JP2006342271A - Flame-retardant thermoplastic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame-retardant thermoplastic resin composition that has good balance between several properties such as flame retardancy, shock resistance, heat resistance, very excellent moist heat deterioration and very excllent surface appearance, good flame-retardancy, impact strength, heat resistance, very excellent surface moist-heat deterioration and surface appearance, and can suitably be used in a variety of products such as electric, electronic and ITE (information technology equipment) fields, thus having very high industrial usefuoness. <P>SOLUTION: To 100 pts.wt. of a resin component composed of 1 to 99 pts.wt. of (A) a polycarbonate resin and 99 to 1 pt.wt. of a rubber-reinforced styrene resin, are combined the following components (C), (D), (E) and (F) components: the component (C) 2 to 25 pts.wt. of phosphate ester flame retarder, the component (D) 0.01 to 6 pts.wt. of a silicone compound in which the main chain has a branched structure or the organic group including aromatic group and hydrocarbon group other than the aromatic group, the component (E) 0.05 to 2 pts.wt. of a mixed powder including polytetrafluoroethylene and the component (F) 0.01 to 2 pts.wt. of an epoxy stabilizer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a flame retardant thermoplastic resin composition. More specifically, by blending a polymer blend of a polycarbonate resin and a rubber-reinforced styrene resin with a phosphate ester flame retardant, a specific silicone compound, a polytetrafluoroethylene-containing mixed powder and an epoxy stabilizer, The present invention provides a flame retardant thermoplastic resin composition having excellent flame retardancy, physical property balance, wet heat degradation, and surface appearance. Moreover, since it does not contain halogen-based flame retardants such as chlorine and bromine compounds, it is extremely excellent in environmental harmony.

  Polymer blends obtained by blending a polycarbonate resin and a rubber-reinforced styrene resin such as ABS resin (acrylonitrile / butadiene / styrene copolymer) are widely used in many products in the electric / electronic and ITE fields.

  In these electric, electronic, and ITE fields, there are many parts that require a high level of flame retardancy (UL94V), fluidity, and physical property balance. A polymer blend obtained by blending a polycarbonate resin and a rubber-reinforced styrene resin such as ABS resin is a highly flame-retardant plastic material, but in order to satisfy safety requirements in the electric, electronic and ITE fields, UL94V-0 and Even higher flame retardancy equivalent to 94V-1 has been demanded, and these resins alone could not sufficiently satisfy the market needs.

  In order to improve the flame retardancy of the resin, a method of blending a large amount of a phosphorus flame retardant such as resorcinol polyphosphate has been proposed.

JP-A-6-240127 JP 59-45351

  However, when a large amount of a phosphorus compound such as resorcinol polyphosphate is added as a flame retardant, the flame retardancy and fluidity of the polycarbonate resin are improved, but the impact resistance and heat resistance are greatly reduced. There was a fatal drawback.

  The above-mentioned impact resistance can not be improved by blending a large amount of elastomer, but new problems such as a decrease in flame retardancy and heat resistance of the resulting composition have occurred, and in the market A suitable material having a high balance of physical properties such as high flame retardancy, impact resistance and heat resistance that sufficiently satisfies the needs has not been obtained.

In addition, a decrease in wet heat degradation (hydrolysis resistance) of the composition due to hydrolysis of the phosphate ester flame retardant is also a problem, and improvement thereof has been desired.

Furthermore, it is pointed out that a composition in which a polytetrafluoroethylene (PTFE resin) for preventing dripping is blended with a polymer blend of polycarbonate resin or polycarbonate resin and ABS resin has a decrease in surface appearance due to aggregation of the PTFE resin. However, these compositions are often used as housings and exterior materials for various devices in fields such as electricity, electronics, and ITE, and it is desired that they always have a good surface appearance.

  As a result of diligent research in view of the above-mentioned problems, the present inventors have used a phosphorus-based flame retardant and a specific silicone compound in combination as a flame retardant to be blended with a polymer blend of a polycarbonate resin and a rubber-reinforced styrene resin. In addition, by blending polytetrafluoroethylene-containing mixed powder and an epoxy-based stabilizer, a flame-retardant thermoplastic resin composition having a high level of physical property balance, heat-and-moisture resistance characteristics, and a good surface appearance can be obtained. As a result, the present invention has been completed.

  That is, the present invention relates to 100 parts by weight of a resin component comprising (A) 1 to 99% by weight of a polycarbonate resin and (B) 99 to 1% by weight of a rubber-reinforced styrene resin. ˜25 parts by weight, (D) a silicone compound in which the main chain has a branched structure and the organic functional group contained is composed of an aromatic group, or is composed of an aromatic group and a hydrocarbon group (excluding an aromatic group). The flame-retardant heat comprising 01-6 parts by weight, (E) 0.05-2 parts by weight of polytetrafluoroethylene-containing mixed powder and (F) 0.01-2 parts by weight of an epoxy-based stabilizer A plastic resin composition is provided.

The thermoplastic resin composition of the present invention is extremely excellent in physical property balance such as flame retardancy, impact resistance and heat resistance, wet heat deterioration, surface appearance, etc., and suitable for various products in fields such as electricity, electronics and ITE. The industrial use value is extremely high.

  The (A) polycarbonate resin used in the present invention is a phosgene method in which various dihydroxydiaryl compounds and phosgene are reacted or a transesterification method obtained by reacting a dihydroxydiaryl compound and a carbonate such as diphenyl carbonate. A typical example is a polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A).

  Examples of the dihydroxydiaryl compound include bisphenol 4-, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2, 2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3) -Tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis ( Bis (hydroxyaryl) alkanes such as 4-hydroxy-3,5-dichlorophenyl) propane, 1,1- (4-hydroxyphenyl) cyclopentane, bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3 Dihydroxy diaryl ethers such as 3,3'-dimethyldiphenyl ether, dihydroxy diaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3 ' -Dihydroxy diaryl sulfoxides such as dimethyldiphenyl sulfoxide, dihydroxy diary such as 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone Sulfone, and the like.

  These are used singly or as a mixture of two or more. However, it is preferable not to be substituted with a halogen from the viewpoint of preventing discharge of a gas containing halogen, which is a concern during combustion, into the environment. In addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4'-dihydroxydiphenyl, and the like may be mixed and used.

  Furthermore, the above dihydroxyaryl compound and a trivalent or higher phenol compound as shown below may be used in combination.

  Trihydric or higher phenols include phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, 2,4,6-dimethyl-2,4,6-tri- (4 -Hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -ethane and 2,2-bis- [4 4- (4,4'-dihydroxydiphenyl) -cyclohexyl] -propane and the like.

  (A) The viscosity average molecular weight of the polycarbonate resin is usually 10,000 to 100,000, preferably 15,000 to 35,000, and more preferably 17,000 to 22,000. In producing such a polycarbonate resin, a molecular weight regulator, a catalyst and the like can be used as necessary.

  The (B) rubber-reinforced styrene resin used in the present invention includes (a) an aromatic vinyl monomer component, (b) a vinyl cyanide monomer component, and (c) a rubbery polymer. It is composed of (B-1) a copolymer containing as a constituent component of a coalescence and (B-2) a copolymer containing (a) and (b) as constituent components of the copolymer. Resin. Examples of preferable (B) rubber-reinforced styrene-based resins include those containing (c) a graft copolymer in which the components (a) and (b) are graft-copolymerized in the presence of a rubbery polymer, Preferably, an ABS resin made by bulk polymerization is used.

(A) Examples of the aromatic vinyl monomer component include styrene, α-methylstyrene, o-, m-, p-methylstyrene, vinylxylene, ethylstyrene, vinylnaphthalene, and the like. More than seeds can be used. Of these components, styrene is preferably used.

(B) As a vinyl cyanide monomer component, acrylonitrile, methacrylonitrile, etc. are mentioned, for example, These can be used 1 type, or 2 or more types. Of these components, acrylonitrile is preferably used.

(C) Examples of the rubbery polymer include polybutadiene, styrene-butadiene random copolymer or block copolymer, hydrogenated product of the block copolymer, acrylonitrile-butadiene copolymer, isoprene-butadiene copolymer, etc. Diene rubber, ethylene-propylene random copolymer or block copolymer, polyisoprene, ethylene and α-olefin copolymer, ethylene-unsaturated such as ethylene-methacrylate, ethylene-butyl acrylate Copolymers with carboxylates, acrylic ester-butadiene copolymers, acrylic elastic polymers such as butyl acrylate-butadiene copolymers, copolymers of ethylene and fatty acid vinyl such as ethylene-vinyl acetate , Ethylene-propylene-hexadiene copolymer, etc. Len - propylene nonconjugated Jienta - polymer -, butylene - Isoburen copolymers, chlorinated polyethylene and the like, may be to use them in one or two or more thereof. Preferred rubbery polymers are diene rubber, ethylene-propylene non-conjugated diene polymer, and acrylic elastic polymer, and polybutadiene and styrene-butadiene copolymers are preferably used.

There is no restriction | limiting in particular in the composition ratio of each component of said (a), (b), (c), It can adjust according to a use. In addition to the components (a), (b), and (c) described above, the copolymer (B-1) does not impair the purpose of the present invention. Can be used in a range.

Examples of such copolymerizable monomers include α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl ( Α, β-unsaturated carboxylic acid esters such as (meth) acrylate, 2-ethyl (meth) acrylate, 2-ethylhexyl methacrylate; α, β-unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride; Monomers of α, β-unsaturated dicarboxylic acids such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, and N-o-chlorophenylmaleimide; Can be used alone or in combination of two or more.

(B-2) The copolymer is composed of the above-mentioned (a) aromatic vinyl monomer component and (b) vinyl cyanide monomer component, preferably SAN resin (styrene-acrylonitrile copolymer). Is used. (B-2) A copolymer contributes to the improvement of the moldability (fluidity) of the obtained flame-retardant thermoplastic resin composition.

There is no restriction | limiting in particular in the composition ratio of each component of said (a), (b), Although it can adjust according to a use, Preferably, it is based on (B-2) copolymer (a) component Is 95 to 50% by weight, component (b) is 5 to 50% by weight, more preferably (a) is 90 to 65% by weight, and (b) is 10 to 35% by weight. In addition to the components (a) and (b), a monomer that can be copolymerized with these components is used in the copolymer (B-2) within a range that does not impair the object of the present invention. be able to.

Examples of such copolymerizable monomers include α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl ( Α, β-unsaturated carboxylic acid esters such as (meth) acrylate, 2-ethyl (meth) acrylate, 2-ethylhexyl methacrylate; α, β-unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride; Monomers of α, β-unsaturated dicarboxylic acids such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, and N-o-chlorophenylmaleimide; Can be used alone or in combination of two or more.

The (C) phosphate ester flame retardant used in the present invention is a compound represented by the following general formula (1).
General formula (1)

In the above general formula, Ar 1, Ar 2, Ar 3 and Ar 4 are the same or different monovalent aromatic groups, and examples thereof include a phenyl group, a cresyl group, a xylyl group, and a t-butylphenyl group. X is an aromatic group derived from divalent phenols, and includes catechol, resorcinol, hydroquinol, 4-t-butylcatechol, 2-tert-butylhydroquinone, bisphenol A, bisphenol S sulfide, bisphenol F, Bis (4-hydroxyphenyl) sulfone, bis (3,5 dimethyl-4-hydroxylphenyl) sulfone, etc. are mentioned. These divalent phenols are preferably resorcinol, hydroquinol, and bisphenol A, and particularly, resorcinol and bisphenol A are preferred.

  Examples of (C) phosphate ester flame retardants include phenyl resorcin polyphosphate, cresyl resorcin polyphosphate, phenyl cresyl resorcin polyphosphate, phenyl hydroquinone polyphosphate, cresyl hydroquinone polyphosphate, phenyl cresyl. Hydroquinone polyphosphate, phenyl 2,2-bis (4-oxyphenyl) propane (: bisphenol A type) polyphosphate, cresyl 2,2-bis (4-oxyphenyl) propane (: bisphenol A type) poly Phosphate, phenyl-cresyl-2,2-bis (4-oxyphenyl) propane (: bisphenol A type) polyphosphate, xylyl resorcin polyphosphate, phenyl, pt-butylphenyl reso Shin polyphosphate, phenyl-isopropylphenyl resorcin polyphosphate, cresyl xylyl resorcinol polyphosphate, phenyl-isopropylphenyl-diisopropylphenyl resorcinol polyphosphate, and the like. These are easily available as commercially available products such as CR741, CR733S, PX-200, etc. manufactured by Daihachi Chemical Industry Co., Ltd.

  (C) The compounding quantity of a phosphate ester type flame retardant is 2-25 weight part with respect to 100 weight part of resin components which consist of (A) polycarbonate resin and (B) rubber reinforcement | strengthening styrene resin. When the blending amount is less than 2 parts by weight, sufficient flame retardancy cannot be obtained, and when it exceeds 25 parts by weight, the mechanical properties and heat resistance are greatly impaired. Preferably it is 5-21 weight part, More preferably, it is the range of 8-18 weight part.

(D) As a silicone compound having a branched main structure and an organic functional group consisting of an aromatic group, or consisting of an aromatic group and a hydrocarbon group (excluding an aromatic group), the following general formula (2) As shown in FIG.
General formula (2)

Here, R1, R2, and R3 represent main chain organic functional groups, and X represents a terminal functional group.
That is, it has a T unit (RSiO _1.5 ) and / or a Q unit (SiO _2.0 ) as a branch unit. These preferably contains more than 20 mol% of the total siloxane units _{(R 3~0 SiO 2~0.5).} (R represents an organic functional group.) In addition, the (D) silicone compound preferably contains 20 mol% or more of aromatic groups among the organic functional groups contained. The aromatic group contained is phenyl, biphenyl, naphthalene or a derivative thereof, but a phenyl group can be preferably used.

  (D) Of the organic functional groups in the silicone compound attached to the main chain or branched side chain, the organic group other than the aromatic group is preferably a hydrocarbon group having 4 or less carbon atoms, and preferably a methyl group. Can be used. Further, the terminal group is preferably one kind selected from methyl group, phenyl group and hydroxyl group, or a mixture of these two kinds to three kinds.

  (D) The average molecular weight (weight average) of the silicone compound is preferably 3000 to 500000, and more preferably 5000 to 270000.

  (D) The compounding quantity of a silicone compound is 0.01-6 weight part with respect to 100 weight part of resin components which consist of (A) polycarbonate resin and (B) rubber-reinforced styrene resin. If the blending amount is outside the range, the flame retardant effect is insufficient in any case, which is not preferable. More preferably, it is 2 to 4 parts by weight.

The (E) polytetrafluoroethylene-containing mixed powder used in the present invention is composed of polytetrafluoroethylene particles having a particle size of 10 μm or less and an organic polymer, and polytetrafluoroethylene has a particle size of Those not exceeding 10 μm and not forming aggregates are preferred. Furthermore, from the viewpoint of dispersibility when blended with a thermoplastic resin, in a dispersion obtained by mixing an aqueous dispersion of polytetrafluoroethylene particles having a particle diameter of 0.05 to 1.0 μm and an aqueous dispersion of organic polymer particles In addition, a polymer obtained by polymerizing a vinyl monomer and then pulverizing by coagulation or spray drying is preferably used. The (E) polytetrafluoroethylene-containing mixed powder used for obtaining the (E) polytetrafluoroethylene-containing mixed powder according to the present invention is an emulsion polymerization using a fluorine-containing surfactant. It is obtained by polymerizing tetrafluoroethylene monomer.

  Fluorine-containing olefins such as hexafluoropropylene, chlorotrifluoroethylene, fluoroalkylethylene, and perfluoroalkyl vinyl ether as copolymerization components in the emulsion polymerization of polytetrafluoroethylene particles as long as the properties of polytetrafluoroethylene are not impaired. Fluorine-containing alkyl (meth) acrylates such as perfluoroalkyl (meth) acrylate can be used. The content of the copolymer component is preferably 10% by weight or less with respect to tetrafluoroethylene.

  Commercially available raw materials for polytetrafluoroethylene particle dispersions include: Fullon AD-1 and AD-936 manufactured by Asahi Glass Fluoropolymer, Polyflon D-1 and D-2 manufactured by Daikin Industries, Ltd., and Teflon manufactured by Mitsui DuPont Fluorochemical Co., Ltd. 30J etc. can be mentioned as a representative example.

  (E) The organic polymer particle aqueous dispersion used for obtaining the polytetrafluoroethylene-containing mixed powder can be obtained by polymerizing a vinyl monomer by a known method such as emulsion polymerization.

  The vinyl monomer used to obtain the organic polymer particle aqueous dispersion, and the polytetrafluoroethylene particle aqueous dispersion having a particle diameter of 0.05 to 1.0 μm and the organic polymer particle aqueous dispersion were mixed. Although it does not restrict | limit especially as a vinyl monomer polymerized in a dispersion liquid, it should have high affinity with the resin component (A) and / or (B) of this invention from a dispersible viewpoint. Is preferred.

  Specific examples of these vinyl monomers include styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, t-butylstyrene, o-ethylstyrene, p-chlorostyrene, o-chlorostyrene, 2, Aromatic vinyl monomers such as 4-dichlorostyrene, p-methoxystyrene, o-methoxystyrene, 2,4-dimethylstyrene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, Butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, cyclohexyl acrylate, cyclohexane methacrylate (Meth) acrylic acid ester monomers such as xylyl; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; α, β-unsaturated carboxylic acids such as maleic anhydride; N-phenylmaleimide, N-methylmaleimide, Maleimide monomers such as N-cyclohexylmaleimide; Epoxy group-containing monomers such as glycidyl methacrylate; Vinyl ether monomers such as vinyl methyl ether and vinyl ethyl ether; Vinyl carboxylates such as vinyl acetate and vinyl butyrate Body; α-olefin monomers such as ethylene, propylene, and isobutylene; and diene monomers such as butadiene, isoprene, and dimethylbutadiene. These monomers can be used alone or in admixture of two or more.

  Among these monomers, (A) from the viewpoint of affinity with the polycarbonate resin, one or more selected from the group consisting of aromatic vinyl monomers and vinyl cyanide monomers is preferable. Mention may be made of monomers containing 30% by weight or more of monomers. Particularly preferred is a monomer containing 30% by weight or more of one or more monomers selected from the group consisting of styrene and acrylonitrile.

  (E) The content ratio of polytetrafluoroethylene in the mixed powder containing polytetrafluoroethylene is preferably 0.1% by weight to 90% by weight. If it is less than 0.1% by weight, the effect of improving flame retardancy becomes insufficient, and if it exceeds 90% by weight, the surface appearance may be adversely affected.

  (E) The polytetrafluoroethylene-containing mixed powder is poured into hot water in which a metal salt such as calcium chloride or magnesium sulfate is dissolved, salted out and solidified, or dried. Can be pulverized.

  While ordinary polytetrafluoroethylene fine powder becomes an aggregate of 100 μm or more in the process of recovering as a powder from the state of a particle dispersion, it is difficult to uniformly disperse it in a thermoplastic resin. In addition, the polytetrafluoroethylene-containing mixed powder (E) used in the present invention is extremely excellent in dispersibility because the polytetrafluoroethylene alone does not form a domain having a particle diameter exceeding 10 μm. As a result, in the thermoplastic resin composition of the present invention, polytetrafluoroethylene is efficiently made into fine fibers in the resin component, and the flame retardancy is excellent, and the surface property and impact property are also excellent.

  (E) The blending amount of the polytetrafluoroethylene-containing mixed powder is based on 100 parts by weight of a resin component consisting of (A) 1 to 99% by weight of a polycarbonate resin and (B) 99 to 1% by weight of a rubber-reinforced styrene resin. 0.05 to 2 parts by weight. If it is less than 0.05 part by weight, the effect of preventing dripping is inferior, so that it is difficult to obtain flame retardancy. On the other hand, if it exceeds 2 parts by weight, impact resistance, surface appearance and the like are lowered, which is not preferable. Preferably it is 0.1-1.5 weight part, More preferably, it is 0.6-1.0 weight part.

  Examples of the (F) epoxy stabilizer used in the present invention include epoxidized soybean oil, epoxidized linseed oil, phenyl glycidyl ether, allyl glycidyl ether, t-butylphenyl glycidyl ether, and 3,4-epoxycyclohexylmethyl-3. ', 4'-epoxycyclohexylcarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3', 4'-epoxy-6'-methylcyclohexylcarboxylate, 2,3-epoxycyclohexylmethyl-3 ', 4 '-Epoxycyclohexylcarboxylate, 4- (3,4-epoxy-5-methylcyclohexyl) butyl-3', 4'-epoxycyclohexylcarboxylate, 3,4-epoxycyclohexylethylene oxide, cyclohexylmethyl-3,4-ethylene Xylcyclohexylcarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6'-methylsiloxycarboxylate, bisphenol A diglycidyl ether, tetrabromobisphenol A glycidyl ether, diglycidyl ester of phthalic acid, hexahydrophthalic acid Diglycidyl ester, bis-epoxy dicyclopentadienyl ether, bis-epoxy ethylene glycol, bis-epoxy cyclohexyl adipate, butadiene diepoxide, tetraphenylethylene epoxide, octyl epoxy talate, epoxidized polybutadiene, 3,4-dimethyl -1,2-epoxycyclohexane, 3,5-dimethyl-1,2-epoxycyclohexane, 3-methyl-5-t-butyl-1,2-epoxycyclohexa , Octadecyl-2,2-dimethyl-3,4-epoxycyclohexylcarboxylate, N-butyl-2,2-dimethyl-3,4-epoxycyclohexylcarboxylate, cyclohexyl-2-methyl-3,4-epoxycyclohexylcarboxylate , N-butyl-2-isopropyl-3,4-epoxy-5-methylcyclohexylcarboxylate, octadecyl-3,4-epoxycyclohexylcarboxylate, 2-ethylhexyl-3 ′, 4′-epoxycyclohexylcarboxylate, 4 , 6-Dimethyl-2,3-epoxycyclohexyl-3 ', 4'-epoxycyclohexylcarboxylate, 4,5-epoxytetrahydrophthalic anhydride, 3-t-butyl-4,5-epoxytetrahydrophthalic anhydride, die -4,5-epoxy-cis-1,2-cyclohexyl dicarboxylate, di-n-butyl-3-tert-butyl-4,5-epoxy-cis-1,2-cyclohexyl dicarboxylate It is done.

  Of these, epoxy soybean oil and alicyclic epoxy resins are preferred, and in particular, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate or bis- (3,4-epoxycyclohexyl) adipate is preferred. Used for. This alicyclic epoxy stabilizer is easily available as R-51 manufactured by Asahi Denka Kogyo Co., Ltd., Celoxide 2021P manufactured by Daicel Chemical Industries, Ltd., or Celoxide 2080. Examples of the epoxy soybean oil include Adeka Sizer O-130P manufactured by Asahi Denka Kogyo Co., Ltd.

  When such an (F) epoxy stabilizer is contained, the heat-and-moisture resistance characteristics of the resin composition can be improved. The blending amount of the (F) epoxy stabilizer of the present invention is 0.01 to 2 parts by weight with respect to 100 parts by weight of the resin component composed of (A) polycarbonate resin and (B) rubber-reinforced styrene resin. If the blending amount is less than 0.01 parts by weight, it is not preferable because improvement in wet heat deterioration is hardly observed. On the other hand, if the blending amount exceeds 2%, it is not preferable because it may cause problems such as a significant decrease in mechanical strength (impact strength) of the composition and mold contamination during molding. Preferably it is 0.1-1 weight part, More preferably, it is the range of 0.2-0.5 weight part.

  In mixing the components (A), (B), (C), (D), (E), and (F) of the present invention, the form and order are not limited. For example, a method of adding (B), (C), (D), (E), (F) to (A) polycarbonate resin in an organic solvent solution, powder, pellet state, or (A) polycarbonate resin in a molten state , (B), (C), (D), (E), and (F). In addition, a method in which all the components are mixed at once with a tumbler, ribbon blender, high-speed mixer, or the like, a method in which arbitrary components are once mixed with these mixers, and then the remaining components are blended. These mixtures are easily melt-kneaded and pelletized using a normal single-screw or twin-screw extruder.

  In the flame-retardant thermoplastic resin composition of the present invention, a known additive such as a phenol-based or phosphorus-based heat stabilizer [2,6-di-t-butyl-4-methylphenol, 2- (1-methyl Cyclohexyl) -4,6-dimethylphenol, 4,4'-thiobis- (6-tert-butyl-3-methylphenol), 2,2-methylenebis- (4-ethyl-6-tert-methylphenol), n -Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, tris (2,4-di-t-butylphenyl) phosphite, 4,4'-biphenylenediphosphinic acid tetrakis- ( 2,4-di-tert-butylphenyl), etc.], UV absorber [pt-butylphenyl salicylate, 2,2′-dihydroxy-4-methoxybenzophenone, 2- ( '-Hydroxy-4'-n-octoxyphenyl) benzotriazole, etc.], lubricant [paraffin wax, n-butyl stearate, synthetic beeswax, natural beeswax, glycerin monoester, montanic acid wax, polyethylene wax, pentaerythritol tetrastearate Rates, etc.], colorants [eg titanium oxide, carbon black, fluorescent brighteners, etc.], fillers [calcium carbonate, clay, silica, glass fibers, glass spheres, glass flakes, organometallic salts (potassium perfluorobutanesulfonate) , Compounds such as sodium paratoluenesulfonate), carbon fiber, talc, mica, various whiskers, etc.], spreading agents [liquid paraffin, etc.], and other thermoplastic resins such as polyamide, polyethylene terephthalate, polybutylene terephthalate, Non Polyesters, polyphenylene ethers, polymethylmethacrylates, and various impact resistance improvers (polybutadiene, polyacrylates, ethylene / propylene rubbers, etc.) are graft polymerized with compounds such as methacrylates, styrene, acrylonitrile, etc. Rubber reinforced resin, etc.) can be added as necessary.

  In order to describe the present invention more specifically, examples will be described below. However, the present invention is not limited by these.

Polycarbonate resin: Caliber 200-13, manufactured by Sumitomo Dow
(Viscosity average molecular weight: 21000, hereinafter abbreviated as “PC”)
ABS resin: Santac AT07 manufactured by A & L Japan
(Bulk-polymerized ABS, hereinafter abbreviated as “ABS”)
Phosphate ester flame retardant:
-ADK STAB FP500 manufactured by Asahi Denka Kogyo Co., Ltd.
(1,3-phenylenebis (dixylenyl phosphate), hereinafter abbreviated as “P-1”.)
-ADK STAB FP700 manufactured by Asahi Denka Kogyo Co., Ltd.
(Bisphenol A bis (diphenyl phosphate), hereinafter abbreviated as “P-2”.)
Silicone compounds:
The silicone compound was produced according to a general production method. That is, an appropriate amount of diorganodichlorosilane, monoorganotrichlorosilane and tetrachlorosilane, or a partially hydrolyzed condensate thereof, dissolved in an organic solvent, hydrolyzed by adding water, and partially condensed silicone compound Then, triorganochlorosilane was added and reacted to terminate the polymerization, and then the solvent was separated by distillation or the like. The structural characteristics of the silicone compound synthesized by the above method are as follows:
・ D / T / Q unit ratio of main chain structure: 40/60/0 (molar ratio)
-Ratio of phenyl group in all organic functional groups (*): 60 mol%
-Terminal group: methyl group only-Weight average molecular weight (**): 15000
*: The phenyl group is first contained in the T unit in the silicone containing the T unit, and the remaining D group is contained in the D unit. When the phenyl group is attached to the D unit, the one attached is preferential, and when the phenyl group remains, two are attached. Except for the terminal group, the organic functional group is a methyl group except for the phenyl group.
**: Weight average molecular weight is two significant digits.
Mixed powder containing polytetrafluoroethylene:
Metablene A3800 manufactured by Mitsubishi Rayon Co., Ltd.
(PTFE content: 50%, hereinafter abbreviated as “PTFE”)
Epoxy stabilizer:
Adeka Sizer O-130P manufactured by Asahi Denka Kogyo Co., Ltd. (hereinafter abbreviated as “EPO”)

  After blending based on the blending ratio of each component shown in Tables 1 and 2, it was dry blended and granulated using a 37 mm twin screw extruder (KTX37) manufactured by Kobe Steel Co., Ltd. under a melting temperature of 240 ° C. . Each test piece was created from the obtained pellets under the condition of a cylinder set temperature of 260 ° C. by an injection molding machine (J100EC5) manufactured by Japan Steel Works, and the following evaluations were performed. The evaluation results are shown in Table 1.

1. Flame retardance:
According to UL94, the flame retardance (self-extinguishing property) was measured with a test piece having a thickness of 1.6 mm. The test piece is allowed to stand for 48 hours in a temperature-controlled room with a temperature of 23 ° C and a humidity of 50%. Was evaluated. UL94V is a method for evaluating flame retardance from the afterflame time and drip properties after indirect flames of a burner for 10 seconds on a test piece of a predetermined size held vertically, and is divided into the following classes: .

  The after-flame time shown above is the length of time that the specimen keeps flaming combustion after moving the ignition source away, and the ignition of cotton by drip is about 300 mm below the lower end of the specimen. It is determined by whether the marking cotton is ignited by a drip from the specimen. As a standard for evaluation, V-0 was accepted in the 1.6 mm thickness test.

2. Impact resistance:
The notched Izod impact strength was measured according to ASTM D-256, and an impact value of 35 kg · cm / cm or more was regarded as acceptable. The thickness is 3.2 mm.

3. Deflection temperature under load:
The deflection temperature under load (test piece thickness: 6.4 mm) was measured according to ASTM D648. 80 degreeC or more was set as the pass.

4). Surface appearance:
The surface appearance of a color chip having a size of 70 × 55 × 3 mm was visually confirmed.
As a result, a good surface appearance was determined to be acceptable (◯), and a defective surface was rejected (×).

5. 3. Moisture and heat degradation resistance under pressure conditions of 120 ° C. × 100% relative humidity using a pressure cooker (TPC-411) manufactured by Tabay Espec. The color chip was exposed for 48 hours. And polycarbonate resin was fractionated from the test piece before and behind exposure, and the molecular weight was measured by the solution viscosity method using a methylene chloride. (Viscosity tube: Canon Fenceke viscosity tube, measuring temperature: 25 ° C.) The polycarbonate molecular weight of the test piece after the vapor exposure test was determined to be 13,000 or more.

  As shown in Table 2, when the composition satisfied the constitution of the present invention (Examples 1 to 5), the standard was satisfied over all the performances.

On the other hand, as shown in Table 3, when the composition did not satisfy the constitution of the present invention (Comparative Examples 1 to 5), it had some defects in any case.
Although the comparative example 1 is a case where the compounding quantity of the silicone compound of this invention is still lower than the minimum of a prescription | regulation range, flame retardance became disqualified.
Although the comparative example 2 is a case where the compounding quantity of the phosphate ester of this invention exceeds the upper limit of a prescription | regulation range, impact resistance and heat resistance became disqualified.
Although the comparative example 3 is a case where the compounding quantity of the polytetrafluoroethylene containing mixed powder of this invention is still lower than the minimum of a regulation range, the flame retardance became disqualified.
Although the comparative example 4 is a case where the compounding quantity of the polytetrafluoroethylene containing mixed powder of this invention exceeds the upper limit of a prescription | regulation range, impact resistance and surface appearance failed.
Although the comparative example 5 is a case where the compounding quantity of the epoxy-type stabilizer of this invention is still lower than the minimum of a regulation range, the heat-and-moisture resistant property failed.

Claims (1)

(A) 2 to 25 parts by weight of a phosphoric ester-based flame retardant with respect to 100 parts by weight of a resin component consisting of 1 to 99% by weight of a polycarbonate resin and (B) 99 to 1% by weight of a rubber-reinforced styrene resin (D) 0.01-6 parts by weight of a silicone compound in which the main chain has a branched structure and the organic functional group contained is composed of an aromatic group, or is composed of an aromatic group and a hydrocarbon group (excluding an aromatic group) And (E) 0.05-2 parts by weight of a polytetrafluoroethylene-containing mixed powder and (F) 0.01-2 parts by weight of an epoxy-based stabilizer.