JP6181394B2 - Thermoplastic resin composition and molded article thereof - Google Patents

Description

  The present invention relates to a thermoplastic resin composition and a molded article thereof. More specifically, the present invention relates to a thermoplastic resin composition having excellent chemical resistance, flame retardancy, impact resistance, heat resistance and excellent appearance, and a molded product thereof.

  Polycarbonate resin is a polymer in which aromatic or aliphatic dioxy compounds are linked by carbonic acid ester, and has excellent properties such as transparency, heat resistance, flame retardancy, and mechanical properties such as impact resistance. It is widely used in the fields of automobile interior and exterior parts, OA equipment, electrical and electronic equipment, and the like. However, the polycarbonate resin has excellent characteristics, but is inferior in chemical resistance, and has a problem that the use environment is limited in the above-mentioned applications. In particular, the demand for flame retardancy and chemical resistance has increased due to the recent hybridization and electrification of automobiles, and the high impact resistance and diversification of the usage environment associated with the thinning of office automation equipment and electrical / electronic equipment. The demand for materials that have both chemical resistance, flame resistance, impact resistance, and heat resistance is increasing.

  On the other hand, polyphenylene sulfide resin has properties suitable as engineering plastics such as excellent chemical resistance, flame resistance, and heat resistance, so that various electrical and electronic parts, mainly for injection molding, Widely used for machine parts and automobile parts. However, since the impact strength peculiar to crystalline resins is not sufficient, further improvement in impact strength is required for expanding the use of polyphenylene sulfide resin.

  In such a background, an example of improving the flame retardancy and impact properties of a polycarbonate resin is a composition in which a polyorganosiloxane-containing graft copolymer is mixed (Patent Document 1). However, the improvement in chemical resistance has not been sufficient. As an example of improving the chemical resistance of the polycarbonate resin, there is a resin composition made of polyethylene terephthalate resin (see Patent Documents 2, 3 and 4). However, both are not preferred because the polyethylene terephthalate resin is flammable and has a problem that the flame retardancy is greatly deteriorated.

On the other hand, as an example in which the impact strength of polyphenylene sulfide resin is improved, a composition in which a polycarbonate resin is mixed can be cited (Patent Document 5). Although the impact strength itself was improved by mixing, the heat resistance was not sufficient, and the appearance of the two-component resin was poor, so the appearance was not practical.
As described above, a thermoplastic resin composition having excellent chemical resistance, flame retardancy, impact resistance, heat resistance and excellent appearance has not been obtained so far.

International Publication No. 2003/091342 Pamphlet Japanese Patent Publication No. 36-14035 Japanese Examined Patent Publication No. 39-20434 JP 59-176345 A JP-A 51-59952

  An object of the present invention is to provide a thermoplastic resin composition excellent in chemical resistance, flame retardancy, impact resistance, heat resistance and appearance, and a molded article comprising the same.

  As a result of intensive studies to achieve the above object, the present inventors have combined a polycarbonate resin, a polyphenylene sulfide resin, and a specific proportion of a polyorganosiloxane-containing graft copolymer to provide chemical resistance and flame retardancy. The present inventors have found that a thermoplastic resin composition excellent in impact resistance, heat resistance and appearance can be obtained, and reached the present invention.

That is, according to the present invention, (C) a polyorganosiloxane-containing graft copolymer with respect to a total of 100 parts by weight of (A) polycarbonate resin (component A) and (B) polyphenylene sulfide resin (component B) A thermoplastic resin composition containing 0.5 to 15 parts by weight of (C component), wherein the thermoplastic resin composition is 0.1% or more in area ratio by Py-GC / MS method (600 ° C.) A thermoplastic resin composition comprising 15% or less of a Si component is provided.
One of the more preferable embodiments of the present invention is the thermoplastic resin composition according to the above configuration (1), wherein (2) the component A is 50 to 99 parts by weight and the component B is 1 to 50 parts by weight.
One of the more preferable embodiments of the present invention is (3) (D) the above-described configuration (1) or (2) including 1 to 30 parts by weight of a thermoplastic resin (D component) other than the A component and the B component. The resin composition according to any one of the above.
One of the more preferred embodiments of the present invention is: (4) an alkyl (meth) acrylate monomer having one or more types of alkyl groups having 1 to 3 carbon atoms in the rubber core in which the C component contains polyorganosiloxane; The resin composition according to any one of the above constitutions (1) to (3), comprising a core-shell elastic polymer obtained by graft polymerization with an aromatic vinyl monomer as required.
One of the more preferable embodiments of the present invention is (5) a graft copolymer in which the C component contains an Si component having an area ratio of 20% or more and 95% or less by the Py-GC / MS method (600 ° C.). It is the resin composition in any one of said structure (1)-(4).
One of the more preferable embodiments of the present invention is (6) any one of the above constitutions (1) to (5) having a property retention of 50% or more at 150 ° C. evaluated by a method defined in ISO 8256 at 500 ° C. It is a resin composition as described above.
One of the more preferable embodiments of the present invention is (7) described in any one of the above configurations (1) to (6), which is evaluated by a method defined by UL94V and has an ability equivalent to V-2 at 3.0 mmt. It is a resin composition.
One of the more preferable embodiments of the present invention is (8) a molded product formed from the polycarbonate resin composition according to any one of the above-mentioned configurations (1) to (7).
One of the more preferable aspects of the present invention is the molded product according to the above-described configuration (8), wherein (9) the molded product is a vehicle interior / exterior member.
One of the more preferable embodiments of the present invention is the molded product according to the above configuration (8), wherein (10) the molded product is an interior / exterior member for OA / electrical electronics.

  Since the resin composition of the present invention has chemical resistance, flame resistance, impact resistance, heat resistance, and excellent appearance, it can be used for buildings, building materials, agricultural materials, marine materials, vehicles, electric / electronic devices. It is widely useful in various fields such as machinery. Therefore, the industrial effect exhibited by the present invention is extremely great.

Hereinafter, the details of the present invention will be described.
<Component A: Polycarbonate resin>
The polycarbonate resin used as the component A of the present invention is usually obtained by reacting a dihydroxy compound and a carbonate precursor by an interfacial polycondensation method or a melt transesterification method, or a carbonate prepolymer by a solid phase transesterification method. Or obtained by polymerizing by a ring-opening polymerization method of a cyclic carbonate compound.

  The dihydroxy component used here may be any one that is usually used as a dihydroxy component of an aromatic polycarbonate, and may be a bisphenol or an aliphatic diol. Examples of bisphenols include 4,4′-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 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-isopropylphenyl) propane, 2,2-bis (3-t- Butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) ) Octane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-) 4-hydroxyphenyl) propane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9- Bis (4-hydroxy-3-methylphenyl) fluorene, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 4,4′-dihydroxydiphenyl ether 4,4′-dihydroxy-3,3′-dimethyldiphenyl 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'-diphenyl Diphenyl 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-hydroxyphenyl) cyclohexane 1,3-bis (4-hydroxyphenyl) cyclohexane, 4,8-bis (4-hydroxyphenyl) tricyclo [5.2.1.02,6] decane, 4,4 ′-(1,3-adamantane) Diyl) diphenol, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane and the following general formula (1)

[Wherein 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 substituted or unsubstituted aryl having 6 to 12 carbon atoms. R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, p is a natural number, and q is 0 or a natural number, and p + q is a natural number less than 100. X is a divalent aliphatic group having 2 to 8 carbon atoms. The bisphenol compound etc. which have a siloxane structure represented by these are mentioned.

  Examples of the aliphatic diols include 2,2-bis- (4-hydroxycyclohexyl) -propane, 1,14-tetradecanediol, octaethylene glycol, 1,16-hexadecanediol, 4,4′-bis (2- Hydroxyethoxy) biphenyl, bis {(2-hydroxyethoxy) phenyl} methane, 1,1-bis {(2-hydroxyethoxy) phenyl} ethane, 1,1-bis {(2-hydroxyethoxy) phenyl} -1- Phenylethane, 2,2-bis {(2-hydroxyethoxy) phenyl} propane, 2,2-bis {(2-hydroxyethoxy) -3-methylphenyl} propane, 1,1-bis {(2-hydroxyethoxy) ) Phenyl} -3,3,5-trimethylcyclohexane, 2,2-bis {4- (2-hydroxy) Ethoxy) -3,3′-biphenyl} propane, 2,2-bis {(2-hydroxyethoxy) -3-isopropylphenyl} propane, 2,2-bis {3-tert-butyl-4- (2-hydroxy) Ethoxy) phenyl} propane, 2,2-bis {(2-hydroxyethoxy) phenyl} butane, 2,2-bis {(2-hydroxyethoxy) phenyl} -4-methylpentane, 2,2-bis {(2 -Hydroxyethoxy) phenyl} octane, 1,1-bis {(2-hydroxyethoxy) phenyl} decane, 2,2-bis {3-bromo-4- (2-hydroxyethoxy) phenyl} propane, 2,2- Bis {3,5-dimethyl-4- (2-hydroxyethoxy) phenyl} propane, 2,2-bis {3-cyclohexyl-4- (2-hydroxyethyl) Xyl) phenyl} propane, 1,1-bis {3-cyclohexyl-4- (2-hydroxyethoxy) phenyl} cyclohexane, bis {(2-hydroxyethoxy) phenyl} diphenylmethane, 9,9-bis {(2-hydroxy) Ethoxy) phenyl} fluorene, 9,9-bis {4- (2-hydroxyethoxy) -3-methylphenyl} fluorene, 1,1-bis {(2-hydroxyethoxy) phenyl} cyclohexane, 1,1-bis { (2-hydroxyethoxy) phenyl} cyclopentane, 4,4′-bis (2-hydroxyethoxy) diphenyl ether, 4,4′-bis (2-hydroxyethoxy) -3,3′-dimethyldiphenyl ether Ter, 1,3-bis [2-{(2-hydroxyethoxy) phenyl} propyl] benzene, 1 , 4-bis [2-{(2-hydroxyethoxy) phenyl} propyl] benzene, 1,4-bis {(2-hydroxyethoxy) phenyl} cyclohexane, 1,3-bis {(2-hydroxyethoxy) phenyl} Cyclohexane, 4,8-bis {(2-hydroxyethoxy) phenyl} tricyclo [5.2.1.02,6] decane, 1,3-bis {(2-hydroxyethoxy) phenyl} -5,7-dimethyl Adamantane, 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, 1,4: 3,6-dianhydro-D-sorbitol (Isosorbide), 1,4: 3,6-dianhydro-D-mannitol (isomannide), 1,4: 3,6-dianhydro-L-iditol Isoidide), and the like.

  Among these, aromatic bisphenols are preferable from the viewpoint of flame retardancy, and 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, and 1,4-bis {2- (4-hydroxyphenyl) propyl} benzene, the above general formula ( In particular, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane (BPZ), 4,4′-sulfonyldiphenol, And 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, bisphenol compounds represented by the above general formula (5) are 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.

  The polycarbonate resin used as the component A of the present invention may be a branched polycarbonate resin by using a branching agent in combination with the dihydroxy compound. The branched polycarbonate resin can impart anti-drip performance and the like to the thermoplastic 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.

  When the polycarbonate resin used as the component A of the present invention is a branched polycarbonate resin, the structural viscosity index (N) is preferably in the range of 1.5 to 2.5, and preferably 1.5 to 2.2. Is more preferable, the range of 1.6 to 2.2 is more preferable, and the range of 1.7 to 2.2 is most preferable. The structural viscosity index (N) referred to in the present invention is used as an index characterizing the melt flow characteristics and is represented by the following formula (1).

  In the above formula (1), D is a shear rate (1 / sec), a is a constant, σ is a shear stress (Pa), and N is a structural viscosity index. This structural viscosity index is measured according to ISO11443.

  Furthermore, the use of a polycarbonate-polydiorganosiloxane copolymer comprising a polycarbonate block represented by the following general formula (2) and a polydiorganosiloxane block represented by the following formula (4) is also possible.

(In the above general formula (2), 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 (3). .)

(In the general formula (3), 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 Represents a group selected from the group consisting of carboxyl groups, and when there are a plurality of them, they may be the same or different, g is an integer of 1 to 10, and h is an integer of 4 to 7).

In (the general formula ^{(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, and p + q (degree of diorganosiloxane polymerization) is a natural number of less than 300. X is a divalent aliphatic group having 2 to 8 carbon atoms.)

  The polycarbonate-polydiorganosiloxane copolymer is obtained by reacting a dihydric phenol and a carbonate precursor. The dihydric phenol used in the method for producing the polycarbonate-polydiorganosiloxane copolymer is represented by the following general formula (5).

（式中、Ｒ^１、Ｒ^２、ｅ、ｆ及びＷは前記と同じである。）

(Wherein R ¹ , R ² , e, f and W are the same as described above.)

  Examples of the dihydric phenol represented by the general formula (5) 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-isopropylphenyl) Propane, 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2 Bis (4-hydroxyphenyl) octane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 9,9-bis (4-hydroxyphenyl) fluorene 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 4,4′- Dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiph Nyl 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-hydroxy) Cyphenyl) 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 and 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane.

  Among them, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4′-sulfonyldiphenol, 2,2′-dimethyl- 4,4′-sulfonyldiphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene, and 1,4-bis {2- (4-hydroxyphenyl) propyl} benzene is preferred, especially 2,2-bis (4-hydroxyphenyl) propane, 1,1-biphenyl. (4-hydroxyphenyl) cyclohexane (BPZ), 4,4'-sulfonyl diphenol, and 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.

  The carbonate precursor used in the method for producing a polycarbonate-polydiorganosiloxane copolymer is a hydroxyaryl-terminated polydiorganosiloxane represented by the following general formula (6).

（式中、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、ｐ、ｑ及びＸは前記と同じである。）

(Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , p, q and X are the same as above).

Here, p + q (degree of diorganosiloxane polymerization) is preferably 2 to 290, more preferably 5 to 100. Above the lower limit of the preferred range, the impact resistance and flame retardancy are excellent, and below the upper limit of the suitable range, the surface appearance of the molded product is excellent. A copolymer having the above lower limit or more has a high effect of modifying rheological properties due to the introduction of a polydiorganosiloxane moiety having a low cohesive force, and tends to increase the structural viscosity index. As a result, it is possible to obtain a highly flame-retardant resin molded article in which drip during combustion is suppressed while maintaining high fluidity during shear flow. Such a copolymer below the upper limit tends to reduce the average size and normalized dispersion of the polydiorganosiloxane domain. As a result, a resin molded product having an excellent surface appearance can be obtained. The number of moles per unit weight of the polydiorganosiloxane unit below the upper limit is increased, and the unit is easily incorporated into the polycarbonate evenly. When the degree of polymerization of the diorganosiloxane is large, the incorporation of polydiorganosiloxane units into the polycarbonate becomes uneven and the proportion of polydiorganosiloxane units in the polymer molecule increases. Polycarbonate is likely to occur, and the compatibility with each other tends to decrease. As a result, large polydiorganosiloxane domains are likely to occur. On the other hand, from the viewpoint of fluidity, impact resistance, and flame retardancy, it is advantageous that the polydiorganosiloxane domain is somewhat large, and therefore there is a preferred range of polymerization degree as described above.
As the hydroxyaryl-terminated polydiorganosiloxane, for example, the following compounds are preferably used.

（式中、ｐおよびｑは前記と同じである。）

(In the formula, p and q are the same as above.)

  Hydroxyaryl-terminated polydiorganosiloxane is a phenol having an olefinically unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, 2-methoxy-4-allylphenol with a predetermined polymerization degree. It is easily produced by hydrosilylation reaction at the end of the polysiloxane chain having Of these, (2-allylphenol) -terminated polydiorganosiloxane, (2-methoxy-4-allylphenol) -terminated polydiorganosiloxane are preferred, and (2-allylphenol) -terminated polydimethylsiloxane and (2-methoxy-) are particularly preferred. 4-Allylphenol) -terminated polydimethylsiloxane is preferred.

The polydiorganosiloxane content in the total weight of the copolymer is preferably 0.1 to 50% by weight, more preferably 0.1 to 10% by weight, still more preferably 0.5 to 8% by weight, and particularly preferably 1 to 1% by weight. 5% by weight. Above the lower limit of the preferable range, the impact resistance and flame retardancy are excellent, and when it is lower than the upper limit of the preferable range, stable transparency that is hardly affected by the molding conditions is easily obtained. Such diorganosiloxane polymerization degree and polydiorganosiloxane content can be calculated by ¹ H-NMR measurement.

  These polycarbonate resins are produced by a reaction means known per se for producing ordinary aromatic polycarbonate resins, for example, a method of reacting an aromatic dihydroxy component with a carbonate precursor such as phosgene or carbonic acid diester. The basic means of the manufacturing method will be briefly described.

  In a reaction using, for example, phosgene as a carbonate precursor, the reaction is usually performed in the presence of an acid binder and a solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. In order to accelerate the reaction, a catalyst such as a tertiary amine or a quaternary ammonium salt can also be used. In that case, reaction temperature is 0-40 degreeC normally, and reaction time is several minutes-5 hours. The transesterification reaction using a carbonic acid diester as a carbonate precursor is performed by a method in which an aromatic dihydroxy component in a predetermined ratio is stirred with a carbonic acid diester while heating with an inert gas atmosphere to distill the generated alcohol or phenols. . The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300 ° C. The reaction is completed while distilling off the alcohol or phenol produced under reduced pressure from the beginning. Moreover, in order to accelerate | stimulate reaction, the catalyst normally used for transesterification can also be used. Examples of the carbonic acid diester used in the transesterification include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Of these, diphenyl carbonate is particularly preferred.

  In the present invention, a terminal terminator is used in the polymerization reaction. The end terminator is used for molecular weight adjustment, and the obtained polycarbonate resin is excellent in thermal stability as compared with the other one because the end is blocked. Examples of such a terminal terminator include monofunctional phenols represented by the following general formulas (7) to (9).

［式中、Ａは水素原子、炭素数１〜９のアルキル基、アルキルフェニル基（アルキル部分の炭素数は１〜９）、フェニル基、またはフェニルアルキル基（アルキル部分の炭素数１〜９）であり、ｒは１〜５、好ましくは１〜３の整数である］。

[In the formula, A is a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an alkylphenyl group (the alkyl portion has 1 to 9 carbon atoms), a phenyl group, or a phenylalkyl group (the alkyl portion having 1 to 9 carbon atoms). And r is an integer from 1 to 5, preferably from 1 to 3].

［式中、ｎは１０〜５０の整数を示す。］

[In formula, n shows the integer of 10-50. ]

［式中、Ｘは−Ｒ−Ｏ−、−Ｒ−ＣＯ−Ｏ−または−Ｒ−Ｏ−ＣＯ−である、ここでＲは単結合または炭素数１〜１０、好ましくは１〜５の二価の脂肪族炭化水素基を示し、ｎは１０〜５０の整数を示す。］

[Wherein, X is —R—O—, —R—CO—O— or —R—O—CO—, wherein R is a single bond or a carbon number of 1 to 10, preferably 1 to 5; A valent aliphatic hydrocarbon group, and n represents an integer of 10 to 50. ]

  Specific examples of the monofunctional phenols represented by the general formula (7) include, for example, phenol, isopropylphenol, p-tert-butylphenol, p-cresol, p-cumylphenol, 2-phenylphenol, 4-phenyl. Phenol, isooctylphenol, etc. are mentioned. The monofunctional phenols represented by the general formulas (8) to (9) are phenols having a long-chain alkyl group or an aliphatic ester group as a substituent, and using these, the terminal of the polycarbonate resin is used. These not only function as end terminators or molecular weight regulators, but also improve the melt flowability of the resin and facilitate molding, as well as reducing the water absorption rate of the resin. used. The substituted phenols represented by the general formula (8) preferably have n of 10 to 30, particularly 10 to 26. Specific examples thereof include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, Examples include eicosylphenol, docosylphenol, and triacontylphenol. Further, as the substituted phenols of the above general formula (9), compounds in which X is —R—CO—O— and R is a single bond are suitable, and n is 10 to 30, particularly 10 to 26. Specific examples thereof include decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate. Among these monofunctional phenols, monofunctional phenols represented by the above general formula (8) are preferable, more preferably alkyl-substituted or phenylalkyl-substituted phenols, particularly preferably p-tert-butylphenol, p -Cumylphenol or 2-phenylphenol. It is desirable that these monofunctional phenolic terminal terminators be introduced at least 5 mol%, preferably at least 10 mol%, based on the total terminals of the obtained polycarbonate resin. Or a mixture of two or more thereof.

  The polycarbonate resin used as the component A of the present invention may be a polyester carbonate copolymerized with an aromatic dicarboxylic acid, for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid or a derivative thereof, as long as the gist of the present invention is not impaired. Good.

The viscosity average molecular weight of the polycarbonate resin used as the component A of the present invention is preferably in the range of 13,000 to 50,000, more preferably 16,000 to 30,000, and in the range of 18,000 to 28,000. Even more preferred is the range of 19,000 to 26,000. If the molecular weight exceeds 50,000, the melt viscosity becomes too high and the moldability may be inferior. If the molecular weight is less than 13,000, not only will the mechanical strength be problematic, but flame retardancy will be difficult to exert. There is a case. In addition, the viscosity average molecular weight as used in the field of this invention was calculated | required and calculated | required first using the Ostwald viscometer from the solution which melt | dissolved the polycarbonate resin 0.7g in 20 ml of methylene chloride in the specific viscosity computed by following Formula. The viscosity average molecular weight M is determined by inserting the specific viscosity 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]
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 polycarbonate resin used as the component A of the present invention has a total Cl (chlorine) amount in the resin of preferably 0 to 200 ppm, more preferably 0 to 150 ppm. If the total Cl content in the polycarbonate resin exceeds 200 ppm, the thermal stability is deteriorated, which is not preferable.

（式中、Ｒ^１及びＲ^２は、それぞれ独立的に水素原子、炭素原子数１〜４のアルキル基、ニトロ基、アミノ基、フェニル基、メトキシ基、エトキシ基を表す。）
で表される構造部位を繰り返し単位とする樹脂である。 <B component: polyphenylene sulfide resin>
The polyphenylene sulfide resin (B) used in the present invention has a resin structure having a repeating unit of a structure in which an aromatic ring and a sulfur atom are bonded. Specifically, the polyphenylene sulfide resin (B) has the following general formula (10).

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a nitro group, an amino group, a phenyl group, a methoxy group, or an ethoxy group.)
It is resin which makes the structural site represented by a repeating unit.

Here, in the structural part represented by the structural formula (10), it is particularly preferable that R ¹ and R ² in the formula are hydrogen atoms from the viewpoint of the mechanical strength of the polyphenylene sulfide resin (B). In this case, those bonded at the para-position represented by the following structural formula (11) and those bonded at the meta-position represented by the following structural formula (12) can be mentioned.

Among these, in particular, the bond of the sulfur atom to the aromatic ring in the repeating unit is a structure bonded at the para position represented by the structural formula (11), and the heat resistance and crystal of the polyphenylene sulfide resin (B). From the viewpoint of sex.

で表される構造部位から選択される少なくとも一つを、前記構造式（１０）で表される構造部位との合計モル数の３０モル％以下で含んでいてもよい。特に本発明では上記構造式（１３）〜（１６）で表される構造部位は１０モル％以下であることが、ポリフェニレンスルフィド樹脂（Ｂ）から構成される成形品の耐熱性、機械的強度が良好となる点から好ましい。 In addition, the polyphenylene sulfide resin (B) includes not only the structural portion represented by the structural formula (10) but also the following structural formulas (13) to (16).

May be included in 30 mol% or less of the total number of moles with the structural moiety represented by the structural formula (10). In particular, in the present invention, the structural part represented by the structural formulas (13) to (16) is 10 mol% or less, and the heat resistance and mechanical strength of the molded article composed of the polyphenylene sulfide resin (B) are high. It is preferable from the point which becomes favorable.

  Further, when the polyphenylene sulfide resin (B) includes a structural portion represented by the structural formulas (13) to (16), the bonding mode thereof may be any of a random copolymer and a block copolymer. It may be.

で表される３官能性の構造部位、或いは、ナフチルスルフィド結合などを有していてもよ
いが、他の構造部位との合計モル数に対して、３モル％以下が好ましく、特に１モル％以
下であることが好ましい。 The polyphenylene sulfide resin (B) has the following general formula (17) in its molecular structure.

May have a trifunctional structural site represented by the formula (1) or a naphthyl sulfide bond, but is preferably 3 mol% or less, particularly 1 mol%, based on the total number of moles with other structural sites. The following is preferable.

Such polyphenylene sulfide resin (B) can be produced by, for example, the following (1) to (4).
(1) A method in which sodium sulfide and p-dichlorobenzene are reacted in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfone solvent such as sulfolane.
(2) A method of polymerizing p-dichlorobenzene in the presence of sulfur and sodium carbonate.
(3) Sodium sulfide is dropped into a mixed solvent of polar solvent and p-dichlorobenzene, a mixture of sodium hydrosulfide and sodium hydroxide is dropped, or a mixture of hydrogen sulfide and sodium hydroxide A method in which polymerization is carried out by dripping water.
(4) A method by self-condensation of p-chlorothiophenol.

  Among these, the method of reacting sodium sulfide with p-dichlorobenzene in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfolane solvent such as sulfolane in (1) is easy to control. From the viewpoint of excellent productivity. In the method (1), it is preferable to add an alkali metal salt of carboxylic acid or an alkali metal salt of sulfonic acid or an alkali hydroxide to adjust the degree of polymerization.

  The polyphenylene sulfide resin (B) has a melt flow rate of 1 to 3000 g / 10 minutes, more preferably 5 to 2300 g / 10 minutes, and still more preferably 10 to 1500 g / 10, in terms of moldability and surface strength. Those in the range of minutes are preferred. The melt flow rate is a value measured by ASTM D1238-86 under a load of 316 ° C./5000 g (orifice: 0.0825 ± 0.002 inch diameter × 0.315 ± 0.001 inch length).

The polyphenylene sulfide resin (B) described in detail above further reduces moisture content by reducing the amount of residual metal ions, and further reduces the residual amount of low molecular weight impurities by-produced during polymerization. It is preferable that after the resin (B) is produced, it is treated with an acid and then washed with water.
The acid that can be used here is that acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid, or propyl acid can effectively reduce the amount of residual metal ions without decomposing the polyphenylene sulfide resin (B). Of these, acetic acid and hydrochloric acid are preferred.

Examples of the acid treatment method include a method of immersing a polyphenylene sulfide resin in an acid or an aqueous acid solution. At this time, further stirring or heating may be performed as necessary.
Here, as a specific method for the acid treatment, for example, when acetic acid is used, an aqueous acetic acid solution having a pH of 4 is first heated to 80 to 90 ° C., and the polyphenylene sulfide resin (B) is immersed in the solution. A method of stirring for ˜40 minutes can be mentioned.

The acid-treated polyphenylene sulfide resin (B) is then washed several times with water or warm water in order to physically remove the remaining acid or salt. The water used at this time is preferably distilled water or deionized water.
Further, the polyphenylene sulfide resin (B) to be subjected to the acid treatment is preferably a granular material, specifically, a granular material such as a pellet is in a slurry state after polymerization. But you can.

  The polyphenylene sulfide resin used as the component B of the present invention is produced by a polymerization process in which a reaction product containing a diiodo aromatic compound and a sulfur compound is polymerized in a melt under reduced pressure to polymerize polyphenylene sulfide, and the free iodine content is 20 ppm. The following polyphenylene sulfide may be used.

  Such polyphenylene sulfide is not limited in the conditions as long as it is a temperature and pressure at which polymerization of the above-described reactants can be initiated. The polymerization reaction can be carried out for 1 to 30 hours while the pressure is reduced and the final reaction conditions are changed from a temperature of 270 to 350 ° C. and a pressure of 0.001 to 20 torr. When polymerization is performed under such initial temperature and pressure conditions while changing the temperature and pressure conditions, the polymerization reaction rate can be increased, and the thermal stability and mechanical properties of the polymerized polyarylene sulfide. Etc. can be improved.

  The polyphenylene sulfide finally obtained by this method has a free iodine content in the polyphenylene sulfide of preferably 20 ppm or less, more preferably 10 ppm or less, and physical properties such as melt viscosity and melting point are the same as those of conventional methods. It has a value that is equivalent to or improved over that produced. By reducing the iodine content in the obtained polyphenylene sulfide to 20 ppm or less, the possibility of corrosion in a process apparatus or the like can be almost eliminated as compared with the existing one. The polyphenylene sulfide preferably has a melting point (Tm) of 265 to 320 ° C, more preferably 268 to 290 ° C, and further preferably 270 to 285 ° C. Thus, by ensuring the high melting point (Tm), the polyphenylene sulfide according to the present invention can exhibit excellent performance such as high strength and improved heat resistance.

  Further, the polyphenylene sulfide finally obtained according to the present method preferably has a melt viscosity of 100 to 100,000 poise, more preferably 150 to 5,000 poise, and still more preferably 200 to 20 poise. 1,000 poise, particularly preferably 300 to 15,000 poise. By ensuring such improved melt viscosity, the polyphenylene sulfide according to the present invention can exhibit excellent performance such as high strength and improved heat resistance.

  The diiodoaromatic compounds that can be used in the method for producing polyphenylene sulfide according to the embodiment of the present invention mainly include diiodobenzene (DIB), diiodonaphthalene, diiodobiphenyl, and diiodo. Examples thereof include diiodobisphenol and diiodobenzophenone, but the present invention is not limited thereto. In addition, alkyl or sulfone groups that serve as substituents can be added to these compounds, or atoms such as oxygen or nitrogen can be included in the aryl compounds. Depending on the position of the iodine atom, various isomers of diiodo compounds can be formed. There are various diiodo compound isomers depending on the attachment position of the iodine atom. Particularly useful are compounds in which iodine is symmetrically added at the farthest distance to both ends of the molecule, for example, pDIB. 2,6-diiodonaphthalene or p, p′-diiodobiphenyl.

  Usable sulfur compounds are not limited to a particular form. Typically, sulfur exists in the cyclooctasulfur form (S8) with 8 atoms linked at room temperature. In addition, any form of commercially available solid sulfur can be used.

  Further, the diiodo aromatic compound may be added in an amount of 0.9 mol or more based on the sulfur compound. The sulfur compound is used in an amount of 15 to 30% by weight based on the weight of polyarylene sulfide obtained by reacting a diiodo aromatic compound and a sulfur compound. When sulfur is added within the above range, heat resistance and chemical resistance can be improved, and polyarylene sulfide having excellent physical properties such as physical strength can be polymerized.

  In addition, the reactant may further include a polymerization terminator to adjust the molecular weight of the polyarylene sulfide to be polymerized. It can be added to prevent excessive loading and to facilitate processing of the polymerized final polymer.

  The polymerization terminators that can be used are monoiodoaryl compounds, benzothiazoles, benzothiazolesulfenamides, thiurams, dithiocarbamates and dithiocarbamates (diphenylcarbamates). It is 1 or more types chosen from the group which consists of. More preferably, the polymerization terminator is iodobiphenyl, iodophenol, iodoaniline, iodobenzophenone, 2-mercaptobenzothiazole, 2-mercaptobenzothiazole, 2-mercaptobenzothiazole, Dithiobisbenzothiazole (2,2′-dithiobisbenzothiazole), N-cyclohexylbenzothiazole-2-sulfenamide (N-cyclohexylbenzothiazole-2-sulfenamide), 2-morpholinothiobenzothiazole (2-morpholinothiozole) Dicyclohexyl -Benzothiazole sulfenamide (N, N-dicycyclohexyl-2-benzothiazosulfenamide), tetramethylthiuram disulfide dimethyl (tetramethylthiadithiodidithiodisulfide) Although it is 1 or more types chosen from the group which consists of mart (Zinc dimethyldithiocarbamate) and diphenyl disulfide (diphenyldisulphide), this invention is not limited to these examples.

  At this time, although there is no restriction | limiting in the usage-amount of the said polymerization terminator, Preferably it is 0.01-10.0 weight% based on the weight of polyphenylene sulfide, More preferably, it is 0.1-5.0 weight%. Used in quantity. If the amount used is less than 0.01% by weight, the desired effect is practically insignificant. On the other hand, when the amount used exceeds 10.0% by weight, the viscosity of the polymerized polyphenylene sulfide tends to be lowered, and the commercial property is lowered due to excessive input of raw materials.

In addition, the method for producing polyphenylene sulfide according to the above-described embodiment may further include a step of melting and mixing the diiodo aromatic compound and the sulfur compound before the polymerization step. The above-described polymerization process is a melt polymerization reaction process performed without an organic solvent. In order to perform such a melt polymerization reaction, a reaction product containing a diiodo aromatic compound is previously melted and mixed, and then the polymerization reaction is performed. Can be done.
Such melting and mixing are not particularly limited as long as the above-described reactants can be completely melted and mixed, but are preferably performed at a temperature of 150 to 250 ° C.

  In the above-described embodiment, the polymerization step can be performed in the presence of a nitrobenzene-based catalyst. In addition, when a melting and mixing step of the reactant is further included before the polymerization reaction, the nitrobenzene-based catalyst may be included in the reactant and melted and mixed during the above-described melting and mixing step of the reactant. Even when a polymerization terminator is included in the reaction product, the polymerization terminator may be further added to the reaction product and mixed during the melting and mixing steps.

  By the way, when polyarylene sulfide is polymerized in the presence of a reaction catalyst, polyphenylene sulfide having a higher melting point than that of PPS single polymer polymerization using only pDIB and sulfur as polymer raw materials is produced. The low melting point of polyphenylene sulfide undesirably causes problems with the heat resistance of the product. Therefore, proper selection of reaction catalyst is very important. Examples of the reaction catalyst include 1,3-diiodo-4-nitrobenzene and 1-iodo-4-nitrobenzene, but are not limited thereto.

  Further, when the reaction is carried out in the presence of such a nitrobenzene-based catalyst, the content of the catalyst is not particularly limited, but is preferably 0.01 to 5% by weight based on the weight of the polyarylene sulfide to be polymerized. Preferably, it is used in an amount of 0.05 to 2% by weight, more preferably 0.1 to 1% by weight. If the amount of catalyst used is less than 0.01% by weight based on the weight of polyphenylene sulfide to be polymerized, in fact, the desired effect is negligible. On the other hand, if the amount of the catalyst used exceeds 5% by weight, the commercial properties may be lowered due to the excessive input of raw materials, and the physical properties such as the strength of polyphenylene sulfide to be finally polymerized may be lowered.

  The blending amount of (B) polyphenylene sulfide resin is preferably 1 to 50 parts by weight, more preferably 1 to 45 parts by weight in a total of 100 parts by weight of (A) polycarbonate resin and (B) polyphenylene resin. More preferably, it is 3-45 weight part, Most preferably, it is 3-30 weight part. (B) When the polyphenylene sulfide resin exceeds 50 parts by weight, the impact strength decreases, and when it is less than 1 part by weight, flame retardancy may decrease.

<C component: polyorganosiloxane-containing graft copolymer>
The polyorganosiloxane-containing graft copolymer used as the component C of the present invention can be produced, for example, by the production method disclosed in JP-A No. 2003-238639.

  That is, (C) polyorganosiloxane-containing graft copolymer is (X) 0.5 to 10 parts by weight of the first vinyl monomer in the presence of 40 to 90 parts by weight of polyorganosiloxane particles. And (Z) 5 to 50 parts by weight of the second vinyl monomer is further polymerized.

  The (X) polyorganosiloxane particles have a toluene insoluble content (the amount of toluene insoluble when 0.5 g of the (X) polyorganosiloxane particles are immersed in 80 ml of toluene at room temperature for 24 hours) is 95% by weight or less, and further 50%. % Or less, particularly 20% by weight or less is preferable from the viewpoint of flame retardancy and impact resistance.

  Specific examples of (X) polyorganosiloxane particles include polydimethylsiloxane particles, polymethylphenylsiloxane particles, dimethylsiloxane-diphenylsiloxane copolymer particles, and the like. These may be used alone or in combination of two or more.

  (Y) The first vinyl monomer is (y-1) a polyfunctional monomer, that is, 100 to 50% by weight of a polyfunctional monomer containing two or more polymerizable unsaturated bonds in the molecule. And (y-2) a vinyl monomer composed of 0 to 50% by weight of other copolymerizable monomers. (Y) A 1st vinyl-type monomer is used in order to improve a flame-retardant effect and an impact-resistant improvement effect.

  (Y) The first vinyl monomer contains (y-1) a polyfunctional monomer, preferably 100 to 80% by weight, more preferably 100 to 90% by weight, (y-2) Other Is preferably 0 to 20% by weight, more preferably 0 to 10% by weight. (Y-1) By including a polyfunctional monomer in a proportion of 50% by weight or more, and (y-2) by including other copolymerizable monomers in a proportion of 50% by weight or less. The impact resistance improving effect of the finally obtained (D) polyorganosiloxane-containing graft copolymer tends to be further improved, which is preferable.

  (Y-1) The polyfunctional monomer is a compound containing two or more polymerizable unsaturated bonds in the molecule, and specific examples thereof include allyl methacrylate, triallyl cyanurate, and divinylbenzene. . These may be used alone or in combination of two or more. Among these, the use of allyl methacrylate is particularly preferred from the viewpoint of economy and effects.

  (Y-2) Specific examples of other copolymerizable monomers include aromatic vinyl monomers such as styrene, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, methyl acrylate, Examples thereof include (meth) acrylic acid ester monomers such as ethyl acrylate, methyl methacrylate and ethyl methacrylate, and carboxyl group-containing vinyl monomers such as (meth) acrylic acid and maleic acid. Two or more of these may be used in combination.

  (Z) The second vinyl monomer is a component constituting (C) a polyorganosiloxane-containing graft copolymer, and (C) the polyorganosiloxane-containing graft copolymer is blended with a thermoplastic resin. In order to improve the flame retardancy and impact resistance, the components used to ensure the compatibility of the graft copolymer and the thermoplastic resin and to uniformly disperse the graft copolymer in the thermoplastic resin But there is.

  (Z) Examples of the second vinyl monomer include (y-2) other in the above (Y) second vinyl monomer such as methyl methacrylate, butyl methacrylate, styrene, acrylonitrile and the like. The same monomer as the copolymerizable monomer can be used, and two or more types may be used in combination.

(Z) The second vinyl monomer preferably has a polymer solubility parameter of 9.15 to 10.15 [(cal / cm ³ ) ^1/2 ], 9.17-10.10 [(cal / cm ³ ) ^1/2 ] is more preferable, and 9.20-10.05 [(cal / cm ³ ) ^1/2 ] is even more preferable. By setting the solubility parameter within the above range, the flame retardancy tends to be further improved, which is preferable.

  The (C) polyorganosiloxane-containing graft copolymer used in the present invention comprises (X) polyorganosiloxane particles in an amount of 20 to 90% by mass, preferably 25 to 90% by mass, more preferably 30 to 90% by mass. Under (Y) the first vinyl monomer is polymerized in an amount of 0.3 to 15% by mass, preferably 0.4 to 12% by mass, more preferably 0.5 to 10% by mass, (Z) The second vinyl monomer is obtained by polymerizing 3 to 60% by mass, preferably 4 to 60% by mass, more preferably 5 to 50% by mass.

(X) When the ratio of the polyorganosiloxane particles is too small or too large, the flame retarding effect is low.
In addition, when the amount of (Y) the first vinyl monomer is too small, the flame retarding effect and the impact resistance improving effect are lowered, and when it is too much, the impact resistance improving effect is lowered.
Furthermore, when (Z) the second vinyl monomer is too little or too much, the flame retarding effect is lowered in both cases.

  A known seed emulsion polymerization can be applied to the (C) polyorganosiloxane-containing graft copolymer. For example, (X) radical polymerization of the first vinyl monomer in the latex of (X) polyorganosiloxane particles. And (Z) radical polymerization of the second vinyl monomer. Further, both (Y) the first vinyl monomer and (Z) the second vinyl monomer may be polymerized in one stage or in two or more stages.

  The (C) polyorganosiloxane-containing graft copolymer obtained by the above method may be used by separating the polymer from the latex, or may be used as it is. Examples of the method for separating the polymer include a usual method, for example, a method of coagulating, separating, washing, dehydrating and drying the latex by adding a metal salt such as calcium chloride, magnesium chloride, magnesium sulfate to the latex. . A spray drying method can also be used.

  Further, at least one vinyl monomer is graft-polymerized to the composite rubber having a structure in which the polysiloxane rubber component and the polyalkyl (meth) acrylate rubber component are intertwined with each other so that they cannot be separated as the C component of the present invention. A polyorganosiloxane-containing composite rubber-based graft copolymer can also be used.

  Among such rubber-based graft copolymers, at least one kind of vinyl monomer is present in the composite rubber having a structure in which the polysiloxane rubber component and the polyalkyl (meth) acrylate rubber component are intertwined so that they cannot be separated. The composite rubber-based graft copolymer obtained by graft polymerization is firstly composed of various cyclic organosiloxanes having three or more members, such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, a crosslinking agent, and the like. A latex of polyorganosiloxane rubber is prepared by emulsion polymerization using a graft crossing agent, and then the polyorganosiloxane rubber latex is impregnated with an alkyl (meth) acrylate monomer, a crosslinking agent and a graft crossing agent. Is obtained by polymerization from

  Examples of the alkyl (meth) acrylate monomer used herein include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, and alkyl methacrylates such as hexyl methacrylate and 2-ethylhexyl methacrylate. Among them, n-butyl acrylate is particularly preferable.

  Examples of vinyl monomers to be graft polymerized to the composite rubber include aromatic vinyl compounds such as styrene and α-methylstyrene, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, and methacrylic compounds such as methyl methacrylate and 2-ethylhexyl methacrylate. Examples thereof include acrylic acid esters such as acid ester, methyl acrylate, ethyl acrylate, and butyl acrylate, and these are used alone or in combination of two or more. The composite rubber graft polymer may be a mixture of a vinyl monomer polymer or copolymer which is released without being grafted with the vinyl monomer to be graft polymerized. A polymer or copolymer of a series monomer may be mixed with a composite rubber graft polymer.

  In this composite rubber-based graft copolymer, the polyorganosiloxane rubber component and the polyalkyl (meth) acrylate rubber component have a structure in which the crosslinking network is entangled with each other. These organic solvents cannot be separated / extracted, and since they have such a structure, a molded product having excellent impact strength can be obtained by blending them. The ratio of the polyorganosiloxane rubber component to the polyalkyl (meth) acrylate rubber component is 10 to 90% by weight of the polyorganosiloxane rubber component and the polyalkyl (meth) acrylate rubber component, assuming that the total amount of both rubber components is 100% by weight. A range of 90 to 10% by weight can be taken. The average particle size of the composite rubber is usually about 0.08 to 0.6 μm. This composite rubber-based graft copolymer is a commercially available product such as METABRENE S-2001 manufactured by Mitsubishi Rayon Co., Ltd., and is easily available.

  The blending amount of the (C) polyorganosiloxane-containing graft copolymer is 0.5 to 15 parts by weight, preferably 1 with respect to 100 parts by weight in total of the (A) aromatic polycarbonate resin and the (B) polyphenylene sulfide resin. -15 parts by weight, more preferably 3-15 parts by weight, and particularly preferably 4-13 parts by weight. (C) When the polyorganosiloxane-containing graft copolymer is below the upper limit, the rigidity is good, and when above the lower limit, the flame retardancy is good.

  (C) The polyorganosiloxane-containing graft copolymer preferably contains 20% or more and 95% or less Si component by area ratio by Py-GC / MS method (600 ° C.), more preferably 25% or more and 90%. % Si component or less, particularly preferably 30% or more and 90% or less Si component. When the Si component contained is higher than the lower limit, impact strength and flame retardancy are good, and when it is lower than the upper limit, the thermal stability is excellent and the appearance is not easily deteriorated due to a decrease in hue, which is preferable.

  The thermoplastic resin composition of the present invention contains 0.1% to 15% Si component in area ratio by Py-GC / MS method (600 ° C.), preferably 0.5% to 15%, 1.0% or more and 10% or less are more preferable. Above the lower limit, heat resistance, low-temperature impact characteristics and chemical resistance are excellent, and below the upper limit, appearance is excellent.

<D component: thermoplastic resin other than A component and B component>
(D) Thermoplastic resins other than the A component and the B component used as the present invention include, for example, general-purpose plastics represented by polyethylene resin, polypropylene resin, polyalkyl methacrylate resin, polyaryl methacrylate resin, polyester resin, Engineering plastics such as styrene resins, polyphenylene ether resins, polyacetal resins, polyamide resins, cyclic polyolefin resins, polyarylate resins (amorphous polyarylate, liquid crystalline polyarylate), etc. And so-called super engineering plastics such as polyetherimide, polysulfone, and polyethersulfone. Furthermore, thermoplastic elastomers such as olefin-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, and polyurethane-based thermoplastic elastomers can also be used. These may be used alone or in combination of two or more.

  The amount of component D is preferably 1 to 30 parts by weight, more preferably 3 to 25 parts by weight, with respect to 100 parts by weight of the total of (A) aromatic polycarbonate resin and (B) polyphenylene sulfide resin. Is more preferable. When the blending amount of component D is less than 1 part by weight, the appearance and chemical resistance are not improved, and when it exceeds 30 parts by weight, the flame retardancy and impact resistance are lowered.

(Other additives)
In the resin composition of the present invention, various stabilizers, mold release agents, colorants, fillers, flame retardants and the like for stabilizing the molecular weight reduction and hue at the time of molding can be used.

(I) Flame retardant Various compounds known as flame retardants are blended in the resin composition of the invention. The compounding of the compound used as a flame retardant not only improves the flame retardancy but also provides, for example, an improvement in antistatic properties, fluidity, rigidity, and thermal stability based on the properties of each compound.
Examples of such flame retardants include (1) organometallic salt flame retardants (for example, alkali (earth) organic sulfonate metal salts, borate metal salt flame retardants, stannate metal salt flame retardants, etc.), (2) Organophosphorous flame retardants (for example, monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, and phosphonic acid amide compounds), (3) silicone flame retardants comprising silicone compounds, and (4) halogens And flame retardant (for example, brominated epoxy resin, brominated polystyrene, brominated polycarbonate (including oligomers), brominated polyacrylate, chlorinated polyethylene, etc.).

(1) Organometallic salt-based flame retardant An organic metal salt-based flame retardant is advantageous in that heat resistance is substantially maintained and antistatic properties can be imparted. The organometallic salt flame retardant most advantageously used in the present invention is a fluorine-containing organometallic salt compound. The fluorine-containing organometallic salt compound of the present invention refers to a metal salt compound comprising an anion component composed of an organic acid having a fluorine-substituted hydrocarbon group and a cation component composed of a metal ion. More preferred specific examples include metal salts of fluorine-substituted organic sulfonic acids, metal salts of fluorine-substituted organic sulfates, and metal salts of fluorine-substituted organic phosphates. Fluorine-containing organometallic salt compounds can be used alone or in combination of two or more. Among them, a metal salt of a fluorine-substituted organic sulfonic acid is preferable, and a metal salt of a sulfonic acid having a perfluoroalkyl group is particularly preferable. Here, the carbon number of the perfluoroalkyl group is preferably in the range of 1-18, more preferably in the range of 1-10, and still more preferably in the range of 1-8.

  The metal constituting the metal ion of the organometallic salt flame retardant is an alkali metal or an alkaline earth metal. Examples of the alkali metal include lithium, sodium, potassium, rubidium and cesium. Examples of the alkaline earth metal include beryllium. , Magnesium, calcium, strontium and barium. More preferred is an alkali metal. Accordingly, a preferred organometallic salt flame retardant is an alkali metal perfluoroalkyl sulfonate. Among such alkali metals, rubidium and cesium are suitable when transparency requirements are higher, but these are not general-purpose and difficult to purify, resulting in disadvantages in terms of cost. is there. On the other hand, although lithium and sodium are advantageous in terms of cost and flame retardancy, they may be disadvantageous in terms of transparency. In consideration of these, the alkali metal in the perfluoroalkylsulfonic acid alkali metal salt can be properly used, but perfluoroalkylsulfonic acid potassium salt having an excellent balance of properties is most suitable in any respect. Such potassium salts and alkali metal salts of perfluoroalkylsulfonic acid composed of other alkali metals can be used in combination.

  Such alkali metal perfluoroalkylsulfonates include potassium trifluoromethanesulfonate, potassium perfluorobutanesulfonate, potassium perfluorobutanedisulfonate, potassium perfluorohexanesulfonate, potassium perfluorooctanesulfonate, pentafluoroethanesulfone. Sodium sulfate, sodium perfluorobutanesulfonate, sodium perfluorooctanesulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutanesulfonate, lithium perfluoroheptanesulfonate, cesium trifluoromethanesulfonate, cesium perfluorobutanesulfonate, Cesium perfluorooctane sulfonate, cesium perfluorohexane sulfonate, perfluorobutene Nsuruhon acid rubidium, and perfluorohexane sulfonic acid rubidium, and these may be used in combination of at least one or two. Of these, potassium perfluorobutanesulfonate is particularly preferred.

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

  The content of the fluorine-containing organometallic salt compound is preferably 0.005 to 0.6 parts by weight, more preferably 0.005 to 0.2 parts by weight, based on the total of 100 parts by weight of component A and component B, Preferably it is 0.008-0.13 weight part. The more preferable range is, the effects (for example, flame retardancy and antistatic property) expected by the addition of the fluorine-containing organometallic salt are exhibited, and the adverse effect on the light resistance of the resin composition is reduced.

  In addition, as an organic metal salt flame retardant other than the above-mentioned fluorine-containing organic metal salt compound, a metal salt of an organic sulfonic acid not containing a fluorine atom is suitable. Examples of the metal salt include an alkali metal salt of an aliphatic sulfonic acid, an alkaline earth metal salt of an aliphatic sulfonic acid, an alkali metal salt of an aromatic sulfonic acid, and an alkaline earth metal salt of an aromatic sulfonic acid (any Also does not contain a fluorine atom).

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

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

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

  On the other hand, the alkali (earth) metal salt of sulfate ester may include, in particular, the alkali (earth) metal salt of sulfate ester of monovalent and / or polyhydric alcohols. Alcohol sulfates include methyl sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, polyoxyethylene alkylphenyl ether sulfate, pentaerythritol mono, di, tri, tetrasulfate, and lauric acid monoglyceride. And sulfuric acid esters of palmitic acid monoglyceride and stearic acid monoglyceride sulfate. The alkali (earth) metal salts of these sulfates are preferably alkali (earth) metal salts of lauryl sulfate.

  Examples of other alkali (earth) metal salts include alkali (earth) metal salts of aromatic sulfonamides such as saccharin, N- (p-tolylsulfonyl) -p-toluenesulfonimide, N Examples include-(N'-benzylaminocarbonyl) sulfanilimide and alkali (earth) metal salts of N- (phenylcarboxyl) sulfanilimide.

  Among the above, preferable metal salts of organic sulfonic acids not containing fluorine atoms are aromatic (earth) metal salts of aromatic sulfonates, and potassium salts are particularly preferable. When blending such an alkali (earth) sulfonate metal salt, its content is preferably 0.001 to 1 part by weight, more preferably 0, based on a total of 100 parts by weight of component A and component B. 0.005 to 0.5 parts by weight, more preferably 0.01 to 0.1 parts by weight.

(2) Organophosphorous flame retardant As the organophosphorous flame retardant of the present invention, an aryl phosphate compound is suitable. This is because such a phosphate compound is generally excellent in hue and hardly adversely affects high light reflectivity. Moreover, since the phosphate compound has a plasticizing effect, it is advantageous in that the moldability of the resin composition of the present invention can be improved. As the phosphate compound, various known phosphate compounds as conventional flame retardants can be used, and more preferably, one or more phosphate compounds represented by the following general formula (18) can be mentioned.

(However, X in the above formula is hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis And a divalent group derived from (4-hydroxyphenyl) sulfide, wherein j, k, l and m are each independently 0 or 1, n is an integer of 0 to 5, or n number In the case of a mixture of phosphoric acid esters having different values, the average value is 0 to 5, and R ¹ , R ² , R ³ , and R ⁴ are each independently substituted or not substituted with one or more halogen atoms From phenol, cresol, xylenol, isopropylphenol, butylphenol, p-cumylphenol This is a derived monohydric phenol residue.)

  The phosphate compound of the above formula may be a mixture of compounds having different n numbers, in which case the average n number is preferably 0.5-1.5, more preferably 0.8-1. 2, More preferably, it is 0.95-1.15, Most preferably, it is the range of 1-1.14.

Preferred specific examples of the dihydric phenol for deriving X are resorcinol, bisphenol A, and dihydroxydiphenyl.
Preferable specific examples of the monohydric phenol for deriving R1, R2, R3 and R4 are phenol and 2,6-dimethylphenol.

  The monohydric phenol may be substituted with a halogen atom. Specific examples of the phosphate compound having a group derived from the monohydric phenol include tris (2,4,6-tribromophenyl) phosphate and tris. Examples include (2,4-dibromophenyl) phosphate, tris (4-bromophenyl) phosphate, and the like.

On the other hand, specific examples of the phosphate compound not substituted with a halogen atom include monophosphate compounds such as triphenyl phosphate and tri (2,6-xylyl) phosphate, and resorcinol bisdi (2,6-xylyl) phosphate). Preferred are phosphate oligomers mainly composed of phosphate oligomers, phosphate oligomers mainly composed of 4,4-dihydroxydiphenyl bis (diphenyl phosphate), and phosphate oligomers mainly composed of bisphenol A bis (diphenyl phosphate). Indicates that a small amount of other components having different degrees of polymerization may be included, and more preferably, the component of n = 1 in the formula (1) is 80% by weight or more, more preferably 85% by weight or more, and still more preferably Contains over 90% by weight Are shown.).
The content of the organophosphorous flame retardant is preferably 1 to 20 parts by weight, more preferably 2 to 10 parts by weight, still more preferably 2 to 7 parts by weight, based on a total of 100 parts by weight of component A and component B. It is.

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

Generally, the structure of a silicone compound is constituted by arbitrarily combining the following four types of siloxane units. That is,
M units: (CH ₃ ) ₃ SiO _1/2 , H (CH ₃ ) ₂ SiO _1/2 , H ₂ (CH ₃ ) SiO _1/2 , (CH ₃ ) ₂ (CH ₂ = CH) SiO _1/2 , (CH ₃ ) ₂ (C ₆ H ₅ ) SiO _1/2 , (CH ₃ ) (C ₆ H ₅ ) (CH ₂ ═CH) SiO _{1/2 and} other monofunctional siloxane units, D units: (CH ₃ ) ₂ SiO, H (CH ₃ ) SiO, H ₂ SiO, H (C ₆ H ₅ ) SiO, (CH ₃ ) (CH ₂ ═CH) SiO, (C ₆ H ₅ ) ₂ SiO, etc. Siloxane units, T units: (CH ₃ ) SiO _3/2 , (C ₃ H ₇ ) SiO _3/2 , HSiO _3/2 , (CH ₂ ═CH) SiO _3/2 , (C ₆ H ₅ ) SiO _{3 /} trifunctional siloxane units ₂ such, Q unit: tetrafunctional white represented by SiO ₂ It is a three-unit.

  Specific examples of the structure of the silicone compound used in the silicone-based flame retardant include Dn, Tp, MmDn, MmTp, MmQq, MmDnTp, MmDnQq, MmTpQq, MmDnTpQq, DnTp, DnQq, and DnTpQq. Among these, preferred structures of the silicone compound are MmDn, MmTp, MmDnTp, and MmDnQq, and a more preferred structure is MmDn or MmDnTp.

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

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

  Further, the silicone compound used as the silicone flame retardant preferably contains an aryl group. More preferably, the ratio (aromatic group amount) of the aromatic group represented by the following general formula (19) is 10 to 70% by weight (more preferably 15 to 60% by weight).

（式（１９）中、Ｘはそれぞれ独立にＯＨ基、炭素数１〜２０の一価の有機残基を示す。ｎは０〜５の整数を表わす。さらに式（１９）中においてｎが２以上の場合はそれぞれ互いに異なる種類のＸを取ることができる。）

(In formula (19), each X independently represents an OH group or a monovalent organic residue having 1 to 20 carbon atoms. N represents an integer of 0 to 5. Further, in formula (19), n is 2) In these cases, different types of X can be taken.)

The silicone compound used as the silicone-based flame retardant may contain a reactive group in addition to the Si-H group and the alkoxy group. Examples of the reactive group include an amino group, a carboxyl group, an epoxy group, and a vinyl group. Examples thereof include a group, a mercapto group, and a methacryloxy group.
Preferred examples of the silicone compound having an Si—H group include silicone compounds containing at least one of the structural units represented by the following general formulas (20) and (21).

(In formula (20) and formula (21), Z ^{1 to} Z ³ each independently represent a hydrogen atom, a monovalent organic residue having 1 to 20 carbon atoms, or a compound represented by the following general formula (22). Α1 to α3 each independently represents 0 or 1. m1 represents 0 or an integer of 1 or more, and in formula (20), when m1 is 2 or more, each repeating unit represents a plurality of repeating units different from each other. Can be taken.)

(In formula (22), Z ^{4 to} Z ⁸ each independently represents a hydrogen atom or a monovalent organic residue having 1 to 20 carbon atoms. Α 4 to α 8 each independently represents 0 or 1. m 2 represents 0. Alternatively, it represents an integer of 1 or more, and in formula (22), when m2 is 2 or more, the repeating unit may take a plurality of repeating units different from each other.

  In the silicone compound used for the silicone-based flame retardant, examples of the silicone compound having an alkoxy group include at least one compound selected from the compounds represented by the general formula (23) and the general formula (24).

(In the formula (23), β1 represents a vinyl group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group or aralkyl group having 6 to 12 carbon atoms. Γ1, γ2, γ3, γ4, γ5, and γ6 represent an alkyl group and a cycloalkyl group having 1 to 6 carbon atoms, and an aryl group and an aralkyl group having 6 to 12 carbon atoms, and at least one group is an aryl group or an aralkyl group. δ1, δ2, and δ3 represent an alkoxy group having 1 to 4 carbon atoms.

(In the formula (24), β2 and β3 represent a vinyl group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group and an aralkyl group having 6 to 12 carbon atoms. γ8, γ9, γ10, γ11, γ12, γ13, and γ14 each represents an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group or aralkyl group having 6 to 12 carbon atoms, and at least 1 (One group is an aryl group or aralkyl. Δ4, δ5, δ6, and δ7 represent an alkoxy group having 1 to 4 carbon atoms.)

  The content of the above components is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, still more preferably 0.1 to 5 parts, based on 100 parts by weight of the total of the A component and the B component. Parts by weight.

(4) Halogen flame retardant As the halogen flame retardant of the present invention, brominated polycarbonate (including oligomers) is particularly suitable. Brominated polycarbonate has excellent heat resistance and can greatly improve flame retardancy. In the brominated polycarbonate used in the present invention, the structural unit represented by the following general formula (25) is at least 60 mol%, preferably at least 80 mol%, particularly preferably substantially the following general formula. A brominated polycarbonate compound composed of the structural unit represented by (25).

（式（２５）中、Ｘは臭素原子、Ｒは炭素数１〜４のアルキレン基、炭素数１〜４のアルキリデン基または−ＳＯ_２−である。）

(In the formula (25), X is a bromine atom, R represents an alkylene group having 1 to 4 carbon atoms, an alkylidene group or -SO ₂ 1 to 4 carbon atoms - a.)

In the formula (25), R preferably represents a methylene group, an ethylene group, an isopropylidene group, —SO ₂ —, and particularly preferably an isopropylidene group.
The brominated polycarbonate has a small number of remaining chloroformate groups and preferably has a terminal chlorine content of 0.3 ppm or less, more preferably 0.2 ppm or less. The amount of terminal chlorine is determined by dissolving a sample in methylene chloride, adding 4- (p-nitrobenzyl) pyridine and allowing it to react with terminal chlorine (terminal chloroformate). -3200). When the amount of terminal chlorine is 0.3 ppm or less, the thermal stability of the resin composition becomes better, and molding at a higher temperature becomes possible, and as a result, a resin composition having better molding processability is provided.

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

The specific viscosity of the brominated polycarbonate is preferably in the range of 0.015 to 0.1, more preferably in the range of 0.015 to 0.08. The specific viscosity of the brominated polycarbonate is calculated according to the above-described specific viscosity calculation formula used for calculating the viscosity average molecular weight of the polycarbonate resin which is the B-1 component of the present invention.
The content of the above component is preferably 0.01 to 10 parts by weight, more preferably 0.01 to 8 parts by weight, and still more preferably 0.05 to 7 parts by weight, based on the total of 100 parts by weight of component A and component B. Parts by weight.

(Ii) Fluorine-containing anti-dripping agent The resin composition of the present invention may contain a fluorine-containing anti-drop agent. By using such a fluorine-containing anti-drip agent in combination with the above flame retardant, better flame retardancy can be obtained. Examples of such a fluorine-containing anti-drip agent include a fluorine-containing polymer having a fibril-forming ability. Examples of such a polymer include polytetrafluoroethylene and tetrafluoroethylene copolymers (for example, tetrafluoroethylene / hexafluoropropylene copolymer). Polymer, etc.), partially fluorinated polymers as shown in US Pat. No. 4,379,910, polycarbonate resins produced from fluorinated diphenols, and the like, preferably polytetrafluoroethylene (hereinafter referred to as PTFE). May be called).

  Polytetrafluoroethylene (fibrillated PTFE) having a fibril-forming ability has a very high molecular weight, and exhibits a tendency to bind PTFE to each other by an external action such as shearing force to form a fiber. Its number average molecular weight ranges from 1.5 million to tens of millions. The lower limit is more preferably 3 million. The number average molecular weight is calculated based on the melt viscosity of polytetrafluoroethylene at 380 ° C. as disclosed in JP-A-6-145520. That is, the fibrillated PTFE has a melt viscosity at 380 ° C. measured by the method described in this publication in the range of 107 to 1013 poise, preferably in the range of 108 to 1012 poise.

  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. Further, as disclosed in JP-A-6-145520, those having a structure having such a fibrillated PTFE as a core and a low molecular weight polytetrafluoroethylene as a shell are also preferably used.

  Examples of commercially available fibrillated PTFE include Teflon (registered trademark) 6J from Mitsui DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500, F-201L from Daikin Chemical Industries, Ltd., and the like. Commercially available aqueous dispersions of fibrillated PTFE include: Fluon AD-1, AD-936 manufactured by Asahi IC Fluoropolymers, Fluon D-1, D-2 manufactured by Daikin Industries, Ltd., Mitsui A representative example is Teflon (registered trademark) 30J manufactured by DuPont Fluorochemical Co., Ltd.

  As a mixed form of fibrillated PTFE, (1) a method in which an aqueous dispersion of fibrillated PTFE and an aqueous dispersion or solution of an organic polymer are mixed and co-precipitated to obtain a co-agglomerated mixture (JP-A-60-258263). (2) A method of mixing an aqueous dispersion of fibrillated PTFE and dried organic polymer particles (Japanese Patent Laid-Open No. 4-272957). Described method), (3) A method in which an aqueous dispersion of fibrillated PTFE and an organic polymer particle solution are uniformly mixed, and the respective media are simultaneously removed from the mixture (Japanese Patent Laid-Open Nos. 06-220210, (Method described in Japanese Patent Application Laid-Open No. 08-188653), (4) A method of polymerizing monomers forming an organic polymer in an aqueous dispersion of fibrillated PTFE (Method described in JP-A-9-95583), and (5) an aqueous dispersion of PTFE and an organic polymer dispersion are uniformly mixed, and then a vinyl monomer is further polymerized in the mixed dispersion. Thereafter, those obtained by a method for obtaining a mixture (a method described in JP-A No. 11-29679) can be used. Commercial products of these mixed forms of fibrillated PTFE include “Metablene A3800” (trade name) manufactured by Mitsubishi Rayon Co., Ltd., “BLENDEX B449” (trade name) manufactured by GE Specialty Chemicals, and “Products manufactured by Pacific Interchem Corporation” “POLY TS AD001” (product name) is exemplified.

The fibrillated PTFE is preferably finely dispersed as much as possible in order not to lower the mechanical strength. As a means of achieving such fine dispersion, the above mixed form of fibrillated PTFE is advantageous. A method of directly supplying an aqueous dispersion in a melt kneader is also advantageous for fine dispersion. However, in the case of the aqueous dispersion form, consideration is required in that the hue is slightly deteriorated. The proportion of fibrillated PTFE in the mixed form is preferably 10 to 80% by weight, more preferably 15 to 75% by weight, in 100% by weight of the mixture. When the ratio of fibrillated PTFE is in such a range, good dispersibility of fibrillated PTFE can be achieved.
The content of the above components is preferably 0.01 to 3 parts by weight, more preferably 0.01 to 2 parts by weight, and still more preferably 0.05 to 1 based on 100 parts by weight of the total of component A and component B. .5 parts by weight.

(Iii) Stabilizer Various known stabilizers can be blended in the resin composition of the present invention. Examples of the stabilizer include phosphorus stabilizers, hindered phenol antioxidants, ultraviolet absorbers, and light stabilizers.

(Iii-1) Phosphorous stabilizer Examples of the phosphorous stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphine. Among these, phosphorous acid, phosphoric acid, phosphonous acid, and phosphonic acid, triorganophosphate compounds, and acid phosphate compounds are particularly preferable. The organic group in the acid phosphate compound includes any of mono-substituted, di-substituted, and mixtures thereof. Any of the following exemplified compounds corresponding to the compound is similarly included.

  Triorganophosphate compounds include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, tridodecyl phosphate, trilauryl phosphate, tristearyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, diphenyl Examples include cresyl phosphate, diphenyl monoorthoxenyl phosphate, and tributoxyethyl phosphate. Among these, trialkyl phosphate is preferable. The carbon number of the trialkyl phosphate is preferably 1 to 22, more preferably 1 to 4. A particularly preferred trialkyl phosphate is trimethyl phosphate.

  Examples of the acid phosphate compound include methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, octyl acid phosphate, decyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, behenyl acid phosphate Nonylphenyl acid phosphate, cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxy polyethylene glycol acid phosphate, bisphenol A acid phosphate, and the like. Among these, long-chain dialkyl acid phosphates having 10 or more carbon atoms are effective for improving thermal stability, and the acid phosphate itself is preferable because of high stability.

  Examples of the phosphite compound include triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl Monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butyl) Phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, distearyl Taerythritol 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 penta Examples include erythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, and dicyclohexylpentaerythritol 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 phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenedi. Phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite Tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl)- 4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, and the like, and tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, bis (Di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl)- More preferred is phenyl-phenylphosphonite. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted.

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

  The tertiary phosphine includes triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolyl. Examples include phosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine.

  Suitable phosphorus stabilizers are a triorganophosphate compound, an acid phosphate compound, and a phosphite compound represented by the following general formula (26). It is particularly preferable to add a triorganophosphate compound.

（式（２６）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 (26), 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 as 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 (13), 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.

(Iii-2) Hindered phenolic antioxidant As the hindered phenolic compound, various compounds that are usually blended in resins 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.

  It is preferable that either a phosphorus stabilizer or a hindered phenol antioxidant is blended. In particular, a phosphorus stabilizer is preferably blended, and a triorganophosphate compound is more blended. The content of the phosphorus-based stabilizer and the hindered phenol-based antioxidant is preferably 0.005 to 1 part by weight, more preferably 0.01 to 0, based on 100 parts by weight of the total of component A and component B, respectively. .3 parts by weight.

(Iii-3) Ultraviolet absorber The resin composition of this invention can contain a ultraviolet absorber. Since the resin composition of the present invention also has a good hue, such a hue can be maintained for a long time even when used outdoors by blending an ultraviolet absorber.
In the benzophenone series, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy- 5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridolate benzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) ) Methane, 2-hydroxy Examples include -4-n-dodecyloxybenzophenone and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

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

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

In the cyclic imino ester system, for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) bis (3,1-benzoxazine) -4-one), 2,2 ′-(2,6-naphthalene) bis (3,1-benzoxazin-4-one), and the like.
Further, as the ultraviolet absorber, specifically, for cyanoacrylate, for example, 1,3-bis-[(2′-cyano-3 ′, 3′-diphenylacryloyl) oxy] -2,2-bis [(2- Examples include cyano-3,3-diphenylacryloyl) oxy] methyl) propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene.

  Further, the ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, whereby the ultraviolet-absorbing monomer and / or the light-stable monomer having a hindered amine structure, and an alkyl (meth) acrylate. A polymer type ultraviolet absorber obtained by copolymerization with a monomer such as may be used. Preferred examples of the UV-absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of (meth) acrylate. The

Among them, benzotriazole and hydroxyphenyltriazine are preferable from the viewpoint of ultraviolet absorption ability, and cyclic imino ester and cyanoacrylate are preferable from the viewpoint of heat resistance and hue. You may use the said ultraviolet absorber individually or in mixture of 2 or more types.
The content of the ultraviolet absorber is preferably 0.01 to 2 parts by weight, more preferably 0.02 to 2 parts by weight, still more preferably 0.03 to 1 based on the total of 100 parts by weight of component A and component B. Parts by weight, most preferably 0.05 to 0.5 parts by weight.

(Iii-4) Other Heat Stabilizers The resin composition of the present invention may contain other heat stabilizers other than the above 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 content of the lactone-based stabilizer is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight, based on 100 parts by weight of the 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 component A and component B.

(Iv) Mold Release Agent The resin composition of the present invention is further made of a fatty acid ester, a polyolefin wax, a silicone compound, a fluorine compound (polyfluoro compound) for the purpose of improving productivity during molding and improving dimensional accuracy of a molded product. Fluorine oil represented by alkyl ether, etc.), known release agents such as paraffin wax and beeswax can also be blended. Since the resin composition of the present invention has good fluidity, the pressure propagation is good and a molded article with uniform strain can be obtained. On the other hand, in the case of a molded product having a complicated shape that increases the mold release resistance, the molded product may be deformed at the time of mold release. The compounding of the specific component solves such a problem without impairing the properties of the resin composition.

  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, carbon number of this alcohol becomes like this. Preferably it is 3-32, More preferably, it is 5-30. On the other hand, the aliphatic carboxylic acid is preferably an aliphatic carboxylic acid having 3 to 32 carbon atoms, more preferably 10 to 30 carbon atoms. Of these, saturated aliphatic carboxylic acids are preferred. The fatty acid ester of the present invention is preferable in that all esters (full esters) are excellent in thermal stability at high temperatures. The acid value in the fatty acid ester of the present invention is preferably 20 or less (can take substantially 0). The hydroxyl value of the fatty acid ester is more preferably in the range of 0.1-30. Further, the iodine value of the fatty acid ester is preferably 10 or less (can take substantially 0). These characteristics can be obtained by a method defined in JIS K 0070.

As the polyolefin wax, an ethylene homopolymer having a molecular weight of 1,000 to 10,000, a homopolymer or copolymer of an α-olefin having 3 to 60 carbon atoms, or ethylene and a carbon atom having 3 to 3 carbon atoms. A copolymer with 60 α-olefins is exemplified. The molecular weight is a number average molecular weight measured in terms of standard polystyrene by GPC (gel permeation chromatography) method. The upper limit of the number average molecular weight is more preferably 6,000, and still more preferably 3,000. The carbon number of the α-olefin component in the polyolefin wax is preferably 60 or less, more preferably 40 or less. More preferred specific examples include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and the like. A suitable polyolefin wax is an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 60 carbon atoms. The proportion of the α-olefin having 3 to 60 carbon atoms is preferably 20 mol% or less, more preferably 10 mol% or less. What is marketed as what is called polyethylene wax is used suitably.
The content of the above releasing agent is preferably 0.005 to 5 parts by weight, more preferably 0.01 to 4 parts by weight, and still more preferably 0.02 based on a total of 100 parts by weight of component A and component B. ~ 3 parts by weight.

(V) Dye / pigment The resin composition of the present invention can further contain various dyes / pigments and can provide molded products that exhibit various design properties. As dyes and pigments used in the present invention, perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as bitumen, perinone dyes, quinoline dyes, quinacridone dyes, Examples thereof include 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, aluminum powder is suitable. Further, by blending a fluorescent brightening agent or other fluorescent dye that emits light, a better design effect utilizing the luminescent color can be imparted.

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

(Vi) Compound having heat absorption ability The resin composition of the present invention may contain a compound having heat absorption ability. Such compounds include phthalocyanine-based near-infrared absorbers, metal oxide-based near-infrared absorbers such as ATO, ITO, iridium oxide, ruthenium oxide and imonium oxide, and metal borides such as lanthanum boride, cerium boride and tungsten boride. Preferable examples include various metal compounds having excellent near-infrared absorptivity such as a system and tungsten oxide near-infrared absorber, and carbon filler. As such a phthalocyanine-based near infrared absorber, for example, MIR-362 manufactured by Mitsui Chemicals, Inc. is commercially available and easily available. Examples of the carbon filler include carbon black, graphite (including both natural and artificial) and fullerene, and carbon black and graphite are preferable. These can be used alone or in combination of two or more. The content of the phthalocyanine-based near infrared absorber is preferably 0.0005 to 0.2 parts by weight, more preferably 0.0008 to 0.1 parts by weight, based on the total of 100 parts by weight of the component A and the component B. 0.001 to 0.07 part by weight is more preferable. The content of the metal oxide near-infrared absorber, the metal boride-based near infrared absorber, and the carbon filler is preferably in the range of 0.1 to 200 ppm (weight ratio) in the resin composition of the present invention. A range of ˜100 ppm is more preferable.

(Vii) Light diffusing agent The resin composition of the present invention can be provided with a light diffusing effect by blending a light diffusing agent. Examples of such light diffusing agents include polymer fine particles, inorganic fine particles having a low refractive index such as calcium carbonate, and composites thereof. Such polymer fine particles are fine particles already known as light diffusing agents for thermoplastic resins. More preferably, acrylic crosslinked particles having a particle size of several μm, silicone crosslinked particles represented by polyorganosilsesquioxane, and the like are exemplified. Examples of the shape of the light diffusing agent include a spherical shape, a disk shape, a column shape, and an indefinite shape. Such spheres need not be perfect spheres, but include deformed ones, and such columnar shapes include cubes. A preferred light diffusing agent is spherical, and the more uniform the particle size is. The content of the light diffusing agent is preferably 0.005 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, still more preferably 0.01 to 3 parts by weight based on the total of 100 parts by weight of the component A and the component B. Parts by weight. Two or more light diffusing agents can be used in combination.

(Viii) White pigment for high light reflection The resin composition of the present invention can be provided with a light reflection effect by blending a white pigment for high light reflection. As such a white pigment, a titanium dioxide (particularly titanium dioxide treated with an organic surface treating agent such as silicone) pigment is particularly preferred. The content of the white pigment for high light reflection is preferably 3 to 30 parts by weight, more preferably 8 to 25 parts by weight based on a total of 100 parts by weight of the component A and the component B. Two or more kinds of white pigments for high light reflection can be used in combination.

(Ix) Antistatic agent The resin composition of the present invention may require antistatic performance, and in such a case, it is preferable to include an antistatic agent. Examples of the antistatic agent include (1) aryl sulfonic acid phosphonium salts represented by dodecylbenzenesulfonic acid phosphonium salts, organic sulfonic acid phosphonium salts such as alkyl sulfonic acid phosphonium salts, and tetrafluoroboric acid phosphonium salts. Examples thereof include phosphonium borate salts. The content of the phosphonium salt is suitably 5 parts by weight or less, preferably 0.05 to 5 parts by weight, more preferably 1 to 3.5 parts by weight, based on 100 parts by weight of the total of component A and component B. More preferably, it is in the range of 1.5 to 3 parts by weight.

  Examples of the antistatic agent include: (2) lithium organic sulfonate, organic sodium sulfonate, organic potassium sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate. And organic sulfonate alkali (earth) metal salts. Such metal salts are also used as flame retardants as described above. More specific examples of such metal salts include metal salts of dodecylbenzene sulfonic acid and metal salts of perfluoroalkane sulfonic acid. The content of the organic sulfonic acid alkali (earth) metal salt is suitably 0.5 parts by weight or less, preferably 0.001 to 0.005, based on the total of 100 parts by weight of the component A, the component B and the component C. 3 parts by weight, more preferably 0.005 to 0.2 parts by weight. In particular, alkali metal salts such as potassium, cesium, and rubidium are preferable.

  Examples of the antistatic agent include (3) organic sulfonic acid ammonium salts such as alkyl sulfonic acid ammonium salt and aryl sulfonic acid ammonium salt. The ammonium salt is suitably 0.05 parts by weight or less based on 100 parts by weight of the total of the A component, B component and C component. Examples of the antistatic agent include (4) a polymer containing a poly (oxyalkylene) glycol component such as polyether ester amide as a constituent component. The polymer is suitably 5 parts by weight or less based on a total of 100 parts by weight of the A component and the B component.

(X) Filler The resin composition of the present invention can contain various known fillers as reinforcing fillers. As such a filler, various fibrous fillers, plate-like fillers, and granular fillers can be used. Here, the fibrous filler has a fibrous shape (including a rod shape, a needle shape, a flat shape, or a shape whose axes extend in a plurality of directions), and the plate-shaped filler has a plate shape. It is a filler which has a shape (including those having irregularities on the surface and those having a curved surface). The granular filler is a filler having a shape other than these including an indefinite shape.
The fiber-like and plate-like shapes are often clear from the observation of the shape of the filler. For example, a difference from a so-called indeterminate shape can be said to be a fiber-like or plate-like one having an aspect ratio of 3 or more.

  As plate-like fillers, glass-flake, talc, mica, kaolin, metal flakes, carbon flakes, and graphite, and these fillers are coated with different materials such as metals and metal oxides. A material etc. are illustrated preferably. The particle size is preferably in the range of 0.1 to 300 μm. The particle size is about 10 μm in terms of the median diameter (D50) of the particle size distribution measured by the X-ray transmission method, which is one of the liquid phase precipitation methods. In the region of 10-50 μm, laser diffraction is performed. -The value by the median diameter (D50) of the particle size distribution measured by the scattering method is referred to, and in the region of 50 to 300 μm, the value is by the vibration sieving method. Such a particle size is a particle size in the resin composition. The plate-like filler may be surface-treated with various coupling agents such as silane, titanate, aluminate, and zirconate, and olefin resin, styrene resin, acrylic resin, polyester resin. Further, it may be a granulated product that has been subjected to a bundling treatment or compression treatment with various resins such as epoxy resins and urethane resins, higher fatty acid esters, and the like.

The fiber diameter of the fibrous filler is preferably in the range of 0.1 to 20 μm. The upper limit of the fiber diameter is preferably 13 μm, more preferably 10 μm. On the other hand, the lower limit of the fiber diameter is preferably 1 μm.
The fiber diameter here refers to the number average fiber diameter. The number average fiber diameter is obtained by scanning the residue collected after dissolving the molded product in a solvent, or decomposing the resin with a basic compound, and the ash residue collected after ashing with a crucible. It is a value calculated from an image observed with an electron microscope.

  Examples of the fibrous filler include glass fiber, flat cross-section glass fiber, glass milled fiber, glass flake, carbon fiber, flat cross-section carbon fiber, carbon milled fiber, metal fiber, basalt fiber, asbestos, rock wool, and ceramic fiber. , Slag fiber, potassium titanate whisker, boron whisker, aluminum borate whisker, calcium carbonate whisker, titanium oxide whisker, wollastonite, zonotolite, palygorskite (attapulgite), sepiolite and other fibrous inorganic fillers, aramid fiber, polyimide Fibrous heat-resistant organic fillers typified by heat-resistant organic fibers such as fibers and polybenzthiazole fibers, vegetable fibers such as hemp hemp and bamboo, and Such as a fibrous filler with different materials and surface coatings, such as with respect to those of fillers such as metal or metal oxide are exemplified. Examples of the filler whose surface is coated with a different material include metal-coated glass fibers, metal-coated glass flakes, titanium oxide-coated glass flakes, and metal-coated carbon fibers. The surface coating method of different materials is not particularly limited. For example, various known plating methods (for example, electrolytic plating, electroless plating, hot-dip plating, etc.), vacuum deposition methods, ion plating methods, CVD methods ( For example, thermal CVD, MOCVD, plasma CVD, etc.), PVD method, sputtering method, etc. can be mentioned.

Here, the fibrous filler means a fibrous filler having an aspect ratio of 3 or more, preferably 5 or more, more preferably 10 or more. The upper limit of the aspect ratio is about 10,000, preferably 200. The aspect ratio of such a filler is a value in the resin composition. The flat cross-section glass fiber has an average value of the major axis of the fiber cross section of 10 to 50 μm, preferably 15 to 40 μm, more preferably 20 to 35 μm, and an average value of the ratio of major axis to minor axis (major axis / minor axis) of 1. .5-8, preferably 2-6, more preferably 2.5-5 glass fiber. The fibrous filler may be surface-treated with various coupling agents in the same manner as the plate-like filler, may be converged with various resins, and may be granulated by compression.
The content of the filler is preferably 200 parts by weight or less, more preferably 100 parts by weight or less, still more preferably 50 parts by weight or less, particularly preferably 30 parts by weight based on 100 parts by weight of the total of the A component and the B component. It is as follows.

(Xi) Other Additives The resin composition of the present invention may contain other flow modifiers, antibacterial agents, dispersants such as liquid paraffin, photocatalytic antifouling agents, and photochromic agents.

(Manufacture of resin composition)
Arbitrary methods are employ | adopted for preparation of the resin composition of this invention. For example, there can be mentioned a method in which the A component, the B component, the C component and optionally other components are premixed and then melt-kneaded and pelletized. Examples of the premixing means include a Nauter mixer, a V-type blender, a Henschel mixer, a mechanochemical apparatus, and an extrusion mixer. In the premixing, granulation can be performed by an extrusion granulator or a briquetting machine as necessary. As another method, for example, when a component having a powder form is included as the component B, a master batch of an additive diluted with powder by blending a part of the powder and an additive to be blended is manufactured. A method using a batch is mentioned. After the preliminary mixing, the mixture is melt-kneaded by a melt-kneader represented by a vent type twin-screw extruder and pelletized by a device such as a pelletizer. Other examples of the melt kneader include a Banbury mixer, a kneading roll, and a constant temperature stirring vessel, but a vent type twin screw extruder is preferred.

  In addition, a method of supplying each component independently to a melt kneader represented by a twin screw extruder without premixing each component can also be employed. Moreover, after premixing some components, the method of supplying to a melt-kneader independently of the remaining components is mentioned. In particular, when an inorganic filler is blended, the inorganic filler is preferably supplied from a supply port in the middle of the extruder into the molten resin using a supply device such as a side feeder. The premixing means and granulation are the same as described above. 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 kneader.

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.

  Furthermore, it is preferable that the moisture contained in the A component and the B component is small before melt kneading. Therefore, it is more preferable to melt-knead after drying either A component or B component, or both by methods, such as various hot air drying, electromagnetic wave drying, and vacuum drying. The vent suction during melt-kneading is preferably in the range of 1 to 60 kPa, preferably 2 to 30 kPa. The prepared resin composition preferably contains 0.001 to 50 ppm, more preferably 0.001 to 45 ppm of titanium element derived from the catalyst. When the amount of Ti remaining is more than 50 ppm, the appearance is deteriorated and the heat and humidity resistance is lowered due to a decrease in thermal stability and hue.

  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.

The resin composition of the present invention preferably has a characteristic retention of 50% or more, more preferably 55% or more, more preferably 60% or more at 150 ° C. as evaluated by a method defined in ISO8256. Is more preferable.
The resin composition of the present invention is preferably evaluated by a method defined by UL94V and preferably has an ability equivalent to V-2 at 3.0 mmt.

  The resin composition of the present invention can be produced in various products by usually injection-molding the pellets produced as described above to obtain molded products. In such injection molding, not only ordinary molding methods but also injection compression molding, injection press molding, gas assist injection molding, foam molding (including a method of injecting a supercritical fluid), insert molding, in-mold coating molding, heat insulation Examples thereof include mold molding, rapid heating / cooling mold molding, two-color molding, multicolor molding, sandwich molding, and ultrahigh-speed injection molding. In addition, either a cold runner method or a hot runner method can be selected for molding.

Moreover, the resin composition of this invention can also be used in the form of various profile extrusion-molded articles, 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.
Thereby, a thermoplastic resin composition and a molded product excellent in chemical resistance, flame retardancy, impact resistance, heat resistance and excellent in appearance are provided. That is, according to the present invention, (C) polyorganosiloxane-containing graft copolymer (C component) is reduced to 0 with respect to 100 parts by weight of polycarbonate resin (A component) and (B) polyphenylene sulfide resin (B component) in total. A molded article obtained by melt-molding a thermoplastic resin composition containing 5 to 15 parts by weight is provided.

  Molded articles in which the resin composition of the present invention is used include various electronic / electric equipment parts, camera parts, OA equipment parts, precision machine parts, machine parts, vehicle parts (particularly interior and exterior parts for vehicles), other agricultural materials, It is useful for various applications such as transport containers, playground equipment, and miscellaneous goods, and the industrial effects that it plays are exceptional.

Furthermore, various surface treatments can be performed on the molded article made of the resin composition of the present invention. Surface treatment here refers to a new layer on the surface of resin molded products such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot dipping, etc.), painting, coating, printing, etc. A method used for ordinary thermoplastic resins is applicable. Specific examples of the surface treatment include various surface treatments such as hard coat, water / oil repellent coat, ultraviolet absorption coat, infrared absorption coat, and metalizing (evaporation). Hard coat is a particularly preferred and required surface treatment.
In addition, since the resin composition of the present invention has improved metal adhesion, application of vapor deposition and plating is also preferable. The molded product thus provided with the metal layer can be used for electromagnetic wave shielding parts, conductive parts, antenna parts, and the like. Such parts are particularly preferably sheet-like and film-like.

The present invention will be further described below with reference to examples, but the present invention is not limited thereto.
The following items were evaluated.

(I) Evaluation of thermoplastic resin composition (i) Si content analysis Measurement was performed by pyrolysis gas chromatography-mass spectrometry (GC-MS). Pellet 0.4 mg obtained from each composition of the examples was heated to 600 ° C. with a double shot pyrolyzer (pyrolysis apparatus) PY-2020iD and pyrolyzed, and the mixed volatile components generated there were separated by GC, and MS Introduce to measure mass spectrum. The area ratio of the Si peak was taken from the obtained pyrogram (spectrum) to obtain the ratio.

(Ii) Charpy impact strength measurement Various pellets obtained from each composition of the examples were dried at 120 ° C. for 5 hours, and then cylinder temperature 300 ° C. and gold by an injection molding machine (Sumitomo Heavy Industries, Ltd. SG-150U). A molded piece was molded at a mold temperature of 80 ° C., and a Charpy impact strength with a notch was measured in accordance with ISO179.

(Iii) Chemical resistance Various pellets obtained from each composition of the examples were dried at 120 ° C. for 5 hours, and then the cylinder temperature was set to 300 ° C. with an injection molding machine (SG-150U, manufactured by Sumitomo Heavy Industries, Ltd.). A flat plate molded product having a length of 150 mm, a width of 150 mm, and a thickness of 2 mmt was molded at a temperature of 80 ° C. After applying strain to this flat molded product and applying commercially available regular gasoline for 10 minutes in an environment of a temperature of 23 ° C. and a relative humidity of 50%, the appearance is visually observed and evaluated. Asked.

(Iv) Flame retardancy The pellets obtained from each composition of the examples were dried at 120 ° C. for 6 hours in a hot air circulating dryer, and the cylinder temperature was 320 using an injection molding machine [Toshiba Machine Co., Ltd. IS150EN-5Y]. A test piece for flame retardancy evaluation was molded at 0 ° C. and a mold temperature of 80 ° C. The vertical combustion test of UL standard 94 was performed at a thickness of 3.0 mm, and the grade was evaluated. When the determination fails to satisfy any of the criteria of V-0, V-1, and V-2, “notV” is indicated.

(V) Heat resistance Various pellets obtained from each composition of the examples were dried at 120 ° C. for 5 hours and then cylinder temperature 300 ° C. and mold temperature by an injection molding machine (SG-150U, manufactured by Sumitomo Heavy Industries, Ltd.). Molded pieces were molded at 80 ° C, and untreated molded product (a) and molded product (b) treated at 150 ° C for 500 hr were measured for tensile impact strength according to ISO8256. The rate was determined.
Tensile impact strength retention rate (%) = [tensile impact strength of (b) / tensile impact strength of (a)] × 100

(Vi) Appearance of molded product Various pellets obtained from each composition of the examples were dried at 120 ° C. for 5 hours and then cylinder temperature 300 ° C. and mold by injection molding machine (Sumitomo Heavy Industries, Ltd. SG-150U). At a temperature of 80 ° C., the appearance of a molded flat product having a length of 150 mm × width 150 mm × thickness 2 mmt was visually observed and evaluated. The evaluation was performed according to the following criteria. In addition, (circle)-(triangle | delta) was judged to be usable.
○: No abnormality is observed. Δ: The hue of the molded product is slightly deteriorated. ×: Silver and peeling are observed in the entire molded product.

[Preparation of resin composition]
After mixing polycarbonate resin, polyphenylene sulfide resin, organosiloxane-containing graft copolymer and other resins listed in Table 1 and various additives in various blending amounts in a blender, they are melt-kneaded using a vent type twin screw extruder. To obtain a pellet. Various additives to be used were prepared in advance by premixing with a polycarbonate resin with a concentration of 10 to 100 times the blending amount as a guide, and then the whole was mixed by a blender. A vent type twin screw extruder (manufactured by Nippon Steel Works, Ltd .: TEX30α (completely meshing, rotating in the same direction, two-thread screw)) was used. Extrusion conditions were a discharge rate of 20 kg / h, a screw rotation speed of 150 rpm, a vent vacuum of 3 kPa, and an extrusion temperature of 300 ° C. from the first supply port to the die part. The obtained pellets were dried with a hot air circulation dryer at 120 ° C. for 5 hours, and then a test piece for evaluation was molded using an injection molding machine. The evaluation results are shown in Table 1.

Each component of the symbol notation of Table 1 is as follows.
(A component)
PC-1: Linear polycarbonate resin (a polycarbonate resin composed of bisphenol A prepared by the phosgene method and p-tert-butylphenol as a terminal terminator. This polycarbonate resin is produced without using an amine catalyst, and is an aromatic polycarbonate. The ratio of terminal hydroxyl groups in the resin terminals was 10 mol%, and the viscosity average molecular weight was 18,000.)
PC-2: Linear polycarbonate resin (a polycarbonate resin comprising bisphenol A prepared by the phosgene method and p-tert-butylphenol as a terminal terminator. This polycarbonate resin is produced without using an amine catalyst, and is an aromatic polycarbonate. The ratio of the terminal hydroxyl group in the resin terminal was 12 mol%, and the viscosity average molecular weight was 23,000.)
(B component)
PPS-1: Linear polyphenylene sulfide resin (50 liter titanium autoclave equipped with a stirrer was charged with 10773 g of N-methyl-2-pyrrolidone, 5607 g of 47% sodium hydrogen sulfide aqueous solution, and 3807 g of 48% sodium hydroxide aqueous solution, under nitrogen flow While stirring, the temperature was gradually raised to 200 ° C. to distill 4533 g of water, the system was cooled to 170 ° C., 7060 g of p-dichlorobenzene and 5943 g of N-methyl-2-pyrrolidone were added, and nitrogen was added. The system was sealed under an air stream, and the system was heated to 225 ° C. and polymerized at 225 ° C. for 1 hour, then heated to 250 ° C. and polymerized at 250 ° C. for 2 hours. 1503 g of water was injected, and the temperature was raised again to 255 ° C., and polymerization was carried out for 2 hours at 255 ° C. After completion of the polymerization, the solution was cooled to room temperature. The polymer slurry was washed with N-methyl-2-pyrrolidone, acetone and water sequentially and dried at 100 ° C. for a whole day and night. The polyphenylene sulfide resin obtained was MVR under the conditions of 300 ° C. and 2.16 kgf. = 200.
PPS-2: Semi-linear polyphenylene sulfide resin (a mixture containing 300.00 g of pDIB and 27.00 g of sulfur was heated to 180 ° C. to completely melt and mix them, then the temperature was raised to 220 ° C. and pressure The polyphenylene sulfide resin produced by the polymerization reaction for 8 hours while changing the temperature and pressure stepwise so that the final temperature and pressure were 320 ° C. and 1 Torr, respectively, was reduced to 200 Torr. (The MVR was 32 under the conditions of 300 ° C. and 2.16 kgf.)
(C component)
SiIM1: a composite rubber system in which methyl methacrylate is graft-polymerized on 90% by weight of a composite rubber having a structure in which a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component cannot be separated from each other. Graft copolymer (containing 30% Si component in area ratio by Py-GC / MS method (600 ° C))
SiIM2: Graft copolymer obtained by graft polymerization of methyl methacrylate and styrene to 90% by weight of polyorganosiloxane rubber component (containing 90% Si component in area ratio by Py-GC / MS method (600 ° C))
MBS: butadiene-based rubbery polymer (Rohm and Haas Co., Ltd .: Paraloid EXL-2602 (trade name), core is polybutadiene 80% by weight, shell is methyl methacrylate and ethyl acrylate, weight average particle Diameter is 0.23μm)
(D component)
ABS1: ABS resin (made by Japan A & L Co., Ltd. UT-61 (trade name), about 80% by weight of free AS polymer component and about 20% by weight of ABS polymer component (acetone insoluble gel content), about 14% of butadiene rubber component PET: Polyethylene terephthalate resin polymerized using a titanium-based catalyst obtained by reacting titanium tetrabutoxide and monolauryl phosphate (IV = IV = weight%, weight average rubber particle diameter 0.56 μm, produced by bulk polymerization) 0.77).
(Other ingredients)
P-1: Trimethyl phosphate P-2: Bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite UV: Benzotriazole ultraviolet absorber (manufactured by Ciba Specialty Chemicals: Tinuvin 234)

Claims (9)

(A) Polyorganosiloxane rubber component and polyalkyl (meth) acrylate rubber component cannot be separated with respect to a total of 100 parts by weight of (A) polycarbonate resin (A component) and (B) polyphenylene sulfide resin (B component). 90% by weight of a composite rubber having a structure intertwined with each other, and a graft copolymer of methyl methacrylate and graft copolymer of methyl methacrylate or 90% by weight of a polyorganosiloxane rubber component of methyl methacrylate and styrene. A thermoplastic resin composition containing 0.5 to 15 parts by weight of the graft copolymer (component C) formed by using the Py-GC / MS method (600 ° C.). A thermoplastic resin composition comprising a Si component in a ratio of 0.1% to 15%.   The thermoplastic resin composition according to claim 1, wherein the component A comprises 50 to 99 parts by weight and the component B comprises 1 to 50 parts by weight.   3. The heat according to claim 1, comprising 1 to 30 parts by weight of a thermoplastic resin (D component) other than (D) A component and B component with respect to 100 parts by weight of the total of A component and B component. Plastic resin composition. The thermoplastic resin composition according to any one of claims 1 to 3 , wherein the C component is a graft copolymer containing 20% to 95% Si component by area ratio by Py-GC / MS method (600 ° C). object. The thermoplastic resin composition according to any one of claims 1 to 4 , wherein the property retention of the sample treated for 500 hours at 150 ° C evaluated by a method defined by ISO8256 is 50% or more. The thermoplastic resin composition according to any one of claims 1 to 5 , which has an ability equivalent to V-2 at 3.0 mmt when evaluated by a method defined by UL94V. The molded article formed from the thermoplastic resin composition in any one of Claims 1-6 . The molded product according to claim 7 , wherein the molded product is a vehicle interior / exterior member. The molded article according to claim 7 , wherein the molded article is an interior / exterior member for OA / electrical electronics.