 to 10 carbon atoms (also referred to as “block polypropylene”), propylene, ethylene, and 4 to 4 carbon atoms. 10 random copolymers with α-olefin (also referred to as “random polypropylene”). “Block polypropylene” and “random polypropylene” are also 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 for 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 are included.
The content of ethylene in the polypropylene copolymer is preferably 5% by mass or less in all monomers. It is preferable that content of a C4-C10 alpha olefin in a polypropylene copolymer is 20 mass% or less in 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 polyolefin-based resin in the present invention is 40 g / 10 min or more, preferably 50 g / 10 min or more, and more preferably 60 g / 10 min or more. When the melt flow rate of the polypropylene resin is less than 40 g / min, high mechanical properties are exhibited, but the appearance and tape peel resistance are poor. The upper limit of the melt flow rate is not particularly limited, but is preferably 300 g / min or less from the viewpoint of mechanical properties. The melt flow rate is also called “MFR”. MFR was measured according to ISO1133.

  In this invention, the polyolefin resin modified | denatured as polyolefin resin is used independently, or the example in which polyolefin resin and modified polyolefin resin are used together is also included. The modified polyolefin resin is a modified polyolefin resin having a polar group. The polar group to be modified includes acid groups such as epoxy groups, glycidyl groups, and carboxyl groups, and acid groups such as acid anhydride groups. It is at least one functional group selected from the group consisting of derivatives. Specifically, a copolymer obtained by copolymerizing a monomer containing a polar group such as an epoxy group, a carboxyl group, and an acid anhydride group with the above-described polyolefin resin can be preferably used. What was made can be used more preferably. Examples of the monomer containing an epoxy group include glycidyl methacrylate, butyl glycidyl malate, butyl glycidyl fumarate, propyl glycidyl fumarate, glycidyl acrylate, N- (4- (2,3-epoxy) -3,5-dimethyl) Preferred is acrylamide. Examples of the monomer containing a carboxyl group include acrylic acid, methacrylic acid, and maleic acid. Examples of the monomer containing an acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. Among the above-mentioned monomers having a polar group, acrylic acid and maleic anhydride are preferable from the viewpoint of reactivity and availability. The melt flow rate (190 ° C., 2.16 kg) of the modified polyolefin resin is preferably 50 g / 10 min or more, more preferably 100 g / 10 min or more, and particularly preferably 150 g / 10 min or more. If the melt flow rate (190 ° C., 2.16 kg) of the modified polyolefin resin is less than 50 g / min, good appearance and tape peel resistance may not be exhibited. The blending amount of the modified polyolefin-based resin is preferably 0 to 100% by weight, more preferably 1 to 50% by weight, and further preferably 2 to 10% by weight in the component B.

  The content of the B component is preferably 5 to 50 parts by weight, more preferably 10 to 45 parts by weight, and more preferably 15 to 40 parts by weight in a total of 100 parts by weight of the A component and the B component. Is more preferable. When the content of component B is less than 5 parts by weight, chemical resistance may not be exhibited, and when it exceeds 50 parts by weight, mechanical properties, flame retardancy, and surface hardness may be greatly reduced.

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

  X in the general formulas (I) and (II) is an aromatic vinyl polymer block, and in the formula (I), the degree of polymerization may be the same or different at both ends of the molecular chain. Y represents 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. It is at least one selected from a polymer 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 copolymers, styrene-ethylene / propylene / styrene copolymers, styrene / ethylene / ethylene / propylene / styrene copolymers, and styrene / butadiene / butene / styrene copolymers. Styrene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-hydrogenated butadiene diblock copolymer, styrene-hydrogenated isoprene block copolymer, styrene-butadiene diblock copolymer, Examples include styrene-isoprene diblock copolymers, among which styrene-ethylene / butylene-styrene copolymers, styrene-ethylene / propylene / styrene copolymers, styrene / ethylene / ethylene / propylene / styrene copolymers, Styrene-Butaji Down - butene - styrene copolymer it is most preferred.

  The content of the X component in the block copolymer is desirably 40 to 80% by weight, preferably 45 to 75% by weight, and more preferably 50 to 70% by weight. If this amount is less than 40% by weight, the effect of improving compatibility is lowered, and the mechanical properties, chemical resistance, and tape peel resistance of the resin composition are hardly exhibited. On the other hand, if it exceeds 80% by weight, molding processability and impact strength may be lowered.

  The weight average molecular weight of the styrenic thermoplastic elastomer is preferably 250,000 or less, more preferably 200,000 or less, and further preferably 150,000 or less. When the weight average molecular weight exceeds 250,000, the moldability is lowered 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, 0 It is particularly preferably 2 to 8 g / 10 min. If the melt flow rate of the styrenic thermoplastic elastomer is less than 0.1 g / 10 min and exceeds 10 g / 10 min, sufficient toughness may not be exhibited. MFR was measured at 230 ° C. and 2.16 kg load according to ISO1133.

Content of C component is 1-20 weight part with respect to a total of 100 weight part of A component and B component, Preferably it is 2-18 weight part, More preferably, it is 3-15 weight part. Addition of component C further improves impact resistance, chemical resistance, appearance, and tape peel resistance. However, when the amount is less than 1 part by weight, the characteristics are not exhibited, and when it exceeds 20 parts by weight, rigidity, surface hardness and difficulty are increased. Flammability decreases.
In the present invention, the C component styrene elastomer may be modified in the same manner as the B component.

(D component: flame retardant)
As the component D of the present invention, various compounds conventionally known as flame retardants for thermoplastic resins, particularly polycarbonate resins can be applied. More preferably, (i) halogen flame retardants (for example, brominated polycarbonates) Compounds) (ii) phosphorus flame retardants (for example, monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, phosphonic acid amide compounds, and phosphazene compounds), (iii) metal salt flame retardants (for example, (Iv) a silicone-based flame retardant comprising a silicone compound, such as an organic sulfonate alkali (earth) metal salt, a borate metal salt-based flame retardant, and a stannate metal salt-based flame retardant. 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 property, fluidity, rigidity, and thermal stability based on the properties of each compound.
Content of D component is 0.01-30 weight part with respect to a total of 100 weight part of A component and B component, Preferably it is 0.05-28 weight part, More preferably, it is 0.08-25 weight. Part. When the content of component D is less than 0.01 parts by weight, sufficient flame retardancy cannot be obtained, and when it exceeds 30 parts by weight, the impact strength, tape peel resistance and chemical resistance are greatly reduced.

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

In 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 —.
In the formula (5), R preferably represents a methylene group, an ethylene group, an isopropylidene group, —SO ₂ —, and particularly preferably an isopropylidene group.
The brominated polycarbonate has a small number of remaining chloroformate groups and preferably has a terminal chlorine content of 0.3 ppm or less, more preferably 0.2 ppm or less. The amount of terminal chlorine is determined by dissolving a sample in methylene chloride, adding 4- (p-nitrobenzyl) pyridine and allowing it to react with terminal chlorine (terminal chloroformate). -3200). When the terminal chlorine content is 0.3 ppm or less, the heat stability of the flame-retardant polycarbonate resin composition becomes better, and molding at a higher temperature becomes possible, and as a result, a resin composition having better molding processability is provided. The

The brominated polycarbonate preferably has a small number of remaining hydroxyl terminals. More specifically, the amount of terminal hydroxyl groups is preferably 0.0005 mol or less, more preferably 0.0003 mol or less with respect to 1 mol of the structural unit of brominated polycarbonate. The amount of terminal hydroxyl groups can be determined by dissolving a sample in deuterated chloroform and measuring it by 1H-NMR method. Such a terminal hydroxyl group amount is preferable because the heat stability of the flame retardant polycarbonate resin composition is further improved.
The specific viscosity of the brominated polycarbonate is preferably in the range of 0.015 to 0.1, more preferably in the range of 0.015 to 0.08. The specific viscosity of the brominated polycarbonate is calculated according to the above-described specific viscosity calculation formula used for calculating the viscosity average molecular weight of the polycarbonate resin which is the component A of the present invention.
When blending such a halogenated flame retardant as a flame retardant, the content is 1 to 30 parts by weight, preferably 2 to 27 parts by weight, more preferably 100 parts by weight in total of the A component and the B component. 3 to 25 parts by weight.

In addition, the halogen-based flame retardant can further enhance the flame retardancy of the resin composition when used in combination with an antimony oxide compound. Examples of the antimony oxide compound include antimony trioxide, antimony tetraoxide, 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 quantity of an antimony oxide compound is 0.5-10 weight part with respect to a total of 100 weight part of A component and B component, Preferably it is 1-5 weight part. If the blending amount is less than 0.5 parts by weight, the flame retarding effect of the composition due to the synergistic action with the halogen-based flame retardant is small.

(D-2 component: phosphorus 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 examples thereof include organic phosphorus compounds such as phosphate esters, condensed phosphate esters, and phosphazene compounds, and red phosphorus. Etc. Phosphate ester refers to an ester compound of phosphoric acid and an alcohol compound or a phenol compound.

  Specific examples of phosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) Phosphate, tris (phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, monoisodecyl phosphate, 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 Mention may be made of condensed phosphate esters such as phenyl phosphate, resorcinol poly (di-2,6-xylyl) phosphate, bisphenol A polycresyl phosphate, hydroquinone poly (2,6-xylyl) phosphate and condensates thereof. Examples of the condensed phosphate ester include resorcinol bis (di-2,6-xylyl) phosphate, resorcinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), and the like. As a commercial product of resorcinol bis (di-2,6-xylyl) phosphate, PX-200 (manufactured by Daihachi Chemical Industry Co., Ltd.) can be mentioned. Examples of commercially available resorcinol bis (diphenyl phosphate) include CR-733S (manufactured by Daihachi Chemical Industry Co., Ltd.). Examples of commercially available products of bisphenol A bis (diphenyl phosphate) include CR-741 (manufactured by Daihachi Chemical Industry Co., Ltd.). Among these, resorcinol bis (di-2,6-xylyl) phosphate is preferably used from the viewpoint of 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 general formulas (6) and (7).

(In the formula, X ₁ , X ₂ , X ₃ , and X ₄ represent hydrogen, a hydroxyl group, an amino group, or an organic group that does not contain a halogen atom. 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 an alkoxy group, a phenyl group, an amino group, and an allyl group. Is mentioned.
Commercially available phosphazene compounds include SPS-100, SPR-100, SA-100, SPB-100, SPB-100L (above, manufactured by Otsuka Chemical Co., Ltd.), FP-100, FP-110 (above, Fushimi Pharmaceutical). Manufactured).

Moreover, as red phosphorus, not only untreated red phosphorus but also the one in which the surface of red phosphorus is coated with a metal hydrate and a resin to improve stability is used. Examples of the metal hydrate include aluminum hydroxide, magnesium hydroxide, zinc hydroxide, titanium hydroxide and the like. There are no particular limitations on the type of resin and the coating amount, but the resin is preferably a phenol resin, an epoxy resin, or the like having high affinity with the polycarbonate resin used in the present invention.
The coating amount is preferably 1% by weight or more with respect to red phosphorus. When 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 coating amount is preferably as large as possible in terms of stability, but it is preferable not to exceed 20% by weight from the viewpoint of flame retardancy.
When blending such a phosphorus-based flame retardant as a flame retardant, the content thereof is 1 to 30 parts by weight, preferably 2 to 27 parts by weight, more preferably 100 parts by weight in total of the A component and the B component. 3 to 25 parts by weight.

(D-3 component: organometallic salt flame retardant)
The organometallic salt flame retardant is advantageous in that the heat resistance is substantially maintained. The organometallic salt flame retardant most advantageously used in the present invention is an alkali (earth) metal sulfonate. Among them, an alkali (earth) metal salt of a fluorine-substituted organic sulfonic acid is preferable, and an alkali (earth) metal salt of a sulfonic acid having a perfluoroalkyl group is particularly preferable. Here, the carbon number of the perfluoroalkyl group is preferably in the range of 1 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 sulfonate alkali (earth) metal salt is an alkali metal or alkaline earth metal, and examples of the alkali metal include lithium, sodium, potassium, rubidium and cesium. Examples of similar metals include beryllium, magnesium, calcium, strontium and barium. More preferred is an alkali metal. Accordingly, a preferred organometallic salt flame retardant is an alkali metal perfluoroalkyl sulfonate. Among such alkali metals, rubidium and cesium are suitable when transparency requirements are higher, but these are not general-purpose and difficult to purify, resulting in disadvantages in terms of cost. is there. On the other hand, although lithium and sodium are advantageous in terms of cost and flame retardancy, they may be disadvantageous in terms of transparency. In consideration of these, the alkali metal in the perfluoroalkylsulfonic acid alkali metal salt can be properly used, but perfluoroalkylsulfonic acid potassium salt having an excellent balance of properties is most suitable in any respect. Such potassium salts and alkali metal salts of perfluoroalkylsulfonic acid composed of other alkali metals can be used in combination.

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

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

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

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

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

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

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

  Among the metal salts of organic sulfonic acids that do not contain fluorine atoms, alkali (earth) metal salts of aromatic sulfonates are preferred, and potassium salts are particularly preferred. When blending the aromatic sulfonic acid alkali (earth) metal salt as a flame retardant, the content thereof is preferably 0.01 to 1 part by weight with respect to 100 parts by weight in total of the component A and the component B, preferably Is 0.05 to 0.8 parts by weight, more preferably 0.08 to 0.6 parts by weight.

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

Generally, the structure of a silicone compound is constituted by arbitrarily combining the following four types of siloxane units. That is,
M units: (CH ₃ ) ₃ SiO _1/2 , H (CH ₃ ) ₂ SiO _1/2 , H ₂ (CH ₃ ) SiO _1/2 , (CH ₃ ) ₂ (CH ₂ = CH) SiO _1/2 Monofunctional siloxane units such as (CH ₃ ) ₂ (C ₆ H ₅ ) SiO _1/2 , (CH ₃ ) (C ₆ H ₅ ) (CH ₂ ═CH) SiO _1/2 ,
D unit: (CH ₃ ) ₂ SiO, H (CH ₃ ) SiO, H ₂ SiO, H (C ₆ H ₅ ) SiO, (CH ₃ ) (CH ₂ ═CH) SiO, (C ₆ H ₅ ) ₂ SiO Bifunctional siloxane units such as
T unit: (CH ₃ ) SiO _3/2 , (C ₃ H ₇ ) SiO _3/2 , HSiO _3/2 , (CH ₂ ═CH) SiO _3/2 , (C ₆ H ₅ ) SiO _3/2 etc. A trifunctional siloxane unit of
Q unit: a tetrafunctional siloxane unit represented by SiO ₂ .
Specifically, the structure of the silicone compound used for the silicone-based flame retardant is as follows: D _n , T _p , M _m D _n , M _m T _p , M _m Q _q , M _m D _n T _{p , M m D n Q q,} M m T p Q q, M m D n T p Q q, D n T p, D n Q q, include _{D n} T p _{Q q.} Among these, preferable structures of the silicone compound are M _m D _n , M _m T _p , M _m D _n T _p , and M _m D _n Q _q , and more preferable structures are M _m D _n or M _m D _n. T _p .

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

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

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

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

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

(In formula (9) and formula (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 represents 0 or 1. m1 represents 0 or an integer of 1 or more, and in formula (9), when m1 is 2 or more, the repeating unit is a plurality of different repeating units. Can take units.)

(In formula (11), Z ^{4 to} Z ⁸ each independently represents a hydrogen atom or a monovalent organic residue having 1 to 20 carbon atoms. Α ^{4 to} α ⁸ each independently represents 0 or 1. m 2 Represents 0 or an integer greater than or equal to 1. Furthermore, in the formula (11), when m2 is 2 or more, the repeating unit may take 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 compounds represented by the general formula (12) and the general formula (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 having 1 to ⁶ carbon atoms and a cycloalkyl group, and an aryl group and aralkyl group having 6 to 12 carbon atoms, and at least one group is aryl. And δ ¹ , δ ² , and δ ³ are each an alkoxy group having 1 to 4 carbon atoms.)

(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 each an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an alkyl group having 6 to 12 carbon atoms. An aryl group and an aralkyl group, and at least one group is an aryl group or an aralkyl group, and δ ⁴ , δ ⁵ , δ ⁶ , and δ ⁷ represent an alkoxy group having 1 to 4 carbon atoms.

When using a silicone-based flame retardant as the flame retardant, the blending amount is 0.1 to 5 parts by weight, preferably 0.2 to 4 parts by weight, with respect to 100 parts by weight of the total of component A and component B. More preferably, it is 0.3 to 3 parts by weight.
The flame retardant D-1 component, D-2 component, D-3 component and D-4 component 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 an E component. Inorganic fillers are generally known as glass fiber, flat glass fiber, milled fiber, carbon fiber, glass flake, wollastonite, kaolin clay, mica, talc and various whiskers (such as potassium titanate whisker and aluminum borate whisker). Various fillers that have been used can be used. The shape of the inorganic filler can be freely selected from fibrous, flaky, spherical and hollow shapes, and in particular, fibrous and plate-like ones are preferably used for improving the strength and impact resistance of the resin composition. . Further, since glass-based inorganic fillers such as glass fibers and glass flakes have a problem that the mold is easily worn during molding, 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 an SiO ₂ component, and orthosilicate, disilicate, cyclic silicate, chain silicate, and the like are suitable. The silicate mineral takes a crystalline state, and the crystal shape can take various shapes such as a fiber shape and a plate shape.

The silicate mineral may be a compound oxide, oxyacid salt (consisting of an ionic lattice), or a solid solution, and the compound oxide may be a combination of two or more of a single oxide, and a single oxide and oxygen. Any of two or more combinations with an acid salt may be used, and also in a solid solution, any of a solid solution of two or more metal oxides and a solid solution of two or more oxyacid salts may be used. The silicate mineral may be a hydrate. The form of crystal water in the hydrate is one that enters as hydrogen silicate ion as Si—OH, one that enters ionically as a hydroxide ion (OH ⁻ ) with respect to the metal cation, and H ₂ O molecules in the gaps in the structure. Any form of entry may be used.

As the silicate mineral, an artificial compound corresponding to a natural product can be used. As the artificial compound, silicate minerals obtained from various synthetic methods using conventionally known various methods such as solid reaction, hydrothermal reaction, and ultrahigh pressure reaction can be used.
Specific examples of the silicate mineral in each metal oxide component (MO) include the following. Here, the description in parentheses is the name of a mineral or the like mainly composed of such a silicate mineral, and means that the compound in parentheses can be used as the exemplified metal salt.

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

As including CaO its components, 3CaO · _SiO 2 (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 (Gerlenite), solid solution (Merellite) of ochermanite and gehlenite, CaO.SiO ₂ (wollastonite (including both α-type and β-type)), CaO.MgO. 2SiO _{2 (Jiopusaido), CaO · MgO · SiO 2} ( ash magnesia _{olivine), 3CaO · MgO · 2SiO 2} ( _{Meruuinaito), CaO · Al 2 O 3} · 2SiO 2 ( anorthite), 5CaO · 6SiO ₂ · 5H ₂ O (Tobermorite, other 5CaO · 6SiO ₂ · 9H ₂ O, etc. Tobermorite group hydrates such as 2CaO · SiO ₂ · H ₂ O (Hillebrandite), and wollastonite group hydrates such as 6CaO · 6SiO ₂ · H ₂ O (zonotolite) Gyrolite group hydrates such as 2CaO · SiO ₂ · 2H ₂ O (gyrolite), CaO · Al ₂ O ₃ · 2SiO ₂ · H ₂ O (lawsonite), CaO · FeO · 2SiO ₂ (headenite), 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 ), As well as clinozoite, pyrolenite, olivine, vesuvite, onolite, Examples include koutite and augite.

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

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

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

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

(talc)
The talc in the present invention is hydrous magnesium silicate in terms of chemical composition, generally expressed by the chemical formula 4SiO ₂ .3MgO.2H ₂ O, and is usually scaly particles 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%. As other minor components, Fe ₂ O ₃ is 0.03 to 1.2% by weight, Al ₂ O ₃ is 0.05 to 1.5% by weight, CaO is 0.05 to 1.2% by weight, K ₂ O. Is 0.2 wt% or less, Na ₂ O is 0.2 wt% or less. As for the particle diameter of talc, the average particle diameter measured by the sedimentation method is 0.1 to 15 μm (more preferably 0.2 to 12 μm, still more preferably 0.3 to 10 μm, particularly preferably 0.5 to 5 μm). A range is preferable. Furthermore, it is particularly preferable to use talc having a bulk density of 0.5 (g / cm ³ ) or more as a raw material. The average particle size of talc refers to D50 (median diameter of particle size distribution) measured by an X-ray transmission method that is one of liquid phase precipitation methods. A specific example of an apparatus for performing such a measurement is Sedigraph 5100 manufactured by Micromeritics.

  In addition, there is no particular restriction on the manufacturing method when talc is crushed from raw stone, and the axial flow mill method, the annular mill method, the roll mill method, the ball mill method, the jet mill method, the container rotary compression shearing mill method, etc. are used. can do. Further, the talc after pulverization is preferably classified by various classifiers and having a uniform particle size distribution. There are no particular restrictions on the classifier, impactor type inertial force classifier (variable impactor, etc.), Coanda effect type inertial force classifier (elbow jet, etc.), centrifugal field classifier (multistage cyclone, microplex, dispersion separator) , Accucut, Turbo Classifier, Turboplex, Micron Separator, and Super Separator).

  Further, talc is preferably in an agglomerated state in view of its handleability and the like, and as such a production method, there are a method by deaeration compression, a method of compression using a sizing agent, and the like. In particular, the degassing compression method is preferable in that the sizing agent resin component which is simple and unnecessary is not mixed into the resin composition of the present invention.

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

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

The wollastonite of the present invention is a magnetic separator that reflects the iron content mixed in the raw material ore and the iron content mixed due to equipment wear when pulverizing the raw material ore in order to sufficiently reflect the inherent whiteness in the resin composition. It is preferable to remove as much as possible. It is preferable that the iron content in wollastonite is 0.5 wt% or less in terms of Fe ₂ O ₃ by such magnetic separator processing.
Silicate minerals (more preferably mica, talc, wollastonite) are preferably not surface-treated, but are surface-treated with various surface treatment agents such as silane coupling agents, higher fatty acid esters, and waxes. It may be. Furthermore, it may be granulated with a sizing agent such as various resins, higher fatty acid esters, and waxes.

  Content of E component is 1-100 weight part with respect to a total of 100 weight part of A component and B component, Preferably it is 3-90 weight part, More preferably, it is 5-80 weight part. 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 100 parts by weight, the impact resistance is greatly lost and appearance defects such as silver are caused. Further, since the stress on the material is increased due to the improvement in rigidity, a decrease in chemical resistance is observed in a chemical resistance test in which a constant strain is applied.

(F component: Graft polymer)
The resin composition of the present invention can contain a graft polymer as the F component. Among the graft polymers, a graft polymer having a core-shell structure is more preferable as an impact modifier. The core-shell type graft polymer is a monomer selected from aromatic vinyl, vinyl cyanide, acrylic acid ester, methacrylic acid ester, and vinyl compounds copolymerizable therewith, with a rubber component having a glass transition temperature of 10 ° C. or lower as a core. It is a graft copolymer copolymerized using one or more kinds as a shell.

  As the rubber component of F component, 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-acrylic rubber, silicone rubber, epichlorohydrin rubber, fluororubber, and those in which hydrogen is added to these unsaturated bonds, but in view of concerns about the generation of harmful substances during combustion, halogen A rubber component containing no atoms is preferable in terms of environmental load. The glass transition temperature of the rubber component is preferably −10 ° C. or lower, more preferably −30 ° C. or lower. As the rubber component, butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, and acrylic-silicone composite rubber are particularly preferable. The composite rubber is a rubber obtained by copolymerizing two kinds of rubber components or a rubber polymerized 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 further preferably 0.15 to 0.5 μm in terms of the weight average particle diameter. If it is 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 ester include methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, octyl acrylate, and the like. Examples of the methacrylate ester include methyl methacrylate, ethyl methacrylate, butyl methacrylate. , Cyclohexyl methacrylate, octyl methacrylate and the like, and methyl methacrylate is particularly preferable. Among these, methacrylic acid esters such as methyl methacrylate are preferably contained as essential components, and from the viewpoints of mechanical properties and thermal stability, it is more preferable not to include an aromatic vinyl component. This is because the core-shell type graft polymer is excellent in affinity with the aromatic polycarbonate resin, so that more rubber components are present in the resin, and the good impact resistance of the aromatic polycarbonate resin is further increased. This is because it is effectively exhibited, and as a result, the impact resistance of the resin composition is improved. More specifically, the methacrylic acid ester is contained in 100% by weight of the graft component (in the case of the core-shell type polymer in 100% by weight of the shell), preferably 10% by weight or more, more preferably 15% by weight or more. Is preferred. The elastic polymer containing a rubber component having a glass transition temperature of 10 ° C. or less may be produced by any polymerization method including bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. It can be a single-stage graft or a multi-stage graft. Moreover, the mixture with the copolymer of only the graft component byproduced in the case of manufacture may be sufficient. Furthermore, 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-stage swelling polymerization method. In the suspension polymerization method, the aqueous phase and the monomer phase are individually maintained, both are accurately supplied to the continuous disperser, and the particle diameter is controlled by the rotation speed of the disperser, and the continuous production is performed. In the method, a method may be used in which the monomer phase is supplied by passing it through a fine orifice having a diameter of several to several tens of μm or a porous filter in an aqueous liquid having dispersibility to control the particle size. In the case of a core-shell type graft polymer, the reaction may be one stage or multistage for both the core and the shell.

  Such polymers are commercially available and can be easily obtained. For example, as a rubber component, butadiene rubber as a main component is Kaneace M series manufactured by Kaneka Co., Ltd. (for example, the shell component is M-711 whose main component is methyl methacrylate, and the shell component is mainly composed of methyl methacrylate / styrene. M-701, etc.), METABRENE C series manufactured by Mitsubishi Rayon Co., Ltd. (for example, C-223A whose shell component is methyl methacrylate / styrene as a main component), E series (for example, shell component is methyl methacrylate / styrene) E-860A with a main component), Paraloid EXL series of DOW Chemical Co., Ltd. (for example, EXL-2690 whose shell component is methyl methacrylate as a main component), and acrylic rubber or butadiene-acrylic composite rubber as a main component As W (For example, W-600A whose shell component has methyl methacrylate as a main component), DOW Chemical Co., Ltd.'s Paraloid EXL series (for example, EXL-2390 whose shell component has methyl methacrylate as its main component), rubber As a component mainly composed of an acrylic-silicone composite rubber, the shell component manufactured by Mitsubishi Rayon Co., Ltd. is Metbrene S-2001 whose main component is methyl methacrylate, or the shell component is SRK- whose main component is acrylonitrile / styrene. The one marketed under the trade name of 200 is mentioned.

  The content of the F component is preferably 1 to 10 parts by weight, more preferably 1 to 8 parts by weight, and further preferably 2 to 7 parts by weight with respect to 100 parts by weight of the total of the A component and the B component. is there. Addition of the F component further improves mechanical properties and chemical resistance, but if it exceeds 10 parts by weight, the rigidity and flame retardancy may decrease.

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

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

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

  As a mixed form of PTFE, (1) a method in which an aqueous dispersion of PTFE and an aqueous dispersion or solution of an organic polymer are mixed and co-precipitated to obtain a co-aggregated mixture (Japanese Patent Laid-Open No. 60-258263, (Method described in JP-A-63-154744), (2) Method of mixing an aqueous dispersion of PTFE and dried organic polymer particles (Method described in JP-A-4-272957) (3) A method in which an aqueous dispersion of PTFE and an organic polymer particle solution are uniformly mixed, and the respective media are simultaneously removed from the mixture (Japanese Patent Laid-Open Nos. 06-220210, 08-188653, etc.) Described method), (4) a method of polymerizing monomers forming an organic polymer in an aqueous dispersion of PTFE (a method described in JP-A-9-95583), and (5) A method in which an aqueous dispersion of PTFE and an organic polymer dispersion are uniformly mixed, and a vinyl monomer is further polymerized in the mixed dispersion, and then a mixture is obtained (described in JP-A-11-29679, etc.). Those obtained by (Method) can be used. Examples of commercially available PTFE in a mixed form include “Metablene A3800” (trade name) manufactured by Mitsubishi Rayon Co., Ltd. and “BLENDEX B449” (trade name) manufactured by GE Specialty Chemicals.

As a ratio of PTFE in the mixed form, 1 to 60% by weight of PTFE is preferable in 100% by weight of the PTFE mixture, and more preferably 5 to 55% by weight. When the ratio of PTFE is within such a range, good dispersibility of PTFE can be achieved. In addition, the ratio of the said G component shows the quantity of a net anti-drip agent, and in the case of PTFE of a mixed form, shows the amount of net PTFE.
The content of the G component is preferably 0.05 to 2 parts by weight, more preferably 0.1 to 1.5 parts by weight, still more preferably 0.1 parts by weight with respect to 100 parts by weight of the total of the A and B components. 2 to 1 part by weight. If the anti-drip agent exceeds the above range and is too small, the flame retardancy may be insufficient. On the other hand, when the amount of the anti-drip agent exceeds the above range, PTFE is not preferable because not only the PTFE is deposited on the surface of the molded product and the appearance is deteriorated, but also the cost of the resin composition is increased.

  Moreover, as a styrene-type monomer used for the organic type polymer used for the polytetrafluoroethylene-type mixture of this invention, a C1-C6 alkyl group, a C1-C6 alkoxy group, and a halogen are used. Styrene optionally substituted with one or more groups selected from the group consisting of, for example, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, dimethylstyrene, ethyl-styrene, para-tert-butylstyrene , Methoxystyrene, fluorostyrene, monobromostyrene, dibromostyrene, and tribromostyrene, vinylxylene, vinylnaphthalene, but are not limited thereto. The styrenic monomer can 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 includes a (meth) acrylate derivative that 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, C1-6 alkyl 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 can be used alone or in admixture of two or more. Among these, (meth) acrylonitrile is preferable.

The amount of the acrylic monomer-derived unit contained in the organic polymer used in the coating layer is preferably 8 to 11 parts by weight, more preferably 8 to 10 parts by weight with respect to 100 parts by weight of the styrene monomer-derived unit. Parts, more preferably 8 to 9 parts by weight. When the acrylic monomer-derived unit is less than 8 parts by weight, the coating strength may be lowered, and when it is more than 11 parts by weight, the surface appearance of the molded product may be deteriorated.
The polytetrafluoroethylene-based mixture of the present invention preferably has a residual water content of 0.5% by weight or less, more preferably 0.2 to 0.4% by weight, and still more preferably 0.1 to 0. 3% by weight. If the residual water content is more than 0.5% by weight, the flame retardancy may be adversely affected.

  In the production process of the polytetrafluoroethylene mixture of the present invention, a coating layer containing one or more monomers selected from the group consisting of styrene monomers and acrylic monomers in the presence of an initiator Forming on the exterior of the branched polytetrafluoroethylene. Further, after the coating layer forming step, the residual moisture content is dried to 0.5 wt% or less, preferably 0.2 to 0.4 wt%, more preferably 0.1 to 0.3 wt%. Preferably a step is included. The drying step can be performed using methods known in the art such as, for example, hot air drying or vacuum drying methods.

  The initiator used in the polytetrafluoroethylene-based mixture of the present invention can be used without limitation as long as it is used in the polymerization reaction of styrene-based and / or acrylic monomers. Examples of the initiator include cumyl hydroperoxide, di-tert-butyl peroxide, benzoyl peroxide, hydrogen peroxide, and potassium peroxide, but are not limited thereto. In the polytetrafluoroethylene-based mixture of the present invention, one or more initiators can be used depending on the reaction conditions. The amount of the initiator is freely selected within the range used in consideration of the amount of polytetrafluoroethylene and the type / amount of monomer, and is 0.15 to 0.00 based on the amount of the total composition. It is preferable to use 25 parts by weight.

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

  Such a suspension polymerization method does not require a polymerization step by emulsion dispersion in the emulsion polymerization method exemplified in Japanese Patent No. 3469391, and therefore does not require an emulsifier and an electrolyte salt for coagulating and precipitating the polymerized latex. In addition, in the polytetrafluoroethylene mixture produced by the emulsion polymerization method, the emulsifier and the electrolyte salt in the mixture are easily mixed and difficult to remove. Therefore, the emulsifier, the sodium metal ion derived from the electrolyte salt, and the potassium metal ion are reduced. It ’s difficult. Since the polytetrafluoroethylene-based mixture used in the present invention is produced by a suspension polymerization method, the use of such emulsifiers and electrolyte salts reduces the amount of sodium metal ions and potassium metal ions in the mixture. It is possible to improve thermal stability and hydrolysis resistance.

  In the present invention, coated branched PTFE can be used as an anti-drip agent. The coated branched PTFE is a polytetrafluoroethylene mixture composed of branched polytetrafluoroethylene particles and an organic polymer, and is derived from an organic polymer, preferably a styrene monomer, outside the branched polytetrafluoroethylene. It has a coating layer made of a polymer containing units and / or units derived from acrylic monomers. The coating layer is formed on the surface of 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 branched polytetrafluoroethylene. When the polytetrafluoroethylene contained is not branched polytetrafluoroethylene, the dripping prevention effect when the amount of polytetrafluoroethylene added 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 diameter is smaller than 0.1 μm, the surface appearance of the molded article is excellent, but it is difficult to obtain polytetrafluoroethylene having a particle diameter smaller than 0.1 μm commercially. On the other hand, 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. Fluoroethylene is more preferred in terms of stability. Either powder or dispersion form may be used.

  The content of branched polytetrafluoroethylene in the coated branched PTFE is preferably 20 to 60 parts by weight, more preferably 40 to 55 parts by weight, still more preferably 47 to 50 parts by weight with respect to 100 parts by weight of the total weight of the coated branched PTFE. 53 parts by weight, particularly preferably 48 to 52 parts by weight, most preferably 49 to 51 parts by weight. When the proportion of the branched polytetrafluoroethylene is within such a range, good dispersibility of the branched polytetrafluoroethylene can be achieved.

(Other additives)
(I) Phosphorous stabilizer Examples of the phosphorous stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphine.
Specific examples of the phosphite compound include triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl. Phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di -N-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, dis 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 dicyclohexyl pentaerythritol diphosphite.

  Further, as other phosphite compounds, those which react with dihydric phenols and have a cyclic structure can be used. For example, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert- Examples include butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite and 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite.

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

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

Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.
The tertiary phosphine includes triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolyl. Examples include phosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine.

  The phosphorus stabilizers can be used alone or in combination of two or more. Among the phosphorus stabilizers, phosphonite compounds or phosphite compounds represented by the following general formula (14) are preferable.

(In formula (14), 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, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite is preferable as the phosphonite compound, and the stabilizer containing phosphonite as a main component is Sandostab P-EPQ (trademark, manufactured by Clariant). ) And Irgafos P-EPQ (trademark, manufactured by CIBA SPECIALTY CHEMICALS) and both can be used.
Among the above formulas (14), more preferred phosphite compounds are distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di). -Tert-butyl-4-methylphenyl) pentaerythritol diphosphite, and bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite.

  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 Industry Co., Ltd.), and any of them can be used. Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite is 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), and Irgafos126 and 126FF (trademark, manufactured by CIBA SPECIALTY CHEMICALS) are also 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 Co., Ltd.) and can be easily used. Further, bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite is produced by ADK STAB PEP-45 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and Doverphos S-9228 (trademark). , Manufactured by Dober Chemical Co.) and any of them can be used.

  The said phosphorus stabilizer can be used individually or in combination of 2 or more types. The content of the phosphorus-based stabilizer is preferably 0.01 to 1.0 part by weight, more preferably 0.03 to 0.8 part by weight, based on 100 parts by weight of the total of component A and component B. More preferably, it is 0.05 to 0.5 parts by weight. If the content is less than 0.01 part by weight, the effect of suppressing thermal decomposition during processing may not be exhibited, and the mechanical characteristics may not be deteriorated. If the content exceeds 1.0 part by weight, the mechanical characteristics may be deteriorated. .

(Ii) Phenol-based stabilizer The resin composition of the present invention may contain a phenol-based stabilizer. Phenol stabilizers generally include hindered phenols, semi-hindered phenols, and less hindered phenol compounds. Particularly, hindered phenol compounds are more preferable from the viewpoint of applying a heat stable formulation to polypropylene resins. Used for 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-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylamino) Methyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl) -6-tert-butylphenol), 4,4'-methylenebis (2,6 Di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol), 2,2 ′ -Ethylidene-bis (4,6-di-tert-butylphenol), 2,2'-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert) -Butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di- tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- (3-tert-butyl) Ru-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1, -Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4'-thiobis (6-tert-butyl-m-cresol), 4,4'-thiobis (3- Methyl-6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4 ′ -Di-thiobis (2,6-di-tert-butylphenol), 4,4'-tri-thiobis (2,6-di-tert-butylphenol), 2,2-thiodie Renbis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-tert- Butylanilino) -1,3,5-triazine, N, N′-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N′-bis [3- (3 , 5-Di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl -2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) iso Cyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, tetrakis [methylene-3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionate] methane, triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, triethylene glycol-N-bis-3- (3- tert-butyl-4-hydroxy-5-methylphenyl) acetate, 3,9-bis [2 {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) acetyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, tetrakis [Methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris (3-tert-butyl-4-hydroxy Examples include -5-methylbenzyl) benzene and tris (3-tert-butyl-4-hydroxy-5-methylbenzyl) isocyanurate. Among the above compounds, tetrakis [methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate is preferably used, and it is represented by the following formula (15) as (3,3 ′, 3 ″, 5,5 ′, 5) which is excellent in suppressing deterioration of mechanical properties due to thermal decomposition during processing. ″ -Hexa-tert-butyl-a, a ′, a ″-(mesitylene-2,4,6-triyl) tri-p-cresol, and 1,3,5 represented by the following formula (16) -Tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione is more preferably used.

The said phenol type stabilizer can be used individually or in combination of 2 or more types. The content of the phenol-based stabilizer is preferably 0.05 to 1.0 part by weight, more preferably 0.07 to 0.8 part by weight, based on 100 parts by weight of the total of component A and component B. More preferably, it is 0.1 to 0.5 part by weight. If the content is less than 0.05 parts by weight, the effect of suppressing thermal decomposition during processing may not be exhibited, and mechanical properties may be deteriorated. If the content exceeds 1.0 parts by weight, mechanical properties may be deteriorated. .
Either a phosphorus stabilizer or a phenol stabilizer is preferably blended, and a combination thereof is more preferred. In the case of combined use, 0.01 to 0.5 parts by weight of a phosphorus stabilizer and 0.01 to 0.5 parts by weight of a phenol stabilizer are blended with respect to 100 parts by weight of the total of the component A and the component B. It is preferable.

(Iii) Ultraviolet Absorber The flame retardant polycarbonate resin composition of the present invention can contain an ultraviolet absorber. As the ultraviolet absorber, in the benzophenone series, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2- Hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridolate benzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2 ′, 4,4 ′ -Tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-benzoyl-4- Hydroxy-2-methoxyphenyl) Examples include methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2′-carboxybenzophenone.

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

  In the hydroxyphenyl triazine series, for example, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol, 2- (4,6-diphenyl-1,3,5) -Triazin-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxyphenol, 2- (4,6-diphenyl) -1,3,5-triazin-2-yl) -5-propyloxyphenol and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-butyloxyphenol Illustrated. Furthermore, the phenyl group of the above exemplary compounds such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol is 2,4-dimethyl. Examples of the compound are phenyl groups.

In the cyclic imino ester system, for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2′-m-phenylenebis (3,1-benzoxazin-4-one) And 2,2′-p, p′-diphenylenebis (3,1-benzoxazin-4-one) and the like.
In the cyanoacrylate type, for example, 1,3-bis-[(2′-cyano-3 ′, 3′-diphenylacryloyl) oxy] -2,2-bis [(2-cyano-3,3-diphenylacryloyl) oxy ] Methyl) propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene.

Further, the ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, so that the ultraviolet absorbing monomer and / or the light-stable monomer and a single amount of alkyl (meth) acrylate or the like. It may be a polymer type ultraviolet absorber copolymerized with a body. Preferred examples of the ultraviolet absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of (meth) acrylic acid ester. The
Among the above compounds, in the present invention, a compound represented by any of the following formulas (17), (18) and (19) is more preferably used.

The said ultraviolet absorber can be used individually or in combination of 2 or more types.
The content of the ultraviolet absorber is preferably 0.1 to 2 parts by weight, more preferably 0.12 to 1.5 parts by weight, and still more preferably 100 parts by weight of the total of component A and component B 0.15 to 1 part by weight. When the content of the ultraviolet absorber is less than 0.1 parts by weight, sufficient light resistance may not be exhibited. When the content is more than 2 parts by weight, it is not preferable from the viewpoints of poor appearance due to gas generation and deterioration of physical properties.

(Iv) Hindered amine light stabilizer The flame-retardant polycarbonate resin composition of the present invention may contain a hindered amine light stabilizer. The hindered amine light stabilizer is generally called HALS (Hindered Amine Light Stabilizer) and is a compound having a 2,2,6,6-tetramethylpiperidine skeleton in 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-piperi Ruoxy) 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 peridyl) -1,6-hexamethylenediamine and 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 and 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, and a condensate with β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethanol.

The hindered amine light stabilizers are roughly classified according to the binding partner of the nitrogen atom in the piperidine skeleton, the NH type (hydrogen is bonded to the nitrogen atom), the NR type (the alkyl group (R) is bonded to the nitrogen atom), There are three types of N-OR type (an alkoxy group (OR) is bonded to a nitrogen atom), but when applied to a polycarbonate resin, N-R has a low basicity from the viewpoint of the basicity of the hindered amine light stabilizer. More preferably, the N-OR type is used.
Among the compounds described above, compounds represented by the following formulas (20) and (21) 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 light stabilizer is preferably 0 to 1 part by weight, more preferably 0.05 to 1 part by weight, and still more preferably 0. It is 08-0.7 weight part, Most preferably, it is 0.1-0.5 weight part. When the content of the hindered amine light stabilizer is more than 1 part by weight, it is not preferable because an appearance defect due to gas generation and a decrease in physical properties due to decomposition of the polycarbonate resin may occur. Further, if it is less than 0.05 parts by weight, sufficient light resistance may not be exhibited.

(V) Mold Release Agent It is preferable to add a mold release agent to the flame retardant polycarbonate resin composition of the present invention for the purpose of improving productivity during molding and reducing distortion of the molded product. Known release agents can be used. For example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax, 1-alkene polymer, etc., which may be modified with a functional group-containing compound such as acid modification), silicone compound, fluorine compound ( And fluorine oil represented by polyfluoroalkyl ether), paraffin wax, beeswax and the like. Among these, fatty acid esters are preferable as a release agent. Such fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids. Such an aliphatic alcohol may be a monohydric alcohol or a dihydric or higher polyhydric alcohol. Moreover, as carbon number of this alcohol, it is the range of 3-32, More preferably, it is the range of 5-30. Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, seryl alcohol, and triacontanol. Examples of such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. In the fatty acid ester of the present invention, a polyhydric alcohol is more preferable.

  On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, and particularly preferably an aliphatic carboxylic acid having 10 to 22 carbon atoms. Examples of the aliphatic carboxylic acid include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), 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 cetreic acid . Among these, aliphatic carboxylic acids having 14 to 20 carbon atoms are preferable. Of these, saturated aliphatic carboxylic acids are preferred. In particular, stearic acid and palmitic acid are preferred.

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

  The fatty acid ester of the present invention may be either a partial ester or a total ester (full ester). However, partial esters are more preferably full esters because they usually have a high hydroxyl value and tend to induce decomposition of the resin at high temperatures. The acid value in the fatty acid ester of the present invention is preferably 20 or less, more preferably 4 to 20 and even more preferably 4 to 12 from the viewpoint of thermal stability. The acid value can be substantially zero. The hydroxyl value of the fatty acid ester is more preferably in the range of 0.1-30. Further, the iodine value is preferably 10 or less. The iodine value can be substantially zero. These characteristics can be obtained by a method defined in JIS K 0070.

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

(Vi) Dye / pigment The flame-retardant polycarbonate resin composition of the present invention can further contain various dyes / pigments and can provide a molded product exhibiting various design properties. By blending a fluorescent brightening agent or other fluorescent dye that emits light, a more favorable design effect can be imparted utilizing the luminescent color. In addition, a flame-retardant polycarbonate resin composition having coloring with a very small amount of dye and pigment and vivid coloring can also be provided.

  Examples of fluorescent dyes (including fluorescent brighteners) used in the present invention include coumarin fluorescent dyes, benzopyran fluorescent dyes, perylene fluorescent dyes, anthraquinone fluorescent dyes, thioindigo fluorescent dyes, and xanthene fluorescent dyes. And xanthone fluorescent dyes, thioxanthene fluorescent dyes, thioxanthone fluorescent dyes, thiazine fluorescent dyes, and diaminostilbene fluorescent dyes. Among these, coumarin fluorescent dyes, benzopyran fluorescent dyes, and perylene fluorescent dyes are preferable because they have good heat resistance and little deterioration during molding of the polycarbonate resin.

Examples of dyes other than the above bluing agents and fluorescent dyes include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as bitumen, perinone dyes, quinoline dyes, quinacridone And dyes such as dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, the resin composition of this invention can mix | blend a metallic pigment, and can also obtain a better metallic color. As the metallic pigment, those having a metal film or a metal oxide film on various plate-like fillers are suitable.
The content of the dye / pigment is preferably 0.00001 to 1 part by weight, and more preferably 0.00005 to 0.5 part by weight with respect to 100 parts by weight of the total of the A component and the B component.

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

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

(Viii) White pigment for high light reflection The flame retardant polycarbonate resin composition of the present invention can be provided with a light reflection effect by blending a white pigment for high light reflection. Examples of such white pigments include titanium oxide, zinc sulfide, zinc oxide, barium sulfate, calcium carbonate, and calcined kaolin. In particular, titanium oxide is publicly used. As the titanium oxide used, titanium oxide having an average particle diameter of 0.1 to 5.0 μm which has been surface-treated with an organic substance is preferable. (In the present invention, the titanium oxide component of the titanium oxide pigment is expressed as “TiO2”, and the entire pigment including the surface treatment agent is expressed as “titanium oxide”) TiO2 has either an anatase type or a rutile type in crystal form. They may be used, and they can be mixed and used as necessary. A rutile type is more preferable in terms of initial mechanical properties and long-term weather resistance. A rutile type crystal may contain an anatase type crystal. Further, the TiO2 can be produced by a sulfuric acid method, a chlorine method, or other various methods, but the chlorine method is more preferred. Further, 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 usually used for various coloring applications, and the average particle size of titanium oxide used as the white pigment of the present invention is preferably 0.10 to 5.0 μm, preferably 0.15 to 2. 0 μm is more preferable, and 0.18 to 1.5 μm is more preferable. When the average particle diameter is smaller than 0.10 μm, appearance defects such as silver are likely to occur when the filling is high, and when it is larger than 5.0 μm, the appearance may be deteriorated and the mechanical properties may be deteriorated. The average particle size is calculated from the number average of individual single particle sizes measured by electron microscope observation.

  The titanium oxide used in the present invention is preferably surface-treated with an organic compound. When titanium oxide that is not organically treated is used, the appearance deteriorates due to yellowing, and the reflectance of the molded product is significantly reduced, so that sufficient solar reflectance may not be obtained. May not be suitable. As such a surface treatment agent, various treatment agents such as polyol, amine, and silicone 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 treatment agent include alkylchlorosilanes (such as trimethylchlorosilane), alkylalkoxysilanes (such as methyltrimethoxysilane), and hydrogen polysiloxane. Examples of the hydrogen polysiloxane include alkyl hydrogen polysiloxane and alkylphenyl hydrogen polysiloxane. Such an alkyl group is preferably a methyl group or an ethyl group. The titanium oxide surface-treated with such an alkylalkoxysilane and / or hydrogen polysiloxane gives good light reflectivity to the resin composition of the present invention. The amount of the organic compound used for the surface treatment is preferably 0.05 to 5 parts by weight, more preferably 0.5 to 3 parts by weight, still more preferably 1.5 to 2.5 parts by weight per 100 parts by weight of titanium oxide. The range is parts by weight. If the surface treatment amount is less than 0.05 parts by weight, sufficient thermal stability may not be obtained. The surface treatment agent for the organic compound is preferably made in advance with titanium oxide (more preferably titanium oxide coated with another metal oxide). However, it may be a method in which the surface treatment agent is separately added when the raw material of the resin composition is melt-kneaded, and the surface treatment of titanium oxide is performed in the melt-kneading step.

  The content of the white pigment for high light reflection is preferably 0.1 to 10 parts by weight, more preferably 0.15 to 7.5 parts by weight, based on 100 parts by weight of the total of the A component and the B component. More preferably, it is 0.15 to 5 parts by weight. If the content of the white pigment for high light reflection is less than 0.1 parts by weight, sufficient white appearance and light shielding properties may not be obtained. If it exceeds 10 parts by weight, molding defects such as silver and physical properties are remarkably increased. It may decrease and is not preferable. Two or more kinds of white pigments for high light reflection can be used in combination.

(Ix) Other resins and elastomers In the resin composition of the present invention, other resins and elastomers other than the component C can be used in a small proportion within a range where the effects of the present invention are exhibited.
Examples of such other resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, and polymethacrylate resins. And resins such as phenol resins and epoxy resins.
Examples of the elastomer include isobutylene / isoprene rubber, ethylene / propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, and the like.

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

(Manufacture of thermoplastic resin composition)
Arbitrary methods are employ | adopted in order to manufacture the thermoplastic resin composition of this invention. For example, components A to E and optionally other additives are sufficiently mixed using a premixing means such as a V-type blender, Henschel mixer, mechanochemical apparatus, extrusion mixer, etc., and then extruded as necessary. There is a method of granulating such a premixed mixture with a vessel or a briquetting machine, then melt-kneading with a melt-kneader represented by a vent type twin screw extruder, and then pelletizing with a pelletizer.

In addition, each component can be independently supplied to a melt kneader represented by a vented twin screw extruder, or a part of each component can be premixed and then supplied to the melt kneader independently of the remaining components. The method of doing is also mentioned. Examples of the method of premixing a part of each component include a method of premixing components other than the component A in advance and then mixing the components with the thermoplastic resin of the component A or supplying them directly to the extruder.
As a premixing method, for example, when a component having a powder form is included as the component A, a part of the powder and an additive to be blended are manufactured to produce a master batch of the additive diluted with the powder. A method using a master batch can be mentioned. Furthermore, the method etc. which supply one component independently from the middle of a melt extruder are mentioned. In addition, when there exists a liquid thing in the component to mix | blend, what is called a liquid injection apparatus or a liquid addition apparatus can be used for supply to a melt extruder.

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

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

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

  Moreover, the resin composition in this invention can also be used in the form of various profile extrusion molded products, a sheet | seat, a film, etc. by extrusion molding. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can also be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. The resin composition of the present invention can be formed into a molded product by rotational molding, blow molding or the like.

  Specific examples of the molded article in which the resin composition of the present invention is used are suitable for application to interior materials and housings of daily life materials, housing equipment materials, building materials, interior products, OA equipment, and home appliances. . These products include, for example, personal computers, notebook computers, CRT displays, printers, mobile terminals, mobile phones, copiers, fax machines, recording media (CD, CD-ROM, DVD, PD, FDD, etc.) drives, parabolic antennas, electric motors. Tools, VTRs, TVs, irons, hair dryers, rice cookers, microwave ovens, audio equipment, audio equipment such as audio / laser discs (registered trademark) / compact discs, lighting equipment, refrigerators, air conditioners, typewriters, word processors, suitcases Resin products formed from the thermoplastic resin composition of the present invention on various parts such as housings and household materials such as bathrooms, toiletries and vanities, etc. Can be used. Examples of other resin products include vehicle parts such as deflector parts, car navigation parts, and car stereo parts.

  Since the flame-retardant polycarbonate resin composition of the present invention has a high level of mechanical properties, flame retardancy, chemical resistance, appearance, tape peel resistance and surface hardness, It is widely useful in various fields such as residential equipment use, building material use, life material use, infrastructure equipment use, automobile use, OA / EE use, outdoor equipment use, and others. Therefore, the industrial effect exhibited by the present invention is extremely great.

  The form for carrying out the present invention is a summary of the preferred ranges of the above-mentioned requirements. For example, typical examples are described in the following examples. Of course, the present invention is not limited to these forms.

  The following examples further illustrate the present invention. Unless otherwise specified, parts in the examples are parts by weight, and% is% by weight. Evaluation was carried out by the following method.

(Evaluation of thermoplastic resin composition)
(I) Appearance The appearance of a sample plate (three-stage plate with holes) obtained by the following method was visually evaluated. The evaluation was performed according to the following criteria.
◎: Weld is not conspicuous and no streak-like appearance defect is observed ○: Weld is slightly conspicuous, but no streak-like appearance defect is seen Δ: Weld is slightly conspicuous and streaky appearance defect is seen ×: Weld is conspicuous, and streaky appearance is strongly seen

(Ii) Tape peel resistance A cellophane tape (cello tape (registered trademark) CT-15 manufactured by Nichiban Co., Ltd.) is pasted on a 2 mm thick part of a sample plate (three-stage plate with holes) obtained by the following method. The sample was pressed with a finger and brought into close contact, and then peeled off vigorously, and the peeled state of the sample on the cellophane tape was visually evaluated. The evaluation was performed according to the following criteria.
◎: No peeling at all ○: Peeling as large as a fine spot is seen Δ: Small peeling is seen ×: Large peeling is seen XX: Peeling over the area of the attached cellophane tape Seen

(Iii) Chemical resistance After applying 1% strain by the three-point bending test method using the ISO tensile test piece obtained by the following method, magiclin, bath magicrin and toilet magiclin (all, A cloth impregnated with Kao Co., Ltd. was applied and allowed to stand at 23 ° C. for 96 hours. The evaluation was performed according to the following criteria.
○: No appearance change is observed Δ: Fine cracks are observed ×: Large cracks leading to breakage are observed

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

(V) Charpy impact strength According to ISO 179, the Charpy impact strength with a notch was measured using the ISO bending test piece obtained by the following method.

(Vi) Surface hardness Pencil hardness was obtained under the following conditions in accordance with JIS K5600-5-4 at a 2 mm thick part of a sample plate (three-stage plate with holes) prepared by the following method. . The surface hardness is preferably 2B or more.
[Used equipment]
Testing machine: Pencil hardness testing machine No. 553-M (manufactured by Yasuda Seiki Seisakusho Co., Ltd.)
Pencil used: Mitsubishi pencil uni (HB ~ 5B)
* Pencil is exposed with a core of about 5-6mm and polished with # 400 sandpaper to have a flat tip and sharp corners [Test conditions]
Load: 750g
Test speed: about 30mm / min
[Criteria]
The test site was visually observed to determine the pencil hardness that was judged as ◯ (not scratched).

(Vii) Flame retardancy Using the UL test piece obtained by the following method, V test was carried out according to UL94.

[Examples 1-36, Comparative Examples 1-11]
The mixture which consists of a component except the polyolefin-type resin of B component with the composition shown in Table 1-Table 3 was supplied from the 1st supply port of the extruder. Such a mixture was obtained by mixing with a V-type blender. B component polypropylene resin was supplied from the second supply port using a side feeder. Extrusion is performed by using a vent type twin screw extruder (Nippon Steel Works TEX30α-38.5BW-3V) with a diameter of 30 mmφ and melt kneading at a screw rotation speed of 230 rpm, a discharge rate of 25 kg / h, and a vent vacuum of 3 kPa. Pellets were obtained. In addition, about extrusion temperature, it implemented at 250 degreeC from the 1st supply port to the die part.
Part of the obtained pellets was dried in a hot air circulation dryer at 90-100 ° C. for 6 hours, and then used for evaluation at an injection molding machine at a cylinder temperature of 270 ° C. and a mold temperature of 70 ° C. Pieces (ISO tensile test pieces (conforming to ISO527-1 and ISO527-2)), ISO bending test pieces (conforming to ISO178, ISO179, ISO75-1 and ISO75-2)), UL test pieces, and sample plate (three-stage plate with holes) ).

In addition, each component of the symbol description in Table 1-Table 3 is as follows.
(A component)
A-1: Aromatic polycarbonate resin (polycarbonate resin powder having a viscosity average molecular weight of 25,100 made from bisphenol A and phosgene by a conventional method, Panlite L-1250WQ (product name) manufactured by Teijin Ltd.)
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 having a viscosity average molecular weight of 19,700 made from bisphenol A and phosgene by a conventional method, Panlite L-1225WX (product name) manufactured by Teijin Limited)

(B component)
B-1: Polypropylene resin (homopolymer, MFR: 70 g / 10 min (230 ° C., 2.16 kg load), Sun Allomer PLB00A (product name))
B-2: Polypropylene resin (homopolymer, MFR: 42 g / 10 min (230 ° C., 2.16 kg load), PHA03A (product name) manufactured by Sun Allomer Co., Ltd.)
B-3: Polypropylene resin (homopolymer, MFR: 20 g / 10 min (230 ° C., 2.16 kg load), PM802A (product name) manufactured by Sun Allomer Co., Ltd.)
B-4: Polypropylene resin (homopolymer, MFR: 2 g / 10 min (230 ° C., 2.16 kg load), PL400A (product name) manufactured by Sun Allomer Co., Ltd.)
B-5: Maleic anhydride-modified polypropylene resin (MFR: 200 g / 10 min (190 ° C., 2.16 kg load), Admer AT2606 (product name) manufactured by Mitsui Chemicals, Inc.)
B-6: Maleic anhydride-modified polypropylene resin (MFR: 180 g / 10 min (180 ° C., 2.16 kg load), Modic P908 (product name) manufactured by Mitsubishi Chemical Corporation)
B-7: Maleic anhydride-modified polypropylene resin (MFR: 9.1 g / 10 min (230 ° C., 2.16 kg load), Admer QE800 (product name) manufactured by Mitsui Chemicals, Inc.)
B-8: Polypropylene resin (block polymer, MFR: 60 g / 10 min (230 ° C., 2.16 kg load), Sun Allomer PMB60A (product name))
B-9: Polypropylene resin (block polymer, MFR: 100 g / 10 min (230 ° C., 2.16 kg load), Sun Allomer VMD81M (product name))

(C component)
C-1: Styrene-ethylene-propylene-styrene block copolymer (styrene content: 65 wt%, MFR: 0.4 g / 10 min (230 ° C., 2.16 kg load), Kuraray Co., Ltd. Septon 2104 (product name ))
C-2: Styrene-ethylene-butylene-styrene block copolymer (styrene content: 67 wt%, MFR: 2.0 g / 10 min (230 ° C., 2.16 kg load), Tuftec H1043 manufactured by Asahi Kasei Chemicals Corporation (product) Name))
C-3: Styrene-butadiene-butylene-styrene block copolymer (styrene content: 67 wt%, MFR: 28 g / 10 min (230 ° C., 2.16 kg load), Tuftec P2000 (product name) manufactured by Asahi Kasei Chemicals Corporation )
C-4: Styrene-ethylene / propylene-styrene block copolymer (styrene content: 30 wt%, MFR: 70 g / 10 min (230 ° C., 2.16 kg load), Kuraray Co., Ltd. Septon 2002 (product name))
C-5: Styrene-ethylene-butylene-styrene block copolymer (styrene content: 42 wt%, MFR: 0.8 g / 10 min (230 ° C., 2.16 kg load), Tuftec H1051 manufactured by Asahi Kasei Chemicals Corporation (product) Name))

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

(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 Co., Ltd .; HTP ultra 5c (trade name), average particle size 0.5 μm)
E-3: Talc (Katsumiyama Mining Co., Ltd .; Victorite SG-A (trade name), average particle size 15.2 μm)
E-4: Wollastonite (manufactured by NYCO: NYGLOS4 (trade name))
E-5: Mica (manufactured by Kinsei Matec Co., Ltd .: Mica powder MT-200B (trade name))

(F component)
F-1: Butadiene-based core-shell type graft polymer (graft copolymer having a core-shell structure in which the core is 70 wt% mainly containing butadiene rubber and the shell is 30 wt% mainly containing methyl methacrylate and styrene, 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 60 wt% in the shell is methyl methacrylate as a main component, Kaneka Corporation) -711 (product name))
F-3: Acrylic core-shell type graft polymer (graft copolymer having a core-shell structure in which the core is composed of butadiene-acrylic composite rubber and butyl acrylate as main components and the shell is composed of methyl methacrylate as the main component and 40 wt%, Mitsubishi Rayon Co., Ltd. Metablen W-600A (product name))
F-4: Silicone-based core-shell type graft polymer (graft copolymer having a core-shell structure in which the core is 70 wt% based on an acrylic-silicone composite rubber and the shell is 30 wt% based on methyl methacrylate, Mitsubishi Rayon Co., Ltd.) ) Madetablen S-2001 (product name))

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

(Other ingredients)
STB-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.)
STB-2: Phosphorus heat stabilizer (Tris (2,4-di-tert-butylphenyl) phosphite, Irgafos 168 (product name) manufactured by BASF Japan Ltd.)
WAX: Fatty acid ester release agent (Rikenmar SL900 (product name) manufactured by Riken Vitamin Co., Ltd.)
TIO: Titanium oxide (titanium oxide, 0.2 to 0.3 μm, RTC-30 (product name) manufactured by Tyoxide Co.)

Claims (10)

100 parts by weight in total of (A) polycarbonate resin (component A) and (B) homopolypropylene resin or maleic anhydride modified polypropylene resin (component B) having an MFR of 40 g / min or more at 230 ° C. and a load of 2.16 kg In contrast, (C) styrene-based thermoplastic elastomer (C component) 1 to 20 parts by weight, (D) flame retardant (D component) 0.01 to 30 parts by weight, and (E) inorganic filler (E component) 1 to 1 A flame retardant polycarbonate resin composition comprising 100 parts by weight.   The flame retardant polycarbonate resin composition according to claim 1, wherein the E component is a silicate mineral.   The flame-retardant polycarbonate resin composition according to claim 1 or 2, comprising 1 to 10 parts by weight of (F) graft polymer (E component) with respect to 100 parts by weight of the total of A component and B component. .   The difficulty according to any one of claims 1 to 3, wherein 0.05 to 2 parts by weight of (G) anti-drip agent (F component) is included with respect to 100 parts by weight of the total of A component and B component. Flammable polycarbonate resin composition.   The flame retardant polycarbonate resin composition according to claim 1, wherein the B component has an MFR at 230 ° C. and a load of 2.16 kg of 60 g / min or more. The flame-retardant polycarbonate resin composition according to any one of claims 1 to 5 , wherein the styrene component in the component C is 40 to 80% by weight. The flame retardant polycarbonate resin composition according to any one of claims 3 to 6 , 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 7 , wherein the viscosity average molecular weight of the component A is 2.2 x 10 ^{4 to} 3.0 x 10 ⁴ . B component 190 ° C., MFR flame retardant polycarbonate resin composition according to any one of claims 1-8, characterized in that it comprises a maleic anhydride-modified polypropylene resin is 50 g / min or more at 2.16kg load object. The proportion of components A and B (weight ratio) (A / B) flame-retardant polycarbonate resin composition according to any one of claims 1 to 9, characterized in that a 50 / 50-95 / 5.