JP6495669B2 - 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 hindered amine compound to a resin composition containing a polycarbonate resin, a polypropylene resin, a styrene thermoplastic elastomer, and a phosphorus flame retardant, mechanical properties, chemical resistance, flame resistance and appearance are added. Relates to an improved polycarbonate resin composition.

  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 resin has poor workability due to its high melt viscosity, and since it is an amorphous resin, it has difficulty in chemical resistance, particularly for household or commercial detergents. For this reason, it is known to add a polyolefin resin to compensate for these drawbacks, but simple addition has low compatibility between the polycarbonate resin and the polyolefin resin, resulting in delamination and the like, and sufficient mechanical properties. Since it is difficult to obtain, it is in a poor state of practical use. 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 it (see Patent Document 8), none of them has achieved both chemical resistance that exceeds the practical range of polycarbonate and mechanical properties that can withstand practical use comparable to PC / ABS.

  In addition, many methods for imparting flame retardancy to a resin composition containing polycarbonate have been reported (see Patent Document 9). However, there are almost no reports on methods for simultaneously imparting non-halogen, high chemical resistance and flame retardancy to a resin composition containing both polycarbonate and polypropylene.

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, chemical resistance, flame retardancy, and appearance while being non-halogen.

  As a result of intensive studies to solve the above problems, the present inventor has added a hindered amine compound to a resin composition containing a polycarbonate resin, a polypropylene resin, a styrene thermoplastic elastomer and a phosphorus flame retardant, A method for obtaining a polycarbonate resin composition satisfying mechanical properties, chemical resistance, flame retardancy and appearance at a high level without halogen has been found, and the present invention has been completed.

  According to the present invention, the above-mentioned problem is that (C) styrene-based thermoplastic elastomer (C component) with respect to a total of 100 parts by weight of (A) polycarbonate-based resin (A component) and (B) polypropylene-based resin (B component). 1) to 15 parts by weight, (D) 1 to 30 parts by weight of a phosphorus flame retardant (D component) and (E) 0.01 to 1 part by weight of a hindered amine compound (E component) This is achieved by the conductive 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 bisphenol A-based polycarbonate, which is a general-purpose polycarbonate, it is possible to use a special polycarbonate produced using other dihydric phenols as the A component.
For example, as part or all of the dihydric phenol component, 4,4 ′-(m-phenylenediisopropylidene) diphenol (hereinafter sometimes abbreviated as “BPM”), 1,1-bis (4-hydroxy) Phenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as “Bis-TMC”), 9,9-bis (4-hydroxyphenyl) Polycarbonate (homopolymer or copolymer) using fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as “BCF”) has dimensions due to water absorption. It is suitable for applications where the demands for change and shape stability are particularly severe. These dihydric phenols other than BPA are preferably used in an amount of 5 mol% or more, particularly 10 mol% or more of the entire dihydric phenol component constituting the polycarbonate.

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 Of 20 to 80 mol% (more preferably 25 to 60 mol%, 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%, still more preferably 35 to 55 mol%).

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

Of 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, etc. have good hydrolysis resistance of the polymer itself, and Since it is remarkably excellent in low warpage after molding, it is particularly suitable in a field where form stability is required.
(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 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 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 × 10 ^{4 to} 5 × 10 ⁴ , more preferably 1.4 × 10. ^{4 to} 3 × 10 ⁴ , more preferably 1.4 × 10 ^{4 to} 2.4 × 10 ⁴ .
With a polycarbonate resin having a viscosity average molecular weight of less than 1 × 10 ⁴ , good mechanical properties cannot be obtained. On the other hand, a resin composition obtained from an aromatic polycarbonate resin having a viscosity average molecular weight exceeding 5 × 10 ⁴ is inferior in versatility in that it is inferior in fluidity during injection molding.

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 , 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 by using an Ostwald viscometer from a solution in which 0.7 g of polycarbonate is dissolved in 100 ml of methylene chloride at 20 ° C. with a specific viscosity (η _SP ) calculated by the following formula:
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
The viscosity average molecular weight M is calculated from the determined specific viscosity (η _SP ) 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

  The viscosity average molecular weight of the polycarbonate resin in the polycarbonate resin composition of the present invention is calculated as follows. That is, the composition is mixed with 20 to 30 times its weight of methylene chloride to dissolve the soluble component in the composition. 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). Polymeric resin.

[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 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 to 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, 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 a reaction of a dihydric phenol (I) and a carbonate-forming compound in a mixed solution of an organic solvent insoluble in water and an alkaline aqueous solution. To do.
In producing the oligomer of the dihydric phenol (I), the whole amount of the dihydric phenol (I) used in the method of the present invention may be converted 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 hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer are subjected to interfacial polycondensation. 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) as described above is added as a post-added monomer to this reaction stage, 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 interfacial polycondensation reaction between the oligomer of dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the above mixture.

In the polymerization reaction, a terminal terminator or a molecular weight regulator is usually used. Examples of the terminal terminator include compounds having a monohydric phenolic hydroxyl group. In addition to ordinary phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, etc., long-chain alkylphenols, aliphatic carboxylic acids Examples include chloride, aliphatic carboxylic acid, hydroxybenzoic acid alkyl ester, hydroxyphenylalkyl acid ester, alkyl ether phenol and the like. The amount used is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, based on 100 mol of all dihydric phenol compounds used, and it is naturally possible to use two or more compounds in combination. is there.
In order to accelerate the polycondensation reaction, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt may be added.
The reaction time of such a polymerization reaction 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 obtain a 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) after 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 polycarbonate resin composition excellent in impact resistance and appearance is provided.

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

In the above formula (1), δ is the standard deviation of the polydiorganosiloxane domain size, and Dav is the average domain size.
The terms “average domain size” and “normalized dispersion” used in connection with the present invention are the measurement of the 1.0 mm thickness of the three-stage plate produced by the method described in the Examples by the small angle X-ray scattering method. The measured values obtained by In addition, the analysis was performed using an isolated particle model that does not take into account the interparticle interaction (interparticle interference).

(B component: polypropylene resin)
The resin composition of the present invention contains a polypropylene resin as the B component. 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 weight or less in all monomers. The content of the α-olefin having 4 to 10 carbon atoms in the polypropylene copolymer is preferably 20% by weight or less in all monomers.
The polypropylene copolymer is preferably a copolymer of propylene and ethylene or a copolymer of propylene and 1-butene, and particularly preferably a copolymer of propylene and ethylene.

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

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

(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 are most preferred.

  The content of the X component in the block copolymer is 20 to 80% by weight, preferably 30 to 75% by weight, more preferably 40 to 70% by weight. If this amount is less than 20% by weight, the rigidity and impact strength of the resin composition are lowered, and if it exceeds 80% by weight, the 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 1-15 weight part with respect to a total of 100 weight part of A component and B component, Preferably it is 2-14 weight part, More preferably, it is 3-13 weight part. When the content is less than 1 part by weight, impact strength and chemical resistance are deteriorated and appearance of the molded product is deteriorated. When the content exceeds 15 parts by weight, rigidity and flame retardancy are deteriorated.

(D 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. Among them, phosphazene compounds are particularly preferable among them.
Phosphate ester refers to an ester compound of phosphoric acid and an alcohol compound or a phenol compound. In this invention, a flame retardance can be provided to a resin composition by mix | blending phosphate ester.

  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 (5) and (6).

(Wherein X ₁ , X ₂ , X ₃ and X ₄ represent hydrogen, a hydroxyl group, an amino group, or an organic group not containing a halogen atom. N represents an integer of 3 to 10).
In the above formulas (5) and (6), examples of the organic group not containing a halogen atom represented by X ₁ , X ₂ , X ₃ , or X ₄ include an alkoxy group, a phenyl group, an amino group, and an allyl group. Is mentioned.

  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, and FP-110T ( As mentioned above, Fushimi Pharmaceutical). The phosphazene compound is more preferably used because it is more excellent in hydrolysis resistance than the phosphoric acid ester and the chemical resistance is not easily lowered.

  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 kneading at a high temperature. The amount of coating 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.
Content of D component is 1-30 weight part with respect to a total of 100 weight part of A component and B component, Preferably it is 3-25 weight part, More preferably, it is 5-20 weight part. When the content of component D is less than 1 part by weight, flame retardancy is not exhibited, and when it exceeds 30 parts by weight, mechanical properties and chemical resistance are remarkably lowered.

(E component: hindered amine compound)
The resin composition of the present invention contains a hindered amine compound as the E component. The hindered amine compound is generally called HALS (Hindered Amine Light Stabilizer) and is used as a light stabilizer, and has a 2,2,6,6-tetramethylpiperidine skeleton in the structure. Examples of hindered amine compounds include 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2, and the like. 6,6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-methoxy-2, 2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine, 4-benzyloxy-2 , 2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, 4- (ethyl Rubamoyloxy) -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-piperidyloxy) ethane, α, α′-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2,6,6-tetramethyl-4- Piperidylt Rylene-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 Polycondensation of '-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine , Poly [{6- (1,1,3,3-te Tramethylbutyl) 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-hydroxyfe L) propionyloxy] 2,2,6,6-tetramethylpiperidine, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β, β , Β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethanol and the like.

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, from the viewpoint of the basicity of the hindered amine compound, the N-R type which is low basicity, It is more preferable to use the N-OR type. Depending on the type of the hindered amine-based compound, the polycarbonate resin composition may be colored yellow or a large molecular weight reduction may occur.
Among the above compounds, compounds represented by the following formulas (7) and (8) are more preferably used in the present invention.

The said hindered amine type compound can be used individually or in combination of 2 or more types.
Content of E component is 0.01-1 weight part with respect to a total of 100 weight part of A component and B component, 0.02-0.8 weight part is preferable, More preferably, 0.05-0 .6 parts by weight, particularly preferably 0.1 to 0.4 parts by weight. If the content of the E component is more than 1 part by weight, poor appearance due to gas generation and deterioration of physical properties and flame retardance due to decomposition of the polycarbonate resin occur. Moreover, sufficient flame retardance is not expressed as it is less than 0.01 weight part.

(F component: rubber-like elastic body other than C component)
The resin composition of the present invention can contain a rubber-like elastic body other than the C component as the F component. The rubber-like elastic body contains 40% by weight or more of a rubber component having a glass transition temperature of 10 ° C. or lower, preferably −10 ° C. or lower, more preferably −30 ° C. or lower. For example, a graft in which one or more monomers selected from aromatic vinyl, vinyl cyanide, acrylic acid ester, methacrylic acid ester, and a vinyl compound copolymerizable therewith are copolymerized with the rubber component Mention may be made of copolymers. On the other hand, it is also possible to use various known thermoplastic elastomers having no cross-linked structure other than the component C, such as polyurethane elastomers, polyester elastomers, polyetheramide elastomers, and the like. The rubber components having a glass transition temperature of 10 ° C. or less here include 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, fluorine rubber, and those obtained by adding hydrogen to the unsaturated bond portion.

  Among these, a core-shell type graft polymer is preferable. The core-shell type graft polymer here is selected from aromatic vinyl, vinyl cyanide, acrylate ester, methacrylate ester, and vinyl compounds copolymerizable therewith, with a rubber component having a glass transition temperature of 10 ° C. or less as a core. A graft copolymer copolymerized with one or more monomers as a shell. The rubber component of the core-shell type graft polymer includes 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 where unsaturated bonds are added with hydrogen can be cited, but from the point of concern about the generation of harmful substances during combustion A rubber component containing no halogen atom is preferable in terms of environmental load. The glass transition temperature of the rubber component is preferably −10 ° C. or lower, more preferably −30 ° C. or lower. 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. 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. Among these, those not containing styrene, which is an aromatic vinyl component, are particularly preferably used in terms of mechanical properties and chemical resistance.

  The content of the F component is preferably 1 to 10 parts by weight, more preferably 1.5 to 7.5 parts by weight, and still more preferably 2 to 2 parts by weight with respect to 100 parts by weight of the total of the A component and the B component. 6 parts by weight. If the content is less than 1 part by weight, impact strength and chemical resistance may be reduced, and if it exceeds 10 parts by weight, rigidity and flame retardancy may be reduced.

(G component: anti-drip agent)
The resin composition of the present invention can contain an anti-drip agent as the 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 include a fluorinated polymer having a fibril-forming ability. Examples of such a polymer include polytetrafluoroethylene, a tetrafluoroethylene copolymer (for example, a tetrafluoroethylene / hexafluoropropylene copolymer, 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 Application Laid-Open No. 60-258263; (Method described in JP-A-63-154744), (2) A 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 each medium is simultaneously removed from the mixture (described in JP-A-06-220210, JP-A-08-188653, etc.) And (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 TFE and an organic polymer dispersion are uniformly mixed, and a vinyl monomer is further polymerized in the mixture 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.
The content of the G component is preferably 0.1 to 3 parts by weight, more preferably 0.15 to 2 parts by weight, and still more preferably 0.2 to 0.2 parts by weight with respect to 100 parts by weight of the total of the A component and the B component. 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 precipitates on the surface of the molded product, resulting in poor appearance and may lead to an increase in the cost of the resin composition. In addition, content of the said G component shows the quantity of a net anti-drip agent, and in the case of PTFE of a mixed form, it shows a net PTFE quantity.

  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. If the acrylic monomer-derived unit is less than 8 parts by weight, the coating strength may be reduced, and if it is more than 11 parts by weight, the surface appearance of the molded 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 with stirring. 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 (component B) used in the present invention is produced by a suspension polymerization method, such an emulsifier and electrolyte salts are not used, so that sodium metal ions and potassium metal ions in the mixture are used. Can be reduced, and thermal stability and hydrolysis resistance can be improved.

  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. Further, when the particle diameter is larger than 0.6 μm, the surface appearance of the molded product may be deteriorated. The number average molecular weight of the polytetrafluoroethylene used in the present invention is preferably 1 × 10 ⁴ to 1 × 10 ⁷ , more preferably 2 × 10 ^{6 to} 9 × 10 ⁶ , and generally a polytetrafluoroethylene having a high molecular weight. 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) Phosphorus stabilizer Examples of the phosphorous stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphine.
Specifically, as the phosphite compound, for example, 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 monoorxenyl 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.
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 (9) are preferable.

（式（９）中、ＲおよびＲ’は炭素数６〜３０のアルキル基または炭素数６〜３０のアリール基を表し、互いに同一であっても異なっていてもよい。）

(In Formula (9), 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 (9), 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.

(Ii) Hindered phenolic antioxidant As the hindered phenolic compound, various compounds that are usually blended in a resin can be used. Examples of such hindered phenol compounds include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-tert -Butyl-6- (3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylamino) Methyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl) -6-tert-butylphenol), 4,4'-methylenebis (2,6 Di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol), 2,2 ′ -Ethylidene-bis (4,6-di-tert-butylphenol), 2,2'-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert) -Butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di- tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- (3-tert-butyl) Ru-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1, -Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4'-thiobis (6-tert-butyl-m-cresol), 4,4'-thiobis (3- Methyl-6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4 ′ -Di-thiobis (2,6-di-tert-butylphenol), 4,4'-tri-thiobis (2,6-di-tert-butylphenol), 2,2-thiodie Renbis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-tert- Butylanilino) -1,3,5-triazine, N, N′-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N′-bis [3- (3 , 5-Di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl -2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) iso Cyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, tetrakis [methylene-3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionate] methane, triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, triethylene glycol-N-bis-3- (3- tert-butyl-4-hydroxy-5-methylphenyl) acetate, 3,9-bis [2 {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) acetyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, tetrakis [Methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris (3-tert-butyl-4-hydroxy Examples include -5-methylbenzyl) benzene and tris (3-tert-butyl-4-hydroxy-5-methylbenzyl) isocyanurate.

  Among the above compounds, tetrakis [methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, octadecyl-3- (3,5-di-tert-butyl-) is used in the present invention. 4-hydroxyphenyl) propionate, and 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4 , 8,10-Tetraoxaspiro [5,5] undecane is preferably used. In particular, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxa Spiro [5,5] undecane is preferred. The said hindered phenolic antioxidant can be used individually or in combination of 2 or more types.

  Either of the phosphorus stabilizer and the hindered phenol antioxidant is preferably blended, and the combination of these is more preferred. The blending amount of the phosphorus stabilizer and the hindered phenol antioxidant is preferably 0.001 to 3 parts by weight, more preferably 0.005 to 100 parts by weight of the total of the component A and the component B, respectively. 2 parts by weight, more preferably 0.01 to 1 part by weight. In the case of combined use, 0.01 to 0.3 parts by weight of a phosphorus-based stabilizer and 0.01 to 0.3 parts by weight of a hindered phenol-based antioxidant with respect to a total of 100 parts by weight of the component A and the component B Is more preferably blended.

(Iii) Mold Release Agent The polycarbonate resin composition of the present invention preferably further contains a mold release agent 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 the above, 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 polycarbonate resin composition has good release properties and release properties. In particular, such an amount of fatty acid ester provides a polycarbonate resin composition having good release properties and roll release properties without impairing good hue.

(Iv) Dye / pigment The polycarbonate resin composition of the present invention can further provide a molded product containing various dyes / pigments and exhibiting various design properties. By blending a fluorescent brightening agent or other fluorescent dye that emits light, a better design effect that makes use of the luminescent color can be imparted. Further, a polycarbonate resin composition having coloring with a very small amount of dye / pigment and vivid coloring can also be provided.

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

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

(Vi) Filler In the polycarbonate resin composition of the present invention, various fillers can be blended as reinforcing fillers as long as the effects of the present invention are exhibited. For example, calcium carbonate, glass fiber, glass bead, glass balloon, glass milled fiber, glass flake, carbon fiber, carbon flake, carbon bead, carbon milled fiber, graphite, vapor grown ultrafine carbon fiber (fiber diameter is 0.1 μm Carbon nanotubes (fiber diameter is less than 0.1 μm, hollow), fullerene, metal flakes, metal fibers, metal coated glass fibers, metal coated carbon fibers, metal coated glass flakes, silica, metal oxide particles, Examples include metal oxide fibers, metal oxide balloons, and various whiskers (such as potassium titanate whiskers, aluminum borate whiskers, and basic magnesium sulfate). These reinforcing fillers may be used alone or in combination of two or more.
The content of these fillers is preferably 0.1 to 60 parts by weight, more preferably 0.5 to 50 parts by weight with respect to 100 parts by weight of the total of component A and component B.

(Vii) White pigment for high light reflection The 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 zinc sulfide, zinc oxide, barium sulfate, calcium carbonate, and calcined kaolin. The content of the white pigment for high light reflection is preferably 3 to 30 parts by weight, more preferably 8 to 25 parts by weight with respect to 100 parts by weight as a total of the A component and the B component. Two or more kinds of white pigments for high light reflection can be used in combination.

(Viii) 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 in which 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, polyethylene, and polypropylene. And other resins such as polyolefin resins, polymethacrylate resins, phenol resins, and epoxy resins.
Examples of the elastomer include isobutylene / isoprene rubber, ethylene / propylene rubber, acrylic elastomer, polyester elastomer, and polyamide elastomer.

(Ix) Other additives In addition, the polycarbonate resin composition of the present invention may contain a small amount of additives known per se for imparting various functions to the molded article and improving properties. 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 polycarbonate resin composition)
Arbitrary methods are employ | adopted in order to manufacture the polycarbonate resin composition of this invention. For example, components A to E and optionally other additives are sufficiently mixed using 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 using 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, a method of supplying each component independently to a melt kneader represented by a vent type twin screw extruder, or a part of each component is premixed and then supplied to the melt kneader independently of the remaining components. The method of doing is also mentioned. Examples of a 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 polycarbonate resin of the component A or directly supplying them to an extruder.

  As a premixing method, for example, when a component having a powder form is included as the component A, a part of the powder and an additive to be blended are mixed to produce a master batch of the additive diluted with the powder. A method using a master batch can be mentioned. 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 is preferably installed for efficiently discharging generated moisture and volatile gas to the outside of the extruder. It is also possible to remove a foreign substance from the resin composition by installing a screen for removing the foreign substance mixed in the extrusion raw material in the zone in front of the extruder die. Examples of such a screen include a wire mesh, a screen changer, a sintered metal plate (such as a disk filter), and the like.
Examples of the melt kneader include a banbury mixer, a kneading roll, a single screw extruder, a multi-screw extruder having three or more axes, in addition to a twin screw extruder.

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

(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. In addition, either a cold runner method or a hot runner method 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 living materials, building materials, interior goods, OA equipment, home appliances, internal parts, housings, and the like. 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 And household materials such as cleaning tools, etc., and resin products formed from the thermoplastic resin composition of the present invention can be used for various parts such as these casings. Examples of other resin products include vehicle parts such as deflector parts, car navigation parts, and car stereo parts.

  Since the polycarbonate resin composition of the present invention has both high mechanical properties, chemical resistance, flame retardancy, and appearance, it is not limited to the outdoors / indoors, but is also used for housing equipment, building materials, living materials, It is widely useful in infrastructure equipment use, automobile use, OA / EE use, outdoor equipment use, and other various fields. Therefore, the industrial effect exhibited by the present invention is extremely great.

  The form of the invention that the present inventor considers to be the best is an aggregation of the preferable ranges of the above requirements. For example, typical examples are described in the following examples. Of course, the present invention is not limited to these forms.

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 polycarbonate resin composition)
(I) Appearance The appearance of an ISO tensile test piece obtained by the following method was visually evaluated. The evaluation was performed according to the following criteria.
○: Almost no appearance defect is observed Δ: The sample is slightly yellowish or there is a slight appearance defect such as flow mark or silver from the gate side ×: The sample is strongly yellowish (Ii) Chemical resistance In the three-point bending test method using an ISO tensile test piece obtained by the following method. After applying a strain of 1%, apply a cloth impregnated with magic phosphorus, bath magic phosphorus and toilet magic phosphorus (all manufactured by Kao Corporation) and leave it at 23 ° C. for 96 hours. confirmed. The evaluation was performed according to the following criteria.
○: No change in appearance Δ: Generation of fine cracks X: Large cracks leading to breakage (iii) Flexural modulus ISO bending test specimen obtained by the following method Was used to measure the flexural modulus according to ISO 178.
(Iv) Charpy impact strength According to ISO 179, the Charpy impact strength with a notch was measured according to ISO 179 using the ISO bending test piece obtained by the following method.
(V) Flame retardancy Using the UL test piece obtained by the following method, a V test was conducted at thicknesses of 1.5 mm and 2.5 mm according to UL94.

[Examples 1 to 33, Comparative Examples 1 to 8]
The mixture which consists of a component except the polypropylene 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 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 vacuum degree of the vent of 3 kPa. Pellets were obtained. In addition, about extrusion temperature, it implemented at 270 degreeC from the 1st supply port to the die part.
A part of the obtained pellets was dried in a hot air circulation dryer at 90 to 100 ° C. for 6 hours, and then evaluated for evaluation at a cylinder temperature of 260 ° C. and a mold temperature of 70 ° C. using an injection molding machine. A piece (ISO tensile test piece (conforming to ISO527-1 and ISO527-2), an ISO bending test piece (conforming to ISO178 and ISO179)) and a UL test piece were molded.

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 Limited)
A-2: Aromatic polycarbonate resin (polycarbonate resin powder having a viscosity average molecular weight of 22,400 made from bisphenol A and phosgene by a conventional method, Panlite L-1225WP (product name) manufactured by Teijin Ltd.)
A-3: Aromatic polycarbonate resin (polycarbonate resin powder having a viscosity average molecular weight of 19,800 made from bisphenol A and phosgene by a conventional method, Panlite L-1225WX (product name) manufactured by Teijin Limited)
A-4: Polycarbonate-polydiorganosiloxane copolymer resin (viscosity average molecular weight 19,800, PDMS amount 8.4%, PDMS polymerization degree 37)

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

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

(D component)
D-1: Cyclic phenoxyphosphazene (Fushimi Pharmaceutical Co., Ltd .: FP-110T (trade name))
D-2: 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: hindered amine compound (polycondensation product of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol (NR type), Tinvin 622 SF manufactured by BASF Japan Ltd.) (product name))
E-2: hindered amine compound (bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl) Malonate (N-R type), Tinuvin PA 144 (product name) manufactured by BASF Japan Ltd.)
E-3: Hindered amine compound (N-OR type, Tinuvin XT 850 FF (product name) manufactured by BASF Japan Ltd.)
E-4: hindered amine compounds (peroxidized 4-butylamino-2,2,6,6-tetramethylpiperidine, 2,4,6-trichloro-1,3,5-triazinecyclohexane and N, N ′ -Reaction product of ethane-1,2-diylbis (1,3-propanamine) (N-OR type), Flamestab NOR 116 FF (product name) manufactured by BASF Japan Ltd.)
E-5: hindered amine compound (olefin (C20-C24), maleic anhydride and 4-amino-2,2,6,6-tetramethylpiperidine copolymer (N-H type), BASF Japan K.K. Uvinul 5050H (product 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 the main component and 60 wt% of the shell is methyl methacrylate as the 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))
F-5: silicone-based core-shell type graft polymer (graft copolymer having a core-shell structure in which the core is 70 wt% mainly composed of acrylic-silicone composite rubber, and the shell is 30 wt% mainly composed of acrylonitrile and styrene, Mitsubishi Rayon ( Metabrene SRK-200A (product name))
F-6: Ethylene-ethyl acrylate copolymer (copolymer of ethylene and ethyl acrylate, Lexpearl EEA A4250 (product name) manufactured by Nippon Polyethylene Co., Ltd.)

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

(Other ingredients)
STAB-1: Phenol-based thermal stabilizer (octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, molecular weight 531, Irganox 1076 (product name) manufactured by BASF Japan Ltd.)
STAB-2: Phosphorus heat stabilizer (Tris (2,4-di-tert-butylphenyl) phosphite, manufactured by Ciba Specialty Chemicals, Inc .; Irgafos 168 (trade name))
WAX: Fatty acid ester release agent (Rikenmar SL900 (product name) manufactured by Riken Vitamin Co., Ltd.)
PIG: Titanium oxide (titanium oxide, 0.2 to 0.3 μm, RTC-30 (product name) manufactured by Tyoxide Co.)

  From the above Tables 1 to 3, it can be seen that the flame retardant polycarbonate resin composition satisfying mechanical properties, chemical resistance, flame retardancy, and appearance at a high level can be obtained by the blending of the present invention by the blending of the present invention.

Claims (7)

The following formula (I) in which the content of (C) styrene units is 40 to 70% by weight with respect to 100 parts by weight of the total of (A) polycarbonate resin (A component) and (B) polypropylene resin (B component ) Or 1-15 parts by weight of a styrene thermoplastic elastomer (C component ) which is a block copolymer represented by (II), (D) 1-30 parts by weight of a phosphorus flame retardant (D component), and (E) a hindered amine A flame retardant polycarbonate resin composition comprising 0.01 to 1 part by weight of a compound (E component). (However, the case where the content of the polycarbonate resin is 0 part by weight is excluded.)
X- (Y-X) n (I)
(XY) n (II)
(Wherein X represents an aromatic vinyl polymer block, and in formula (I), the degree of polymerization may be the same or different at both ends of the molecular chain. Y is a butadiene polymer. Block, isoprene polymer block, butadiene / isoprene copolymer block, hydrogenated butadiene polymer block, hydrogenated isoprene polymer block, hydrogenated butadiene / isoprene copolymer block, partially hydrogenated It represents at least one block selected from a butadiene polymer block, a partially hydrogenated isoprene polymer block and a partially hydrogenated butadiene / isoprene copolymer block, and n is an integer of 1 or more. is there.)   The flame retardant according to claim 1, comprising 1 to 10 parts by weight of a rubber-like elastic body (F component) other than (F) C component with respect to 100 parts by weight of the total of A component and B component. Polycarbonate resin composition.   The flame retardant polycarbonate according to claim 1 or 2, comprising 0.1 to 3 parts by weight of (G) an anti-drip agent (G component) with respect to 100 parts by weight of the total of A component and B component. Resin composition.   D component is a phosphazene compound, The flame-retardant polycarbonate resin composition in any one of Claims 1-3 characterized by the above-mentioned.   The flame retardant polycarbonate resin composition according to claim 2, 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 5 , wherein the E component is an NR type hindered amine compound. E component is a compound which has a structure represented by following formula (7) or (8), The flame-retardant polycarbonate resin composition in any one of Claims 1-6 characterized by the above-mentioned.