JP2009203269A - Incombustible aromatic polycarbonate resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an incombustible aromatic polycarbonate resin composition further improved in color development characteristics without deteriorating mechanical characteristics. <P>SOLUTION: The incombustible aromatic polycarbonate resin composition is formed by including 0.1-10 pts.wt. of a graft copolymer (component B) with an average particle diameter of 100-180 nm obtained by emulsion polymerization of latex containing a butadiene-based rubber polymer with a refractive index of 1.535 or more, an unsaturated carboxylic acid alkyl ester, and an aromatic vinyl monomer to 100 pts.wt. of an aromatic polycarbonate resin (component A); and by including 5-30 pts.wt. of an organophosphate flame retardant (component D), and 0.05-2 pts.wt. of a fluorine-containing dripping inhibitor (component E) to 100 pts.wt. of a resin component formed by including 0-40 pts.wt. of at least one kind of copolymer (component C) selected from the group consisting of a thermoplastic graft copolymer (component C-1) obtained by graft reaction of a vinyl cyanide compound and an aromatic vinyl compound with a diene-based rubber component and an AS resin (acrylonitrile-styrene copolymer) (component C-2). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an aromatic polycarbonate resin, a specific rubber elastic body, a thermoplastic graft copolymer obtained by graft-reacting a vinyl cyanide compound and an aromatic vinyl compound to a diene rubber component, and an AS resin (acrylonitrile- The present invention relates to a flame retardant aromatic polycarbonate resin composition having improved flame retardancy comprising at least one copolymer selected from the group consisting of a styrene copolymer), an organic phosphorus flame retardant and a fluorine-containing anti-dripping agent. More specifically, the present invention relates to a flame-retardant aromatic polycarbonate resin composition that provides a molded article having high color development, impact resistance, and flame retardancy by blending the specific graft copolymer.

  Aromatic polycarbonate resins are widely used industrially because they have excellent mechanical properties, thermal properties, and flame resistance. Many polymer alloys of aromatic polycarbonate resins and other thermoplastic resins and elastomers have been developed and are widely used in the fields of OA equipment, electrical / electronic equipment, automobiles, and other miscellaneous goods.

  In recent years, especially in the electric and electronic fields, the weight and size of products have been remarkably reduced, and the thickness of molded products to which aromatic polycarbonate resins are applied has also been reduced. In such a thin molded article, a rubber elastic polymer is often added as an impact modifier in order to increase strength, particularly impact strength.

  In addition, recycling of used products has become indispensable, and recycling of resin products has been attempted in various fields. In order to facilitate the recycling of resin products, resin products that have been painted in the past have been omitted, and resin products that perform coloring required for products only with a colorant mixed in the resin are increasing. Such resin products are required to have higher color developability with respect to the resin. In particular, when a rubber elastic body is blended with an aromatic polycarbonate resin, deep black coloration may be inferior. For example, a resin composition in which a polyorganosiloxane composite rubber graft polymer is blended with an aromatic polycarbonate resin, or a resin composition in which a graft polymer composed of an enlarged diene rubber with a small particle diameter is blended with an aromatic polycarbonate resin is disclosed. (Patent Documents 1 and 2) have a problem that jetness is inferior.

On the other hand, there is a strong demand for non-halogen flame retardant resin materials used mainly for OA equipment, home appliances, etc., and in order to meet these demands, in the polymer alloy of aromatic polycarbonate resin and ABS resin, especially safety standards There is a high demand for flame retardancy such as V-0 in UL94. For example, there is disclosed a resin composition in which an ABS obtained by graft polymerization of rubber having a high refractive index and an aromatic polycarbonate are blended (Patent Document 3), but a flame retardant resin composition having both sufficient impact resistance and flame retardancy. There is a problem that it is difficult to get.
That is, the present situation is that a rubber-reinforced aromatic polycarbonate resin composition has not yet been proposed as a resin composition having a thin flame retardant property and having good impact resistance and colorability (particularly jet black).

JP-A-10-120893 JP-A-11-140295 JP 2007-254507 A

  An object of the present invention is to provide a thermoplastic graft copolymer and an AS resin (acrylonitrile-styrene copolymer) obtained by graft reaction of an aromatic polycarbonate resin and a diene rubber component with a vinyl cyanide compound and an aromatic vinyl compound. ) In an alloy material with at least one copolymer selected from the group consisting of: an organic phosphorus flame retardant, satisfying UL94 standard V-0 test for thin wall, and excellent in coloration and impact resistance The object is to provide a flammable aromatic polycarbonate resin composition.

  As a result of earnest studies to solve such problems, the present inventors have found that a resin composition containing a rubber elastic body having a specific refractive index and particle size is a resin material that solves the above problems, Further studies were made to complete the present invention. According to the present invention, (B) a latex containing a butadiene-based rubbery polymer having a refractive index of 1.535 or more, an unsaturated alkyl carboxylate, based on (A) 100 parts by weight of an aromatic polycarbonate resin (component A) 0.1 to 10 parts by weight of a graft copolymer (component B) having an average particle size of 100 nm to 180 nm obtained by emulsion polymerization of an ester and an aromatic vinyl monomer, and (C) a diene rubber From a thermoplastic graft copolymer (component C-1) obtained by grafting a vinyl cyanide compound and an aromatic vinyl compound to the component (component C-1) and AS resin (acrylonitrile-styrene copolymer) (component C-2) An organophosphorus flame retardant for 100 parts by weight of a resin component comprising 0 to 40 parts by weight of at least one copolymer (component C) selected from the group consisting of Component D) 5 to 30 parts by weight of a fluorine-containing anti-dripping agent (E component) from 0.05 to 2 comprising by weight parts flame retardant aromatic polycarbonate resin composition is provided.

Hereinafter, the details of the present invention will be described.
(Component A: aromatic polycarbonate)
The aromatic polycarbonate resin as the component A of the present invention is obtained by reacting a dihydric phenol and a carbonate precursor. Examples of the reaction method include an interfacial polycondensation method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

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

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

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

  The branched polycarbonate resin increases the melt tension of the resin composition of the present invention, and can improve the molding processability in extrusion molding, foam molding and blow molding based on such properties. As a result, a molded product by these molding methods, which is superior in dimensional accuracy, is obtained.

  Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin include 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, and 4- {4- [1,1- Trisphenol such as bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol is preferably exemplified. Other polyfunctional aromatic compounds include phloroglucin, phloroglucid, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene. And trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, and acid chlorides thereof. Of these, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable, and 1,1,1-tris (4- Hydroxyphenyl) ethane is preferred.

  The structural unit derived from the polyfunctional aromatic compound in the branched polycarbonate resin is 0 in a total of 100 mole parts of the structural unit derived from the dihydric phenol and the structural unit derived from the polyfunctional aromatic compound. 0.03 to 1 mol part, preferably 0.07 to 0.7 mol part, particularly preferably 0.1 to 0.4 mol part.

Further, such a branched structural unit is not only derived from a polyfunctional aromatic compound but also derived without using a polyfunctional aromatic compound, such as a side reaction during a melt transesterification reaction. Also good. The ratio of such a branched structure can be calculated by ¹ H-NMR measurement.

  On the other hand, the aliphatic bifunctional carboxylic acid is preferably α, ω-dicarboxylic acid, and specific examples thereof include sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, icosane diacid. Examples thereof include linear saturated aliphatic dicarboxylic acids such as acids and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. As the bifunctional alcohol, an alicyclic diol is suitable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecane dimethanol. Further, a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units can also be used.

  The component A may be a mixture of two or more of polycarbonates having different dihydric phenol components, polycarbonates containing branched components, various polyester carbonates, polycarbonate-polyorganosiloxane copolymers, and the like. Furthermore, what mixed 2 or more types of polycarbonates from which a manufacturing method differs, a polycarbonate from which a terminal terminator differs, etc. can also be used. The reaction forms such as interfacial polymerization, melt transesterification, solid phase transesterification of carbonate prepolymer, and ring-opening polymerization of cyclic carbonate compounds, which are methods for producing the polycarbonate resin of the present invention, are various documents and patent publications. This is a well-known method.

  As the A component aromatic polycarbonate of the present invention, not only virgin raw materials but also polycarbonate resins regenerated from used products, so-called material-recycled aromatic polycarbonates, can be used. Used products include soundproof walls, glass windows, translucent roofing materials, various glazing materials represented by automobile sunroofs, transparent members such as windshields and automobile headlamp lenses, containers such as water bottles, and optical recording media Etc. are preferred. These do not contain a large amount of additives or other resins, and the desired quality is easily obtained stably. In particular, an automotive headlamp lens, an optical recording medium, and the like are preferred as preferred embodiments because they satisfy the more preferable conditions of the viscosity average molecular weight. In addition, said virgin raw material is a raw material which is not yet used in the market after the manufacture.

The viscosity average molecular weight of the aromatic polycarbonate is preferably 1 × 10 ^{4 to} 5 × 10 ⁴ , more preferably 1.4 × 10 ^{4 to} 3 × 10 ⁴ , and still more preferably 1.8 × 10 ^{4 to} 2.5 ×. 10 is ^four. In the range of 1.8 × 10 ^{4 to} 2.5 × 10 ⁴ , both excellent impact resistance and fluidity are particularly excellent. Most preferably, it is 1.9 × 10 ^{4 to} 2.4 × 10 ⁴ . The viscosity average molecular weight may be satisfied as the whole component A, and includes those satisfying such a range by a mixture of two or more kinds having different molecular weights.

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

(B component: unsaturated carboxylic acid alkyl ester-butadiene rubber-aromatic vinyl monomer graft copolymer)
The B component used in the present invention is obtained by emulsion polymerization of a latex containing a butadiene rubber polymer having a refractive index of 1.535 or more, an unsaturated carboxylic acid alkyl ester, and an aromatic vinyl monomer. It is an unsaturated carboxylic acid alkyl ester-butadiene rubber-aromatic vinyl monomer graft copolymer having an average particle diameter of 100 nm to 180 nm, preferably a methyl methacrylate-butadiene-styrene copolymer (MBS). Resin).

  The latex containing the butadiene rubber polymer of the present invention includes polybutadiene, hydrogenated (partial) polybutadiene, butadiene-styrene copolymer, hydrogenated (partial) butadiene-styrene copolymer, and styrene-butadiene block copolymer. One type capable of copolymerizing butadiene and butadiene, such as a polymer, a hydrogenated (partial) styrene-butadiene block copolymer, a butadiene-acrylonitrile copolymer, and an acrylic rubber copolymer based on butadiene-isobutyl acrylate Examples thereof include copolymers with the above vinyl monomers, among which 50 to 75 parts by weight of 1,3-butadiene and one or more vinyl monomers that can be copolymerized with 1,3-butadiene. What is obtained by copolymerizing 25 to 50 parts by weight of the body is preferable.

  Examples of the vinyl monomer include aromatic vinyl such as styrene and α-methylstyrene; alkyl methacrylate such as methyl methacrylate and ethyl methacrylate; alkyl acrylate such as ethyl acrylate and n-butyl acrylate; acrylonitrile. Unsaturated nitriles such as methacrylonitrile; vinyl ethers such as methyl vinyl ether and butyl vinyl ether; vinyl halides such as vinyl chloride and vinyl bromide; vinylidene halides such as vinylidene chloride and vinylidene bromide; glycidyl acrylate, glycidyl methacrylate, allyl Vinyl monomers having a glycidyl group such as glycidyl ether and ethylene glycol glycidyl ether can be used.

Furthermore, aromatic polyfunctional vinyl compounds such as divinylbenzene and divinyltoluene; polyhydric alcohols such as ethylene glycol dimethacrylate and 1,3-butanediol diacrylate; trimethacrylic acid ester, triacrylic acid ester, allyl acrylate, methacrylic acid Crosslinkable monomers such as di- and triallyl compounds such as carboxylic acid allyl esters such as acid allyl, diallyl phthalate, diallyl sebacate, and triallyl triazine can also be used in combination.
These vinyl monomers and crosslinkable monomers can be used alone or in combination of two or more.

  The refractive index of the latex containing the butadiene rubber polymer of the present invention is 1.535 or more, preferably 1.536 or more, and more preferably 1.538 or more. When the refractive index is less than 1.535, the colorability (particularly jetness) is inferior. A refractive index exceeding 1.550 is not preferable because an effect of improving impact properties cannot be obtained. The refractive index of the latex containing a butadiene rubber polymer can be measured using an Abbe refractometer according to JIS K7142. Specifically, the blending ratio of styrene-butadiene rubber using the refractive index values of polystyrene (n = 1.589) and butadiene rubber (n = 1.516) measured by molding a 300-600 μm film by press molding. Can be obtained by calculation.

  An acid group-containing copolymer can be added to the latex containing the butadiene-based rubbery polymer as described above, whereby the latex containing the butadiene-based rubbery polymer can be enlarged. What is enlarged by the acid group-containing copolymer contains many particles having a large particle size, so that the impact resistance of the resulting graft copolymer can be improved, and a resin composition having excellent impact resistance can be obtained. it can.

  As the acid group-containing copolymer, a mixture containing an alkyl acrylate and at least one unsaturated acid monomer copolymerizable with the alkyl acrylate in the presence of at least one anionic surfactant. Latex having a pH of 4 or more obtained by polymerization is preferred. In addition, as for carbon number of an alkyl group, 1-12 are preferable.

  Examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, and lauryl acrylate.

  Examples of the unsaturated acid monomer include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, cinnamic acid, maleic anhydride, and butenetricarboxylic acid.

  Examples of the emulsifier used in the production of the acid group-containing copolymer include anionic, cationic and nonionic emulsifiers, preferably anionic surfactants, more preferably anionic interfaces other than phosphate ester salts and alkylsulfosuccinates. It is an activator.

  Sufficient enlargement of the butadiene rubber polymer can be achieved only by adding a small amount of the acid group-containing copolymer latex polymerized as described above to the butadiene rubber polymer latex. The addition amount of the acid group-containing copolymer is 0.01 parts by mass or more as a solid content in order to realize sufficient enlargement with respect to 100 parts by mass (as a solid content) of a butadiene rubber polymer. Part by weight or less is preferred.

   The graft copolymer is a monomer containing at least one of an aromatic vinyl monomer and an unsaturated carboxylic acid alkyl ester in a latex obtained by enlarging a butadiene rubber polymer with an acid group-containing copolymer. Alternatively, it can be obtained by graft polymerization of a monomer mixture.

  Examples of the unsaturated carboxylic acid alkyl ester used in the present invention include methyl methacrylate, ethyl methacrylate, ethyl acrylate, n-butyl acrylate, etc. Among them, methyl methacrylate is preferable.

  Examples of the aromatic vinyl monomer used in the present invention include styrene, α-methylstyrene, various halogen-substituted and alkyl-substituted styrenes, and among them, styrene is preferable.

  The polymerization method of the graft copolymer of the present invention is emulsion polymerization, and multistage emulsion polymerization is particularly preferable. Examples of the multistage emulsion polymerization include polymerization methods described in JP-A No. 2003-261629.

  Polymerization can be carried out in the range of about 40 to 80 ° C. depending on the type of polymerization initiator. That is, it is preferable to polymerize by a method in which a monomer to be grafted to a latex containing a butadiene rubber polymer is added in a divided manner or continuously. By taking such a polymerization method, a graft copolymer having a desired structure can be obtained relatively easily. In addition, when setting it as multistage emulsion polymerization, you may change even if it makes the monomer composition charged initially and the monomer composition charged later become the same. The composition ratio of the latex containing the butadiene rubber polymer in the graft copolymer, the unsaturated carboxylic acid alkyl ester, and the aromatic vinyl monomer is preferably 40 to 90%: 10 to 60%: 0 to 60%. 50-80%: 10-40%: 10-40% is more preferable.

The average particle diameter of the graft copolymer in the present invention is 100 nm to 180 nm, preferably 120 nm to 175 nm, and more preferably 150 nm to 170 nm. When the average particle diameter exceeds 180 nm, the total light transmittance of the flame retardant resin composition is lowered, which causes deterioration of colorability. Conversely, if the average particle diameter is less than 100 nm, sufficient impact resistance may not be obtained. The average particle size here is a particle size corresponding to an integrated amount of 50 parts by weight when measuring an integrated amount (parts by weight) of smaller particles for each particle size. This average particle diameter is obtained by immersing the graft copolymer in a solution of OsO4 or RuO4, then observing with a transmission electron microscope, and averaging the particle diameters measured for 1000 or more particles. It is done.
The amount of the rubber component of the graft copolymer is 40 to 90% by weight, preferably 50 to 80% by weight.

  Content of B component is 0.1-10 weight part with respect to 100 weight part of A component, 3-9 weight part is preferable and 5-7 weight part is more preferable. When the content is larger than 10 parts by weight, the flame retardancy is lowered.

<C Component: Thermoplastic Graft Copolymer (C-1 Component) and AS Resin (Acrylonitrile-Styrene Copolymer) Obtained by Graft Reaction of Cyanide Vinyl Compound and Aromatic Vinyl Compound to Diene Rubber Component At least one copolymer selected from the group consisting of (C-2 component)>
Thermoplastic graft obtained by graft-reacting vinyl cyanide compound and aromatic vinyl compound to diene rubber component as C component for the purpose of improving fluidity and the like for flame retardant aromatic polycarbonate resin of the present invention At least one copolymer selected from the group consisting of a copolymer (C-1 component) and an AS resin (acrylonitrile-styrene copolymer) (C-2 component) can be contained.

(C-1 component: thermoplastic graft copolymer obtained by graft reaction of vinyl cyanide compound and aromatic vinyl compound to diene rubber component)
The thermoplastic graft copolymer obtained by graft-reacting a vinyl cyanide compound and an aromatic vinyl compound to the diene rubber component of the C-1 component of the present invention has a rubber component amount of 0.1 to 80 parts by weight. A thermoplastic graft copolymer obtained by grafting a vinyl cyanide compound and an aromatic vinyl compound to a diene rubber component, preferably 0.2 to 50 parts by weight, more preferably 0.3 to 30 parts by weight. Specifically, acrylonitrile-acrylic rubber-styrene copolymer (AAS resin), acrylonitrile-ethylenepropylene rubber-styrene copolymer (AES resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), and the like can be mentioned. Among these, ABS resin is preferable. Hereinafter, the ABS resin preferable as the C-1 component will be described.

  As the diene rubber component forming the ABS resin, rubber having a glass transition point of 10 ° C. or less such as polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene, or the like is used. Examples of the vinyl cyanide compound grafted on the diene rubber component include acrylonitrile and methacrylonitrile, and examples of the aromatic vinyl compound grafted on the diene rubber component include styrene and α-methylstyrene. And nucleus-substituted styrene such as p-methylstyrene.

  In the ABS resin used in the present invention, the proportion of the diene rubber component in 100 parts by weight of the ABS resin component is preferably 0.1 to 80 parts by weight, more preferably 0.2 to 50 parts by weight, particularly preferably 0. 3 to 30 parts by weight.

  In the ABS resin, the rubber particle diameter is preferably 0.05 to 5 [mu] m, more preferably 0.1 to 2.0 [mu] m, and still more preferably 0.2 to 0.5 [mu] m in weight average particle diameter. As the distribution of the rubber particle diameter, either a single distribution or a rubber particle having two or more peaks can be used, and the rubber particles form a single phase in the morphology. Alternatively, it may have a salami structure by containing an occluded phase around the rubber particles.

  Further, it is well known that an ABS resin contains a copolymer of a vinyl cyanide compound and an aromatic vinyl compound that are not grafted to a diene rubber component. The ABS resin of the present invention may contain a free polymer component generated during such polymerization as described above, and a vinyl compound heavy polymer obtained by separately copolymerizing an aromatic vinyl compound and a vinyl cyanide compound. A blended blend may be used. The ratio of the free AS resin can be obtained by dissolving the ABS resin in a good solvent for the AS resin such as acetone and collecting the soluble resin. On the other hand, the insoluble matter (gel) becomes a net ABS resin.

The ratio of the vinyl cyanide compound and aromatic vinyl compound grafted to the diene rubber component in the ABS resin (the ratio of the weight of the graft component to the weight of the diene rubber component), that is, the graft ratio (% by weight) is 20 to 200. % Is preferable, and more preferably 20 to 80%.
Such ABS resin may be produced by any method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.

(C-2 component: AS resin (acrylonitrile-styrene copolymer))
The proportion of each component in the AS resin is 5 to 50 parts by weight, preferably 15 to 35 parts by weight of acrylonitrile, and 95 to 50 parts by weight, preferably 85 to 85 parts by weight of styrene resin, when the total is 100 parts by weight. 65 parts by weight. Further, styrene may be copolymerized with another vinyl compound copolymerizable with styrene. These contents are preferably 15 parts by weight or less in the AS resin. Moreover, conventionally well-known various things can be used for the initiator, chain transfer agent, etc. which are used by reaction as needed.

  Such an AS resin may be produced by any method such as bulk polymerization, solution polymerization, suspension polymerization, suspension bulk polymerization, and emulsion polymerization, but is preferably based on bulk polymerization. The copolymerization method may be either one-stage copolymerization or multistage copolymerization.

The reduced viscosity of the AS resin is such that the reduced viscosity (30 ° C.) determined by the method described below is 0.2 to 1.0 dl / g, more preferably 0.3 to 0.7 dl / g. .
The reduced viscosity is a value obtained by precisely weighing 0.25 g of AS resin and measuring a solution obtained by dissolving in 50 ml of dimethylformamide over 2 hours in an environment of 30 ° C. using an Ubbelohde viscometer. A viscometer having a solvent flow time of 20 to 100 seconds is used. The reduced viscosity is determined from the following formula from the solvent flow down seconds (t ₀ ) and the solution flow down seconds (t).
Reduced viscosity (η _sp / C) = {(t / t ₀ ) −1} /0.5

  Content of C component is 0-40 weight part with respect to 100 weight part of A component, 5-38 weight part is preferable and 10-35 weight part is more preferable. When the content is larger than 40 parts by weight, the flame retardancy is remarkably lowered.

(D component: organophosphorus flame retardant)
Examples of the organic phosphorus flame retardant (D component) of the present invention include a phosphoric ester compound represented by the following formula (1).

（但し上記式中のＸは、ハイドロキノン、レゾルシノール、ビスフェノールＡ、およびジヒドロキシジフェニルよりなる群より選ばれるジヒドロキシ化合物の水酸基を除去して得られる二価の基を表し、Ｒ_１、Ｒ_２、Ｒ_３、およびＲ_４はそれぞれ独立し炭素数６〜１２のアリル基を表し、ｊ、ｋ、ｌ及びｍはそれぞれ独立して０または１であり、ｎは、０〜５の整数を表す。）

(However, X in the above formula represents a divalent group obtained by removing a hydroxyl group of a dihydroxy compound selected from the group consisting of hydroquinone, resorcinol, bisphenol A, and dihydroxydiphenyl, and R ₁ , R ₂ , R ₃ , And R ₄ each independently represent an allyl group having 6 to 12 carbon atoms, j, k, l and m are each independently 0 or 1, and n represents an integer of 0 to 5).

  The phosphate compound of the above formula (1) may be a mixture of compounds having different n numbers, and in the case of such a mixture, the average n number is preferably 0.5 to 1.5, more preferably 0. 0.8 to 1.2, more preferably 0.95 to 1.15, and particularly preferably 1 to 1.14.

  X in the above formula is a divalent group derived from a dihydroxy compound selected from the group consisting of hydroquinone, resorcinol, bisphenol A, and dihydroxydiphenyl, and is preferably derived from resorcinol, bisphenol A, and dihydroxydiphenyl. Divalent group.

R ₁ , R ₂ , R ₃ , and R ₄ in the above formula are exemplified by monovalent groups derived from hydroxy compounds such as phenol, cresol, xylenol, isopropylphenol, butylphenol, and p-cumylphenol. Of these, phenol and 2,6-dimethylphenol are preferred.

  Such a monohydric phenol may substitute 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 phosphate compounds not substituted with halogen atoms 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 above formula (1) is 80 parts by weight or more, more preferably 85 parts by weight or more, and still more preferably 90 parts. To contain more than parts by weight Be.).

  The acid value of the phosphoric ester compound is preferably 0.2 mgKOH / g, more preferably 0.15 mgKOH / g or less, still more preferably 0.1 mgKOH / g or less, particularly preferably 0.05 mgKOH / g or less. It is. The lower limit of the acid value can be substantially 0, and 0.01 mgKOH / g or more is practically preferable. On the other hand, the content of the half ester is more preferably 1.1 parts by weight or less, and still more preferably 0.9 parts by weight or less. As a minimum, 0.1 weight part or more is preferable practically, and 0.2 weight part or more is more preferable. When the acid value exceeds 0.2 mgKOH / g, or when the half ester content exceeds 1.5 mg, the thermal stability at the time of molding becomes inferior. Hydrolysis resistance decreases. The C component can be a mixture of two or more different phosphate ester compounds.

  Content of D component is 5-30 weight part on the basis of a total of 100 weight part of A component, B component, and C component, 6-25 weight part is preferable and 7-20 weight part is especially preferable. Such a suitable composition ratio provides an aromatic polycarbonate resin composition having good flame retardancy.

(E component: fluorine-containing anti-dripping agent)
The fluorine-containing anti-dripping agent for component E used in the present invention is for preventing melt dripping during combustion and further improving flame retardancy, and polytetrafluoroethylene having fibril-forming ability is preferably used. . Hereinafter, polytetrafluoroethylene may be simply referred to as PTFE. PTFE having a fibril forming ability has a very high molecular weight, and tends to be bonded to each other by an external action such as shearing force to form a fiber. The molecular weight is 1 million to 10 million, more preferably 2 million to 9 million in the number average molecular weight determined from the standard specific gravity. Such PTFE can be used in solid form or in the form of an aqueous dispersion. In addition, PTFE having such fibril-forming ability can improve the dispersibility in the resin, and it is also possible to use a PTFE mixture in a mixed form with other resins in order to obtain better flame retardancy and mechanical properties. is there.

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

  As a mixed form of PTFE, (1) a method in which an aqueous dispersion of PTFE and an aqueous dispersion or solution of an organic polymer are mixed and co-precipitated to obtain a co-aggregated mixture (Japanese Patent Application Laid-Open No. 60-258263; (Method described in JP-A-63-154744), (2) A method of mixing an aqueous dispersion of PTFE and dried organic polymer particles (method described in JP-A-4-272957), (3) A method in which an aqueous dispersion of PTFE and an organic polymer particle solution are uniformly mixed, and each medium is simultaneously removed from the mixture (described in JP-A-06-220210, JP-A-08-188653, etc.) And (4) a method of polymerizing monomers forming an organic polymer in an aqueous dispersion of PTFE (a method described in JP-A-9-95583), and (5) A method in which an aqueous dispersion of TFE and an organic polymer dispersion are uniformly mixed, and then a vinyl monomer is further polymerized in the mixed dispersion, and then a mixture is obtained (described in JP-A-11-29679, etc.). Those obtained by (Method) can be used. These PTFE commercial products in the form of mixed products include “Maybrene A3800” (trade name), “Metebrane A3700” (trade name) manufactured by Mitsubishi Rayon Co., Ltd., and “BLENDEX B449” (trade name) manufactured by GE Specialty Chemicals. And so on.

The proportion of PTFE in the mixed form is preferably 1 to 60 parts by weight, more preferably 5 to 55 parts by weight in 100 parts by weight of the PTFE mixture. When the ratio of PTFE is within such a range, good dispersibility of PTFE can be achieved.
The content of component E is 0.05 to 2 parts by weight, preferably 0.05 to 1 part by weight, more preferably 0.1 to 0 parts, based on a total of 100 parts by weight of component A, component B, and component C. .6 parts by weight. Such a suitable composition ratio provides an aromatic polycarbonate resin composition having good flame retardancy.

(F component: higher fatty acid ester of monohydric or polyhydric alcohol)
The F component in the present invention is a higher fatty acid ester of a monohydric or polyhydric alcohol and a higher fatty acid. The higher fatty acid preferably contains 60 parts by weight or more of a fatty acid having 20 or more carbon atoms (more preferably 20 to 32 carbon atoms, still more preferably 26 to 32 carbon atoms). As such a higher fatty acid, a higher fatty acid mainly composed of montanic acid is preferably exemplified. Such higher fatty acids are usually produced by oxidizing montan wax. On the other hand, examples of the monohydric alcohol include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, seryl alcohol, and triacontanol.

  Examples of the polyhydric alcohol include glycerin, diglycerin, polyglycerin (such as decaglycerin), pentaerythritol, dipentaerythritol, trimethylolpropane, diethylene glycol, and propylene glycol. The alcohol component in the E component is more preferably a polyhydric alcohol. Among these, glycerin, pentaerythritol, dipentaerythritol, and trimethylolpropane are preferable, and glycerin is particularly preferable.

Esters of higher fatty acids mainly composed of montanic acid and mono- or polyhydric alcohols (preferably polyhydric alcohols) have a density of 0.94 to 1.10 g / cm ³ , an acid value of 1 to 200, and a saponification value. : It is suitable that it is the range of 50-200.

  The content of the F component is preferably 0.2 to 1 part by weight, more preferably 0.35 to 0.7 part by weight, still more preferably based on 100 parts by weight of the total of the A component, the B component, and the C component. 0.45 to 0.65 parts by weight. With such a suitable composition ratio, an aromatic polycarbonate resin composition having good releasability is provided.

(Other additives)
In the polycarbonate resin composition of the present invention, various stabilizers and coloring materials can be used to stabilize the molecular weight and hue at the time of molding. Examples of such stabilizers include phosphorus stabilizers, hindered phenol stabilizers, ultraviolet absorbers, facial cleansers, heat stabilizers, antistatic agents, and the like.

(I) Phosphorus stabilizer Examples of the phosphorous stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphine.
Specifically, as the phosphite compound, for example, triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl Phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di -N-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, dis Allyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite, phenylbisphenol A Examples include pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, and dicyclohexyl pentaerythritol diphosphite.

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

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

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

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

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

  The phosphorus stabilizers can be used alone or in combination of two or more. Among the phosphorus stabilizers, phosphonite compounds or phosphite compounds represented by the following general formula (2) are preferable.

（式（２）中、Ｒ^５およびＲ^６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 (2), R ⁵ and R ⁶ represent an alkyl group having 6 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and may be the same or different from each other.)

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

  Among the above formulas (2), more preferred phosphite compounds are distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di). -Tert-butyl-4-methylphenyl) pentaerythritol diphosphite, and bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite.

  Distearyl pentaerythritol diphosphite is commercially available as ADK STAB PEP-8 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and JPP681S (trademark, manufactured by Johoku Chemical Industry Co., Ltd.), and any of them can be used. Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite is ADK STAB PEP-24G (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.), Alkanox P-24 (trademark, manufactured by Great Lakes), Ultranox. P626 (trademark, manufactured by GE Specialty Chemicals), Doverphos S-9432 (trademark, manufactured by Dover Chemical), and Irgafos 126 and 126FF (trademark, manufactured by CIBA SPECIALTY CHEMICALS) are also available. Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is commercially available as ADK STAB PEP-36 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and can be easily used. Further, bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite is produced by ADK STAB PEP-45 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and Doverphos S-9228 (trademark). , Manufactured by Dober Chemical Co.) and any of them can be used.

(Ii) Hindered phenolic antioxidant As the hindered phenolic compound, various compounds that are usually blended in a resin can be used. Examples of such hindered phenol compounds include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-tert -Butyl-6- (3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylamino) Methyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl) -6-tert-butylphenol), 4,4'-methylenebis (2,6 Di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol), 2,2 ′ -Ethylidene-bis (4,6-di-tert-butylphenol), 2,2'-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert) -Butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di- tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- (3-tert-butyl) Ru-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1- Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4′-thiobis (6-tert-butyl-m-cresol), 4,4′-thiobis (3-methyl) -6-tert-butylphenol), 2,2'-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4'- Di-thiobis (2,6-di-tert-butylphenol), 4,4′-tri-thiobis (2,6-di-tert-butylphenol), 2,2-thiodiethyl Bis- [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) isocyanate Anurate, 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 compounding amounts of the phosphorus stabilizer and the hindered phenol antioxidant are 0.005 to 1 part by weight, preferably 0.01 to 100 parts by weight based on the total of 100 parts by weight of the component A, component B and component C, respectively. 0.3 parts by weight.

(Iii) Ultraviolet Absorber The polycarbonate resin composition of the present invention can contain an ultraviolet absorber. Since the resin composition of the present invention may be inferior in weather resistance due to the influence of a rubber component or a flame retardant, the incorporation of an ultraviolet absorber is effective to prevent such deterioration.

  Specific examples of the ultraviolet absorber of the present invention include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4 in the benzophenone series. -Benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridolate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2, 2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-benzoyl-4-hydro Shi-2-methoxyphenyl) methane, 2-hydroxy -4-n-dodecyloxy benzoin phenone, and 2-hydroxy-4-methoxy-2'-carboxy benzophenone may be exemplified.

  Specific examples of the ultraviolet absorber include, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole in the benzotriazole series. 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-chlorobenzotriazol 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-benzoxazin-4-one), and 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, and 2- (2'-Hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole and co-polymerized with the monomer 2 such as a copolymer with a possible vinyl monomer and a copolymer of 2- (2′-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole with a vinyl monomer copolymerizable with the monomer Examples include polymers having a -hydroxyphenyl-2H-benzotriazole skeleton.

  Specific examples of the ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol and 2- (4) in hydroxyphenyltriazine series. , 6-Diphenyl-1,3,5-triazin-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxy Phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-propyloxyphenol, and 2- (4,6-diphenyl-1,3,5-triazine-2- Yl) -5-butyloxyphenol and the like. 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.

  As the ultraviolet absorber, specifically, in the cyclic imino ester type, for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) ) Bis (3,1-benzoxazin-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

  Of these, benzotriazoles and hydroxyphenyltriazines are preferred from the viewpoint of ultraviolet absorbing ability, and cyclic iminoesters and cyanoacrylates are preferred from the viewpoint of heat resistance and hue (transparency). You may use the said ultraviolet absorber individually or in mixture of 2 or more types.

  The content of the ultraviolet absorber is 0.01 to 2 parts by weight, preferably 0.03 to 2 parts by weight, more preferably 0.02 to 2 parts by weight based on the total of 100 parts by weight of the A component, B component, and C component. 1 part by weight, more preferably 0.05 to 0.5 part by weight.

(Iv) Dye / pigment The polycarbonate resin composition of the present invention can further provide a molded product containing various dyes / pigments and exhibiting various design properties.
Examples of the fluorescent dye (including a fluorescent brightening agent) used in the present invention include a coumarin fluorescent dye, a benzopyran fluorescent dye, a perylene fluorescent dye, an anthraquinone fluorescent dye, a thioindigo fluorescent dye, and a xanthene fluorescent dye. And xanthone fluorescent dyes, thioxanthene fluorescent dyes, thioxanthone fluorescent dyes, thiazine fluorescent dyes, and diaminostilbene fluorescent dyes. Among these, coumarin fluorescent dyes, benzopyran fluorescent dyes, and perylene fluorescent dyes are preferable because they have good heat resistance and little deterioration during molding of the polycarbonate resin.

  Examples of dyes other than the above bluing agents and fluorescent dyes include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as bitumen, perinone dyes, quinoline dyes, quinacridone And dyes such as dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, the resin composition of this invention can mix | blend a metallic pigment, and can also obtain a better metallic color. As the metallic pigment, those having a metal film or a metal oxide film on various plate-like fillers are suitable.

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

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

  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, component B, and component C. Part.

(Vi) Antistatic agent The polycarbonate 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 parts based on a total of 100 parts by weight of the component A, the component B and the component C. The amount is 5 parts by weight, more preferably 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 sulfonate alkali (earth) metal salt is suitably 0.5 parts by weight or less based on the total of 100 parts by weight of the component A, the component B, and the component C, preferably 0.001 to 0.00. 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 a total of 100 parts by weight of component A, component B, and component C. 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, the B component, and the C component.

(Vii) Other additives The polycarbonate resin composition of the present invention includes thermoplastic resins other than the component A and component B and component C, other flow modifiers, antibacterial agents, dispersants such as liquid paraffin, A soiling agent, a heat ray absorbent, a photochromic agent, etc. can be mix | blended.

  As thermoplastic resins other than A component, B component and C component, aromatic polyester resin (polyethylene terephthalate resin (PET resin), polybutylene terephthalate resin (PBT resin), cyclohexanedimethanol copolymerized polyethylene terephthalate resin (so-called PET-G) Resin), polyethylene naphthalate resin, and polybutylene naphthalate resin), polymethyl methacrylate resin (PMMA resin), cyclic polyolefin resin, polylactic acid resin, polycaprolactone resin, thermoplastic fluororesin (eg, polyvinylidene fluoride resin) And polyolefin resins (polyethylene resin, ethylene- (α-olefin) copolymer resin, polypropylene resin, propylene- (α-olefin) copolymer resin, etc.) Is done. The other thermoplastic resin is preferably 20 parts by weight or less, more preferably 10 parts by weight or less based on the total of 100 parts by weight of component A, component B, and component C.

(Manufacture of polycarbonate resin composition)
Arbitrary methods are employ | adopted for manufacture of the flame-retardant aromatic polycarbonate resin composition of this invention. For example, after thoroughly mixing (so-called dry blend) the A component to the F component, and optionally other additives, using a premixing means such as a V-type blender, a Henschel mixer, a mechanochemical apparatus, and an extrusion mixer, If necessary, granulate the pre-mixture obtained by an extrusion granulator or briquetting machine, and then melt and knead it with a melt kneader typified by a vent type twin screw extruder. The method of pelletizing a thing with apparatuses, such as a pelletizer, is mentioned.

  In addition, a method of supplying each component independently to a melt kneader represented by a vent type twin screw extruder, or a part of each component is premixed and then supplied to the melt kneader independently of the remaining components. The method of doing is also mentioned. Examples of the premixing method include a method of dry blending a part of the powder of the A component and the additive such as the D component and the D component to prepare a master batch of the additive diluted with the powder. It is done. Furthermore, the method etc. which supply one component independently from the middle of a melt extruder are mentioned. The heating temperature at the time of melt kneading is usually selected in the range of 250 to 300 ° C.

  In addition, when there exists a liquid thing in the component to mix | blend, what is called a liquid injection apparatus or a liquid addition apparatus can be used for supply to a melt extruder. As such a liquid injection device or a liquid addition device, one provided with a heating device is preferably used. In particular, the phosphoric acid ester oligomer contained in the component D of the present invention becomes a liquid rather than a solid depending on the distribution of the condensation degree n. Therefore, a method of using a so-called liquid injection device or a liquid addition device is used for supply to the extruder. Therefore, the extruder used in the present invention is preferably one having a raw material supply port for liquid injection. Moreover, the addition of the phosphate ester oligomer is supplied from a feed port provided in a barrel of a normal extruder at a pressure higher than the discharge pressure in the extruder by a known liquid conveying device such as a gear pump. In addition, the phosphate ester oligomer at the time of this supply uses what was heated at the temperature of 20 to 100 degreeC, Preferably it is 30 to 90 degreeC, More preferably, it is 40 to 80 degreeC. Below 20 ° C, the viscosity of the phosphate ester is too high to add with high quantitative accuracy, and above 100 ° C, volatilization, decomposition, or deterioration of the phosphate ester may occur in long-term production.

  The extruded resin can be directly cut into pellets, or after forming strands, the strands can be 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. Although the shape of the obtained pellet can take general shapes, such as a cylinder, a prism, and a spherical shape, it is more preferably a cylinder. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and still more preferably 2 to 3.3 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and still more preferably 2.5 to 3.5 mm.

  The flame-retardant aromatic polycarbonate 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, sandwich molding, and ultra-high speed injection molding. In addition, either a cold runner method or a hot runner method can be selected for molding.

  The polycarbonate resin composition of the present invention can also be used in the form of various shaped extruded products, sheets, films, 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. Further, the polycarbonate resin composition of the present invention can be formed into a molded product by rotational molding or blow molding.

  Specific examples of the molded article in which the flame retardant aromatic polycarbonate resin composition of the present invention is used are suitable for application to internal parts and housings of OA equipment and home appliances. As these products, for example, resin products formed from the flame-retardant thermoplastic resin composition of the present invention can be used for various parts such as copiers, printers, and liquid crystal television casings.

  The flame-retardant aromatic polycarbonate resin composition of the present invention exhibits high color development properties, particularly jet blackness, without deteriorating flame retardancy and mechanical properties. It can be used as a molding material in a wide range of fields. The industrial effect exhibited by the present invention is extremely great.

  The form of the present invention considered to be the best by the present inventor is a collection of the preferable ranges of the above requirements. For example, typical examples are described in the following examples. Of course, the present invention is not limited to these forms.

Evaluation was carried out by the following method.
(I) Evaluation of Flame Retardant Aromatic Polycarbonate Resin Composition (i) Charpy Impact Strength According to ISO 179, measurement of notched Charpy impact strength was performed.
(Ii) Total light transmittance In accordance with JIS K 7361-1, measurement was performed using a D65 light source. The test piece was 2.0 mm in thickness. The total light transmittance is preferably 40% or more, more preferably 45% or more.
(Iii) Flame retardance According to UL standard 94V, a combustion test was performed at a thickness of 1.5 mm.
(Iv) L value In accordance with JIS K 7105, reflection measurement was performed using a D65 light source. A three-dimensional coordinate axis expressed as Lab is used for the color solid (color space). The L value in the table represents L lightness, where L = 0 is the darkest (black) and L = 100 is the brightest (white). When ΔL = 0 to 1.5, a slight brightness difference is obtained, when ΔL = 1.5 to 3.0, a perceivable brightness difference is obtained, and when ΔL = 3 or more, a noticeable brightness difference is obtained. The test piece was 2.0 mm in thickness. The L value is preferably the same as that when MBS is not added (Comparative Example 10).

[Examples 1 to 10, Comparative Examples 1 to 14]
The mixture which consists of a component except a C component and D component with the composition shown in Table 1 and Table 2 was supplied from the 1st supply port of the extruder. Such a mixture was obtained by mixing the following premix (i) with other components using a V-type blender. That is, (i) is a mixture of an E component (fluorine-containing anti-dripping agent) and an A component aromatic polycarbonate, and the entire bag is shaken in a polyethylene bag so that the E component is 2.5 parts by weight. Thus, the mixture is uniformly mixed. The C component was supplied from the second supply port using a side feeder. Furthermore, the D component is heated to 80 ° C., and the liquid supply device (HYM-JS-08 manufactured by Fuji Techno Co., Ltd.) is used to connect the third supply port (second supply port and vent exhaust port) in the middle of the cylinder. From an intermediate position, each was supplied to the extruder at a predetermined ratio. The liquid injection device was set to supply a constant amount, and the supply amounts of other raw materials were precisely measured with a measuring instrument [CWF manufactured by Kubota Corporation]. Extrusion was performed by using a bent type twin screw extruder (Nippon Steel Works TEX30α-38.5BW-3V) with a diameter of 30 mmφ, melt kneading at a screw speed of 200 rpm, a discharge rate of 20 kg / h, and a vent vacuum of 3 kPa. Pellets were obtained. In addition, about extrusion temperature, it was 260 degreeC from the 1st supply port to the die part.

  The obtained pellets were dried in a hot air circulation dryer at 80 to 90 ° C. for 6 hours, and then the cylinder temperature was 240 ° C. and the mold temperature was 60 ° C. using an injection molding machine [SG150U manufactured by Sumitomo Heavy Industries, Ltd.]. Test specimens for evaluation were molded under the conditions.

The respective components indicated by symbols in Table 1 and Table 2 are as follows.
(A component)
PC1: aromatic polycarbonate resin [polycarbonate resin powder having a viscosity average molecular weight of 22,400 made from bisphenol A and phosgene by a conventional method, Panlite L-1225WP manufactured by Teijin Chemicals Ltd.]
PC2: aromatic polycarbonate resin [polycarbonate resin powder having a viscosity average molecular weight of 25,100 made from bisphenol A and phosgene by a conventional method, Panlite K-1250WQ manufactured by Teijin Chemicals Ltd.]
(B component)
IM-1: Core-shell graft copolymer; a latex in which the core contains styrene and a butadiene rubber polymer, and a graft copolymer in which the shell is styrene and methyl methacrylate. The refractive index (calculated value) of the core part is 1.538. The average particle size of the graft polymer is 160 nm. (Metablen C-215A (trade name) manufactured by Mitsubishi Rayon Co., Ltd.)
IM-2: Core-shell graft copolymer; a latex in which the core contains styrene and a butadiene rubber polymer, and a graft copolymer in which the shell is styrene and methyl methacrylate. The refractive index (calculated value) of the core part is 1.545. The average particle size of the graft polymer is 100 nm.
IM-3: Core-shell graft copolymer; a latex in which the core contains styrene and a butadiene rubber polymer, and a graft copolymer in which the shell is styrene and methyl methacrylate. The refractive index (calculated value) of the core part is 1.531. The average particle size of the graft polymer is 200 nm.
IM-4: Core-shell graft copolymer; a latex in which the core contains styrene and a butadiene rubber polymer, and a graft copolymer in which the shell is styrene and methyl methacrylate. The refractive index (calculated value) of the core part is 1.538. The average particle size of the graft polymer is 200 nm.
IM-5: Core-shell graft copolymer; a latex in which the core contains styrene and a butadiene rubber polymer, and a graft copolymer in which the shell is styrene and methyl methacrylate. The refractive index (calculated value) of the core part is 1.538. The average particle size of the graft polymer is 80 nm.
IM-6: Silicon acrylic composite rubber; (Mettablen S-2100 (trade name) manufactured by Mitsubishi Rayon Co., Ltd.)
(C component)
AS: AS resin (manufactured by Nippon A & L Co., Ltd. Litec-A BS-207 (trade name)) emulsion polymerization AS resin ABS: ABS resin (made by CHEIL INDUSTRIES INC .: CH-T (trade name))
(D component)
FR: Phosphate ester mainly composed of bisphenol A bis (diphenyl phosphate) (manufactured by Daihachi Chemical Industry Co., Ltd .: CR-741 (trade name))
(E component)
PTFE1: Polytetrafluoroethylene (Daikin Industries, Ltd., Polyflon MP FA500 (trade name))
PTFE2: Polytetrafluoroethylene-containing mixed powder (Mettablen A3700 (trade name) manufactured by Mitsubishi Rayon Co., Ltd.)
(F component)
SL: Fatty acid ester release agent (Riken Vitamin Co., Ltd .; Riquemar SL900 (trade name))
(Other ingredients)
IRG: Phenol heat stabilizer (Ciba Specialty Chemicals KK; IRGANOX 1076 (trade name))
CB: Carbon Black Master (Koshigaya Kasei Kogyo Co., Ltd., Royal Black 904S (trade name))

  From the above table, it can be seen that by adding a specific amount of the specific MBS resin of the present invention, the colorability, particularly jet blackness, can be greatly improved without lowering the impact strength and flame retardancy.

Claims (5)

  (A) 100 parts by weight of an aromatic polycarbonate resin (component A), (B) a latex containing a butadiene rubber polymer having a refractive index of 1.535 or more, an unsaturated carboxylic acid alkyl ester, and an aromatic 0.1 to 10 parts by weight of a graft copolymer (component B) having an average particle size of 100 nm to 180 nm obtained by emulsion polymerization of a vinyl monomer and (C) a vinyl cyanide compound as a diene rubber component And a thermoplastic graft copolymer (component C-1) obtained by graft reaction of an aromatic vinyl compound and at least selected from the group consisting of AS resin (acrylonitrile-styrene copolymer) (component C-2) 100 parts by weight of a resin component comprising 0 to 40 parts by weight of one type of copolymer (component C) (D) an organophosphorus flame retardant (component D) 30 parts by weight of (E) a fluorine-containing anti-dripping agent (E component) from 0.05 to 2 comprising by weight parts flame retardant aromatic polycarbonate resin composition.   The flame-retardant aromatic polycarbonate resin composition according to claim 1, wherein the graft copolymer (component B) has a rubber component amount of 40 to 90% by weight.   The flame retardant aromatic according to claim 1 or 2, wherein the thermoplastic graft copolymer (C-1 component) is an acrylonitrile-styrene-butadiene copolymer having a rubber component amount of 0.1 to 30% by weight. Polycarbonate resin composition. The flame retardant aromatic polycarbonate resin according to any one of claims 1 to 3, wherein the D component is an organophosphorus flame retardant having an acid value represented by the following formula (1) of 0.2 mgKOH / g or less. Composition.

(However, X in the above formula represents a divalent group obtained by removing a hydroxyl group of a dihydroxy compound selected from the group consisting of hydroquinone, resorcinol, bisphenol A, and dihydroxydiphenyl, and R ₁ , R ₂ , R ₃ , And R ₄ each independently represents an aryl group having 6 to 12 carbon atoms, j, k, l and m are each independently 0 or 1, and n represents an integer of 0 to 5).   5. The composition according to claim 1, comprising 0.2 to 1.0 part by weight of (F) a higher fatty acid ester (F component) of a monohydric or polyhydric alcohol with respect to 100 parts by weight of the resin component. The flame retardant aromatic polycarbonate resin composition according to claim 1.