Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
  • C08L25/02—Homopolymers or copolymers of hydrocarbons
  • C08L25/04—Homopolymers or copolymers of styrene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C08L27/18—Homopolymers or copolymers or tetrafluoroethene

Definitions

• the present invention relates to a polycarbonate resin composition and an injection-molded article, and more particularly, to a polycarbonate resin composition which is excellent in mold releasability, significantly improves the appearance of a molded article, and has excellent weld strength and surface impact strength. And injection molded products.
• Polycarbonate resin is widely used in various fields such as office automation (OA) equipment, electrical and electronic equipment, automobiles, and construction, due to its excellent impact resistance, heat resistance, and electrical properties. .
• OA office automation
• electrical and electronic equipment electrical and electronic equipment
• automobiles and construction, due to its excellent impact resistance, heat resistance, and electrical properties.
• polycarbonate resins have problems that the molding temperature is high and the melt fluidity is poor.
• Polycarbonate resins are molded into various molded products by injection molding, similar to general thermoplastic resins.
• the molded product when the molded product is a part of OA equipment such as copiers and Laattas, electrical and electronic equipment, and housing, etc., the shape becomes complicated, and irregularities such as ribs and bosses are formed. In some cases, it may be difficult to remove the molded product from the mold because it is formed into a molded product. Deformation occurs, whitening and distortion remain, and the dimensional accuracy, strength, and appearance of the molded product deteriorate. '
• polycarbonate resin is generally a self-extinguishing resin
• these fields of application there are fields that require a high degree of flame retardancy, mainly in the fields of OA equipment and electric and electronic equipment, and improvements are being made by adding various flame retardants.
• ABS resin atalylrotrilu-butadiene-styrene resin
• AS resin acrylonitrile-styrene
• Japanese Patent Application Laid-Open No. 61-51545 discloses-(A) aromatic polycarbonate resin, (B) ABS resin, (C) AS resin, and '(D) halogenated A thermoplastic resin composition comprising a compound, (E) a phosphate ester, and (F) a polytetrafluoroethylene component is described.
• Japanese Unexamined Patent Publication No. Hei 2-332154 discloses (A) an aromatic polycarbonate resin, (B) an ABS resin, (C) an AS resin, (D) a phosphate ester, and (E) polytetrafluoroethylene.
• a flame-retardant, high-impact polycarbonate molding composition comprising the components is described.
• Japanese Patent Application Laid-Open No. 8-2399565 discloses that (A) an aromatic polycarbonate, (B) an impact-resistant polystyrene resin containing a rubber-like elastic material, (C) a halogen-free phosphate ester, and (D) a core shell. It describes a polycarbonate resin composition containing a type graph rubber-like elastic material and (D) talc.
• parts and housings are used to reduce the weight and thickness of the equipment, or form factors, that is, ribs and bosses on molded products It is required to be able to cope with complicated and large-sized structures such as fine irregularities and lattice structures ''
• Japanese Patent Publication No. 61-41939 discloses a molding composition containing an ester of a specific alcohol and an acid.
• this publication does not specifically disclose the mixing of the styrene resin with the polycarbonate resin and the flame retardancy.
• JP-A-8-48844 discloses that (A) polycarbonate, (B) styrene resin, (C) resorcinol polyphosphate compound, and (D) polytetrafluoroethylene. (E) an average molecular weight of 100 to 50,000, a saturated fatty acid ester-based resin of 0.1 to 2 parts by weight, and (F) an average molecular weight of 100 parts by weight of the resin composition. 1 0 0 0 to 3 0 0 0 Poly A flame-retardant resin composition comprising ethylene wax in an amount of 0.01 to 2 parts by weight and having excellent releasability is described.
• Japanese Patent Application Laid-Open No. 2000-63649 discloses a thermoplastic composition having improved releasability and capable of being easily molded even in a thin and complicated shape. Also, there is a possibility that silver-like appearance defects may occur, or surface layer peeling may occur when injection molding is performed at high speed.
• the surface impact strength may vary, leading to brittle rupture.
• a technique of adding a polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene particles and organic polymer particles to a polycarbonate resin or a thermoplastic resin is disclosed in Japanese Patent Application Laid-Open No. H10-3031. 0707, JP-A-11-29679, JP-A-2000-143966, JP200-2977187, etc. .
• the present invention provides a flame-retardant, excellent mold-releasing, and injection-molded polycarbonate resin molded article used in OA equipment, electric / electronic equipment, automobiles, etc., which is thinner and more complex. It is an object of the present invention to provide a polycarbonate resin composition and an injection-molded article, which have significantly improved appearance of the molded article, and have excellent ⁇ eld strength and surface impact strength. Disclosure of the invention
• thermoplastic resins and the like In addition to the moldability and physical properties of the composition in which the composition was blended with the polycarbonate resin at various ratios, the combination with various additives was studied diligently with respect to the mold releasability.
• the styrene resin is selected from high impact polystyrene resin (HIPS), acrylonitrile styrene copolymer (AS resin), and acrylonitrile relubutadiene-styrene copolymer (ABS resin).
• HIPS high impact polystyrene resin
• AS resin acrylonitrile styrene copolymer
• ABS resin acrylonitrile relubutadiene-styrene copolymer
• the difficult agent is at least one compound selected from a phosphate ester, an organic alkali metal salt, an organic alkaline earth metal salt and a silicone compound.
• injection-molded article according to the above item 8, wherein the injection-molded article is a housing or a part of a device A, an electric device or an electronic device.
• the polycarbonate resin as the component (A) in the polycarbonate resin composition of the present invention is not particularly limited, and may be various ones. Usually, an aromatic polycarbonate produced by reacting a divalent phenol with a carbonate precursor can be used.
• a product produced by reacting a divalent phenol with a carbonate precursor by a solution method or a melting method that is, a reaction of a divalent phenol with phosgene, or a transesterification method of a divalent phenol with diphenyl carbonate, etc.
• a solution method or a melting method that is, a reaction of a divalent phenol with phosgene, or a transesterification method of a divalent phenol with diphenyl carbonate, etc.
• phenols can be mentioned, and in particular, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), bis (4-hydroxyphenyl) methane, 1,1-bis ( 4—Hydroxyfene Nore) ethane, 2,2-bis (4-hydroxy3,5'-dimethylphenole), propane, 4,4,1-dihydroxydiphenyl, bis (4-hydroxythifenole) cycloanolecan; bis (4-Hydroxyphen-nore) Oxide, Bis (4-Hydroxypheninole) Snorefide, Bis (4-Hydroxyphenil) Sulfone, Bis (4-Hydroxypheninole) Snorefoxide, Bis
• preferred divalent phenols are bis (hydroxyphenyl) alkanes, particularly those containing bisphenol A as a main raw material.
• Examples of the carbonate precursor include carbonyl halide, carbonyl ester, and haloformate. Specific examples thereof include phosgene, diphenol monoformate of divalent phenol, dipheninocarbonate, dimethinorecarbonate, and getylcarbonate. Etc.
• examples of the divalent phenol include hydroquinone, resonoresin, and force tecole.
• divalent phenols may be used alone or in combination of two or more.
• the polycarbonate resin may have a branched structure.
• branching agent examples include 1,1,1-tris (4-hydroxyphenyl) ethane, a, ⁇ ′, and tris (4-hydroxy).
• (Droxyphenyl) 1, 3, 5 — Triisop Oral Pinolebenzene, phloroglysin, trimellitic acid, isatin bis ( ⁇ -cresol), etc.
• Alkyl phenol or the like is used as a terminal stopper for controlling the molecular weight.
• the number of carbon atoms in the alkyl group of the phenol is preferably from 0 to 30, and for high fluidity, the number of carbon atoms is preferably 12 or more.
• phenomena include phenomena, p-cresole, p-tert-butynolephene, p-tert-octenolephene, p-minolenofenore, and p-noninolefenore.
• Takoshinorefenol and triacontinolefenol can be exemplified. ''
• These may be one kind or a mixture of two or more kinds.
• the polycarbonate resin used in the present invention may be a copolymer having a polycarbonate part and a polyorganosiloxane part, or a polycarbonate resin containing this copolymer.
• a polyester-polycarbonate obtained by performing a polymerization reaction of a polycarbonate in the presence of a bifunctional carboxylic acid such as terephthalic acid or an ester precursor such as an ester-forming derivative thereof is used. It may be a resin.
• various polycarbonate resins can be used by appropriately mixing them.
• the polycarbonate resin of the component (A) used in the present invention preferably has a viscosity-average molecular weight of 100,000 to 100,000 from the viewpoint of mechanical strength and moldability. Those with a range of 13, 000 to 25, 000 are preferred.
• the styrene-based resin of the component (B) in the polycarbonate resin composition of the present invention styrene, shed over monovinyl aromatic single-mer 2 0-1 0 0 mass 0/0 methyl styrene, acrylonitrile, methacrylonitrile Tali nitrile such uninstall vinylic monomer 0-6 0% by weight, and copolymerizable with these maleimidyl de, (meth) other vinyl monomer of methyl acrylate 0-5 0 weight 0/0
• polystyrene examples include polystyrene (GPPS), acrylonitrile-styrene copolymer (AS resin), and the like.
• GPPS polystyrene
• AS resin acrylonitrile-styrene copolymer
• styrene resin a rubbery polymer-modified styrene resin can be preferably used.
• the modified styrene resin is preferably an impact-resistant styrene resin in which at least a styrene monomer is graft-polymerized to a rubbery polymer.
• the rubber-modified styrene resin examples include impact-resistant polystyrene (HIPS) in which styrene is polymerized in a rubber polymer such as polybutadiene, ABS resin in which acrylonitrile and styrene are polymerized in polybutadiene, and polybutadiene.
• HIPS impact-resistant polystyrene
• ABS resin in which acrylonitrile and styrene are polymerized in polybutadiene
• polybutadiene There are MBS resins and the like in which methyl methacrylate and styrene are polymerized.
• Two or more rubber-modified styrene resins can be used in combination, and they can also be used as a mixture with the rubber-unmodified styrene resin described above. it can.
• the content of the rubbery polymer in the rubber-modified styrenic resin is, for example, 2 to 50% by mass, and preferably 5 to 30% by mass.
• the proportion of the rubbery polymer is less than 2% by mass, the impact resistance becomes insufficient, and when it exceeds 50% by mass, the thermal stability decreases, the melt fluidity decreases, and the gel Problems such as generation and coloring may occur.
• the rubbery polymer examples include a rubbery polymer containing polybutadiene, acrylate and / or methacrylate, styrene-butadiene-styrene (SBS) rubber, styrene-butadiene rubber (SBR), butadiene —Acrynole rubber, isoprene rubber, isoprene styrene rubber, isoprene-acrylic rubber, ethylene-propylene rubber and the like.
• SBS styrene-butadiene-styrene
• SBR styrene-butadiene rubber
• butadiene —Acrynole rubber isoprene rubber, isoprene styrene rubber, isoprene-acrylic rubber, ethylene-propylene rubber and the like.
• polybutadiene particularly preferred is polybutadiene.
• the polybutadiene used here is a low cis polybutadiene (eg, 1, 2-vinylinole 1 to 30 monooles 0 / o, 1,4-monocis bond containing 30 to 42 monoles 0 / o), high cis polybutadiene (for example, 1,2-bule bond 20 mol% Hereinafter, those containing 78 mol% or more of 1,4-cis bonds) may be used, or a mixture thereof may be used.
• a low cis polybutadiene eg, 1, 2-vinylinole 1 to 30 monooles 0 / o, 1,4-monocis bond containing 30 to 42 monoles 0 / o
• high cis polybutadiene for example, 1,2-bule bond 20 mol%
• those containing 78 mol% or more of 1,4-cis bonds may be used, or a mixture thereof may be used.
• impact-resistant polystyrene resin HIPS
• acrylonitrile-styrene copolymer AS resin
• acrylonitrile-butadiene-styrene copolymer ABS resin
• MS resin methyl methacrylate Styrene copolymer
• MVS resin methyl methacrylate-butadiene-styrene copolymer
• AS resin acrylonitrile-methyl acrylate monostyrene copolymer
• AES resin acrylonitrile Mono- (ethylene / propylene-gen) -mono-methyl acrylate-co-styrene
• HIPS impact-resistant polystyrene resin
• AS resin atalylonitrile-co-styrene copolymer
• ABS resin acrylonitrile Tolyl-butadiene-styrene copolymer
• styrene-based resin forms a polymer alloy with the polycarbonate resin
• a bulk polymerized product is preferred.
• the polycarbonate resin composition of the present invention is basically a composition comprising (A) a polycarbonate resin and (B) a styrene-based resin.
• both ⁇ mixing ratio (A) polycarbonate resin 6 0-9 7 mass 0/0, preferably from 7 0-5 mass 0/0, '(B) a styrene resin is 3 to 40 mass% Preferably, it is 5 to 30% by mass.
• the content of the polycarbonate resin (A) is less than 60% by mass, the flame retardancy, weld strength, surface impact strength, etc. may not be sufficient. If the content exceeds 97% by mass, the fluidity and heat resistance may be reduced. Solvent properties decrease.
• the content of the styrene resin (B) is less than 3% by mass, the fluidity and solvent resistance may be poor. It may be difficult to achieve one or more.
• the polytetrafluoroethylene of the present invention has a particle size of 10 ⁇ m or less, and preferably 0.05 to 1.0 Om.
• the polytetrafluoroethylene particles are dispersed in water containing an emulsifier, etc., and the aqueous dispersion of polytetrafluoroethylene particles is obtained by emulsifying a tetrafluoroethylene monomer by emulsion polymerization using a fluorinated surfactant. It can be obtained by polymerization. .
• Fluorinated olefins such as alkyl vinyl ethers and fluorinated alkyl (meth) acrylates such as perfluoroalkyl (meth) acrylate can be used.
• the content of the copolymer component is preferably 10% by mass or less based on tetrafluoroethylene. .
• the organic polymer particles of the present invention are not particularly limited, but those having an affinity for polycarbonate resin from the viewpoint of the dispersibility of polytetrafluoroethylene when blended into the polycarbonate resin. It is preferable that there is.
• monomers for forming the organic polymer particles include styrene, p-methinolestyrene, 0-methinolestyrene, p-chloronostyrene, o-chloronostyrene, p-methoxystyrene, o -Styrene-based monomers such as methoxystyrene, 2,4-dimethinolestyrene and -methinolestyrene; Methyl acrylate, Methyl methacrylate, Ethyl acrylate, Ethyl methacrylate, Butyl acrylate, Butyl methacrylate, 2-Acetyl hexyl acrylate, 2-Ethyl hexyl methacrylate, Dodecyl acrylate, Metata Acrylonitrile (meth) acrylate monomers such as dodecyl rilate, tridecyl acrylate, tridecyl
• Vinyl cyanide monomers such as butyl methacrylate and vinyl methacrylate; vinyl ether monomers such as butyl methyl ether and vinyl ethyl ether; vinyl carboxylate monomers such as vinyl acetate and butyl butyrate; ethylene, propylene, and isobutylene Etc.
• Gon-based monomers such as butadiene, isoprene, dimethyl butadiene and the like.
• the method for producing the aqueous dispersion of the organic polymer particles of the present invention is not particularly limited, and includes, for example, an emulsion polymerization method using an ionic emulsifier, a soap free emulsion polymerization method using an ionic polymerization initiator, and the like. Can be mentioned.
• any of an anionic emulsifier, a cationic emulsifier and an amphoteric ionic emulsifier can be used.
• nonionic emulsifier can be used in combination with these ionic emulsifiers.
• anionic emulsifiers include fatty acid salts, higher alcohol sulfate salts, liquid fatty oil sulfate salts, aliphatic amine and aliphatic amide sulfates, aliphatic alcohol phosphate esters, and dibasic fatty acid ester sulfones. Examples thereof include acid salts, fatty acid amide sulfonates, alkylaryl sulfonates, and naphthalene sulfonates of formalin condensate.
• the cationic emulsifier include aliphatic amine salts, ammonium salts and alkylpyridinium salts.
• amphoteric emulsifier examples include alkyl betaine.
• ionic polymerization initiator examples include persulfates (eg, potassium persulfate and ammonium persulfate), azobis (isobutyrate-tolylsulfonate), and 4,4′-azobis (4-cyanovaleric acid).
• Polymerization initiator 2,2'-azobis (amidinopropane) dihydrochloride, 2,2,1-azobis [2- (5-methyl-2-imidazoline-1-yl) propane] dihydrochloride, 2,2, Cationic polymerization initiators such as monoazobis [2- (2-imidazolin_2-2-yl) propane] dihydrochloride and 2,2,1-azobisisobutylamidonihydrate .
• the particle diameter d of the organic polymer particles of the present invention is not particularly limited, but from the viewpoint of the stability of the aggregation state with the polytetrafluoroethylene particles, the particle diameter D of the polytetrafluoroethylene particles Is preferably in the range of the following formula.
• the polytetrafluoroethylene-containing mixed powder of the present invention is obtained by mixing a polytetrafluoroethylene particle dispersion and an organic polymer particle dispersion and coagulating or powdering by spray drying. It includes agglomerated particles in which fluorethylene particles and organic polymer particles are aggregated due to a difference in surface charge, and single particles that remain without being agglomerated.
• the agglomerated particles have a structure in which polytetrafluoroethylene particles and organic polymer particles are combined, and there are various morphologies depending on the mixing ratio of both particles and the particle diameter.
• a nonionic emulsifier is added to polytetrafluoroethylene-based particles and a (meth) acrylate unit having an alkyl group having 4 or more Z or carbon atoms. Can be adsorbed on the surface of the (co) produced particles.
• the nonionic emulsifier is not particularly limited, and examples thereof include polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, dialkylphenoxypoly (ethyleneoxy) ethanol, polybutyl alcohol, polyacrylic acid, and alkyl cellulose. it can.
• the polytetrafluoroethylene-containing mixed powder of the present invention is obtained by emulsion polymerization of a monomer having an ethylenically unsaturated bond in a dispersion obtained by mixing the polytetrafluoroethylene particle dispersion and the organic polymer particle dispersion. Then, it can also be obtained by pulverization by solidification or spray drying.
• Examples of the ethylenically unsaturated monomer to be emulsion-polymerized in the mixed dispersion include styrene, p-methynolestyrene, o-methynolestyrene, and p, depending on the use of the mixed powder containing polytetrafluoroethylene.
• —Styrene monomers such as chloronostyrene, o—chlorostyrene, p-methoxystyrene, 0-methoxystyrene, 2,4-methylstyrene, CK-methylstyrene; methyl acrylate, methyl methacrylate, and acrylic acid Ethyl, Ethyl methacrylate, Butyl acrylate, Butyl methacrylate, _2-Ethylhexyl acrylate, _2-Ethylhexyl methacrylate, Dodecyl acrylate, Dodecyl methacrylate, Cyclohexyl acrylate, Methacrylic acid Acrylate monomers such as cyclohexyl; acrylonitrile, methacrylic acid Vinyl cyanide monomers such as lonitrile; vinyl ether monomers such as vinylinolemethyl ether and vinyl ethyl ether; vinyl carboxylate monomers such as vinyl
• the content of polytetrafluoroethylene in the polytetrafluoroethylene-containing mixed powder of the present invention is 0.1 mass 0 /. It is preferably from 90 to 90% by mass, more preferably from 40 to 90% by mass.
• the polytetrafluoroethylene-containing mixed powder of the present invention is obtained by pouring the aqueous dispersion into hot water in which a metal salt such as calcium chloride or magnesium sulfate is dissolved, salting out, coagulating, and then drying, or It can be pulverized by spray drying.
• a metal salt such as calcium chloride or magnesium sulfate
• the polytetrafluoroethylene-containing mixed powder comprising (C) polytetrafluoroethylene particles and organic polymer particles in the polycarbonate resin composition of the present invention is added to prevent dripping and improve the gate appearance.
• the content is 0.05 to 1 part by mass with respect to 100 parts by mass of the total of (A) the polycarbonate resin and (B) the styrene-based resin.
• the content of the polytetrafluoroethylene-containing mixed powder composed of the organic polymer particles is less than 0.05 part by mass, the target flame retardancy is hardly obtained, and if it exceeds 1 part by mass, Flame retardancy may be reduced.
• Examples of the releasing agent of the component (D) in the polycarbonate resin composition of the present invention include higher alcohols, carboxylic esters, polyolefin waxes and polyalkylene glycols.
• Examples of the higher alcohol of the present invention include monohydric alcohols having 6 to 40 carbon atoms. Specifically, octyl alcohol, decyl alcohol, and dode alcohol Shinole alcohol, Tetradecyl alcohol, Hexadesinole alcohol, Octa desinoleone reconole, Icosinoreanorecone, Docosizoleanorecone, Triacontinoleanorecone, Tetracontinoleanorecole Nore, garbet alcohol (carbon number is 20), uren alcohol (carbon number is 30) and the like.
• Examples of the carboxylic acid ester of the present invention include a long-chain carboxylic acid ester of a monohydric or polyhydric alcohol, and specifically, at least one of a monohydric or polyhydric alcohol having 2 to 40 carbon atoms.
• a hydroxyl group forms an ester with a mono- or dicarboxylic acid having 8 to 40 carbon atoms.
• Examples of the monohydric or polyhydric alcohol having 2 to 40 carbon atoms include octyl alcohol, desinole alcohol, dodecinole alcohol, tetradecyl alcohol, hexadecinoleanol, and octadecinoleanol.
• Examples of mono- or dicarboxylic acids having 8 to 40 carbon atoms include octanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, octadecanoic acid, docosanoic acid, tetracosanoic acid, hexacosanoic acid, octacosanoic acid, triacontanic acid, and tetracontantan. Acid, octane diacid, nonanniic acid, decandioic acid and the like.
• carboxylic acid ester of the present invention include: Ota decyl octa, desylate, docosoledocosarate, docosylocota cosanate, ethylene glycolono monooctadecylate, glycerin monooctadecylate, Glycerin didodecylate, glycerin dioctadecylate, glycerin 'trioctadecylate, glycerin tridocosanate, trimethylol lip mouth monooctadecylate, trimethylonolepropanediolet, trimethylolpropane tridecylate Rate, Trimethyl octapropane octadecylate, pentaerythritol monosodium docosylate, pentaerythritol monooctadecylate, pentaerythritol toloctadecylate
• polyolefin wax examples include low-, medium-, and high-density polyethylene waxes and polypropylene waxes.
• polyethylene wax those having a molecular weight of about 1,000 to 5,000 and a melting point in the range of 100 to 120 ° C are preferable.
• tas a molecular weight of 15,000 to 4 (approximately 3000 is preferable. Among them, polyethylene wax is preferable.
• polyalkylene glycol of the present invention examples include polyethylene glycol, polypropylene glycol, and polyethylene glycol glycol, and the like.
• the molecular weight is in the range of 500 to 20000.
• a silicone-based release agent and a bis-amide-based release agent can also be suitably used.
• the above (D) release agents may be used alone or in combination of two or more.
• the content of the (D) release agent in the polycarbonate resin composition of the present invention is 0.05 to 3 parts by mass based on 100 parts by mass of the total amount of (A) the polycarbonate resin and (B) the styrene-based resin. Parts, preferably 0.1 to 2 parts by mass.
• the content of the release agent is less than 0.05 parts by mass, the molded appearance, release properties and surface The impact resistance may not be improved, and if it exceeds 3 parts by mass, the surface impact strength, the green strength and the heat resistance may be reduced.
• the flame retardant of the component (E) in the polycarbonate resin of the present invention includes a phosphorus-based flame retardant, an organic alkali metal salt, an organic alkaline earth metal salt, a silicone-based flame retardant, a halogen-based flame retardant, a nitrogen-based flame retardant, Known materials such as metal hydroxide, red phosphorus, antimony oxide, and expandable graphite can be used according to the purpose.
• halogen-based flame retardants include tetrabromobisphenol A, halogenated polycarbonate and halogenated polycarbonate (co) polymers and their oligomers, (TBA oligomer), decabromodiphenyl ether, (tetrapromobisphenol).
• TSA oligomer halogenated polycarbonate and halogenated polycarbonate (co) polymers and their oligomers
• TSA oligomer halogenated polycarbonate
• decabromodiphenyl ether tetrapromobisphenol
• Epoxy oligomers, halogenated polystyrene, halogenated polyolefin and the like can be exemplified.
• nitrogen-based flame retardant examples include melamine and melamine substituted with an alkyl group or an aromatic group
• metal hydroxide examples include magnesium hydroxide and aluminum hydroxide.
• halogen-based flame retardants have relatively good flame-retardant efficiency, but may generate harmful gases during molding, corrode molds, and emit harmful substances during incineration of molded products, resulting in environmental pollution and safety.
• a flame retardant containing no halogen is preferable.
• Halogen-free phosphorus-based flame retardants include halogen-free organic phosphorus-based flame retardants.
• organic phosphorus flame retardant any organic compound having a phosphorus atom and containing no halogen can be used without any particular limitation.
• a phosphate compound having at least one ester oxygen atom directly bonded to a phosphorus atom is preferably used.
• Halogen-free phosphorus-based flame retardants other than organic phosphorus compounds include Etc.
• the phosphate compound is not particularly limited, and preferably does not contain halogen.
• the following formula (1) is not particularly limited, and preferably does not contain halogen.
• R 1 R 2, 1 3 and 1 4 are each independently, represent a hydrogen atom or an organic group, X represents a divalent or higher organic group, p is 0 or 1, q Is an integer of 1 or more, and r represents an integer of 0 or more.
• the organic group is an alkyl group, a cycloalkyl group, an aryl group, which may or may not be substituted.
• the substituent When substituted, the substituent includes an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylthio group and the like.
• an arylalkoxyalkyl group or the like which is a group obtained by combining these substituents, or an arylsulfuryl group or the like obtained by combining these substituents by bonding with an oxygen atom, a nitrogen atom, a zeo atom, or the like. And the like as a substituent.
• the divalent or higher valent organic group X means a divalent or higher valent group formed by removing one or more hydrogen atoms bonded to a carbon atom from the above organic group. .
• it is derived from an alkylene group, a (substituted) phenyl group, or a bisphenol which is a polynuclear phenol.
• the esterified phosphate compound may be a monomer, a dimer, an oligomer, a polymer, or a mixture thereof.
• trimethyl phosphate triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributylbutyshethyl phosphate, triphenylenophosphate, tricresinophosphate, cresinoresphenolephosphate.
• Octinoresifeninolephosphate tri (2-ethylhexyl) phosphate, diisopropinorefle-phosphate, trixyleneenophosphate, imis (isopropinolefeninole) phosphate, trinaphtinolephosphate, bisphenole A Bisphosphate, Hydroquinone Bisphosphate 7ate, Resonoresin Bisphosphate, Resorcinol Diphenyl Phosphate, Trioxybenzene Triphosphate, Cresyl Diphenyl Phosphate, or substituted versions thereof, condensates, and the like.
• halogen-free phosphoric acid ester compounds examples include, for example, TPP (triphenyl phosphate), TXP (trixylenyl phosphate), and CR-7 available from Daihachi Chemical Industry Co., Ltd.
• organic alkali metal salts and organic alkali earth salts there are various types of organic alkali metal salts and organic alkali earth salts, but alkali metal salts and alkaline earth metal salts of organic acids or organic acid esters having at least one carbon atom. It is.
• the organic acid or organic acid ester is organic sulfonic acid, organic carboxylic acid, or the like.
• the alkali metal is sodium, potassium, lithium, cesium, etc.
• the alkaline earth metal is magnesium, calcium, strontium, barium, etc.
• salts of sodium, potassium and cesium are preferably used.
• the salt of the organic acid may be substituted with a halogen such as fluorine, chlorine or bromine.
• n represents an integer of 1 to 10
• M is an alkali metal such as lithium, sodium, potassium, cesium, or the like, or an alkaline earth metal such as magnesium, calcium, stonium, barium, or the like. Represents a class of metals, and m represents the valence of M.
• An alkali metal salt or an alkaline earth metal salt of perfluoroalkanesulfonic acid represented by the following formula (1) is preferably used.
• the perfluoroalkanesulfonic acid includes, for example, perfluoroenomethanesulfonic acid, perfluoroethanesulfonic acid, perfluoropropanesulfonic acid, norfluorobutanes
• Examples include norephonic acid, norfluoromethylbutanesnolefonic acid, hexansnolefonic acid, perfluoroheptanesnolefonic acid, and perfluorootatansulfonic acid.
• potassium salts are preferably used.
• 2,5-dichloromouth benzene sulfonic acid; 2,4,5—tric mouth benzenesnolephonic acid; dipheninolenolesone-3-sonorefonic acid; dipheninolenolesone-1,3,3'-disnolephonic acid; naphthalene examples thereof include alkali metal salts of organic sulfonic acids such as tris-norefonic acid and alkaline earth metal salts.
• thermoplastic resin in which a sulfonic acid group, a borate group, a phosphate group, or the like is substituted on the aromatic ring of the bullet-based thermoplastic resin can be used.
• aromatic vinyl-based resin examples include thermoplastic resins having at least a styrene structure, such as polystyrene, rubber-modified polystyrene, styrene-atarilonitrile copolymer, and ABS resin. Among them, polystyrene resin is preferably used. ,
• examples of the acid base include metal salts of alkaline earth metal and earth salts of alkaline earth metal.
• organic carboxylic acid examples include perfluorogic acid, perfluoro methane carboxylic acid, norfanoleo ethanecanolevonic acid, perfluoropropane phenolic olevonic acid, perphnoleolobutane carboxylic acid, perph oleolomethinolev tan phenolic olevonic acid, and perphnoleic acid.
• Hexane-force olevonic acid ', perphnoleo-heptane carboxylic acid, perfluorooctane carboxylic acid, and the like, and an alkali metal salt and an earth metal salt of these organic carboxylic acids are used. .
• the Al metal and the Al earth metal are the same as described above.
• Silicone flame retardants include silicone oil and silicone corn resin.
• silicone-based flame retardant include silicone compounds having a specific structure containing a reactive group such as an alkoxy group and an epoxy group, and silicone resins having a specific molecular weight in which the amount of oxygen in the repeating unit is different (Japanese Unexamined Patent Application Publication No. _ 3 0 6 2 6 5 Publication, Japanese Patent Application Laid-Open No. Hei 6-3336 547, Japanese Patent Application Publication No. Japanese Patent Application Laid-Open No. H10-1039964, etc.).
• silicone-based flame retardant there are various compounds inter alia, functional group-containing silicone compound, for example, a has a functional group (poly) organosiloxanes, as its backbone, wherein R 5 a R 6 b S i O ( 4 - a _ b ) / 2 (R 5 is a functional group-containing group, R 6 is a hydrocarbon group having 1 to 12 carbon atoms, 0 ⁇ a ⁇ 3, 0 ⁇ b ⁇ 3, 0 ⁇ a + b ⁇ 3) ⁇ ) A polymer or copolymer having a basic structure.
• a has a functional group (poly) organosiloxanes, as its backbone, wherein R 5 a R 6 b S i O ( 4 - a _ b ) / 2 (R 5 is a functional group-containing group, R 6 is a hydrocarbon group having 1 to 12 carbon atoms, 0 ⁇ a ⁇ 3, 0 ⁇ b ⁇ 3, 0
• the functional group contains an alkoxy group, aryloxy, polyoxyalkylene group, hydrogen group, hydroxyl group, carboxyl group, cyanol group, amino group, mercapto group, epoxy group and the like.
• a silicone compound having a plurality of functional groups and a silicone compound having different functional groups can be used in combination.
• the silicone compound having this functional group has a functional group (R 5 ) / hydrocarbon group (R 6 ) power of usually about 0.1 to 3, preferably about 0.3 to 2.
• silicone compounds are liquids, powders and the like, but those having good dispersibility in melt kneading are preferred.
• a liquid having a viscosity at room temperature of about 10 to 500,000 cst can be used.
• the silicone compound has a functional group, even if the silicone compound is in a liquid state, the silicone compound is uniformly dispersed in the composition, and is less likely to bleed during molding or on the surface of the molded article.
• the above (E) flame retardant may be used alone or in combination of two or more.
• the content of (E) the flame retardant in the polycarbonate resin composition of the present invention is as follows: (A) the total amount of the polycarbonate resin and (B) the styrene resin. It is 0 to 20 parts by mass, preferably 0 to 15 parts by mass with respect to 00 parts by mass.
• phosphate esters organic alkali metal salts, organic alkaline earth metal salts and silicone compounds are particularly preferred.
• the rubbery elastomer of the component (F) includes polybutadiene, polyisoprene, styrene 'butadiene' styrene (SBS) rubber, styrene-butadiene rubber (SBR), and butadiene 'aqua.
• SBS polyisoprene
• SBR styrene-butadiene rubber
• Ryl rubber isoprene styrene rubber, isoprene acryl rubber, ethylene propylene rubber, ethylene propylene rubber and the like.
• the elastic body itself is in the form of powder (particle state).
• core-shell type rubber-like elastic body various types can be cited.
• Hyprene B621 manufactured by Nippon Zeon Co., Ltd.
• KM_330 KM—35.7P
• EXL_2602 manufactured by Kureha Chemical Industry Co., Ltd.
• EXL-2603 manufactured by Kureha Chemical Industry Co., Ltd.
• Metaprene S2001 manufactured by Mitsubishi Rayon Co., Ltd.
• alkyl acrylate and alkyl methacrylate obtained by polymerizing one or more vinyl monomers in the presence of a rubbery polymer obtained from a monomer mainly composed of dimethylsiloxane.
• alkyl acrylate / acryl methacrylate those having a C2-C10 alkyl group are preferable.
• Specific examples include ethyl acrylate, butyl acrylate, 21-ethylhexyl acrylate, and n-octyl methacrylate.
• a rubber-like elastic body obtained from a monomer mainly composed of these alkyl acrylates includes 70% by mass or more of alkyl acrylates and another butyl monomer copolymerizable therewith, for example, And methyl methacrylate, acrylonitrile, butyl acetate, styrene, and the like, and a polymer obtained by reacting with 3% by mass or less.
• a polyfunctional monomer such as divinylbenzene, ethylenedimethacrylate, triaryl cyanurate, or triaryl isocyanurate may be appropriately added as a crosslinking agent for the reaction.
• Examples of the vinyl monomer to be reacted in the presence of the rubbery polymer include, for example, aromatic butyl compounds such as styrene and ⁇ -methylstyrene, and acrylates such as methyl acrylate and ethyl acrylate. And methacrylic esters such as methyl methacrylate and ethyl methacrylate.
• These monomers may be used alone or in combination of two or more.Other vinyl polymers, for example, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, and butyl acetate and propionic acid It may be copolymerized with a vinyl ester compound such as a bullet.
• vinyl cyanide compounds such as acrylonitrile and methacrylonitrile
• butyl acetate and propionic acid It may be copolymerized with a vinyl ester compound such as a bullet.
• This polymerization reaction can be performed by various methods such as bulk polymerization, suspension polymerization, and emulsion polymerization. In particular, an emulsion polymerization method is preferred.
• the core-shell type graft rubber-like elastic material thus obtained preferably contains the rubber-like polymer in an amount of 20% by mass or more.
• Such core-shell type graph Togomu like elastic body specifically, of 6 0-8 0 weight 0/0 n-heptyl and Atari rate, styrene, graphs bets copolymer of Metaku acrylic acid methyl MA S resin elastic body is exemplified.
• polysiloxane rubber component 5-9 5 mass 0/0 and polyacrylamide Lil (meth) and Atari rate rubber component 9 5-5 mass 0/0 has mutually entangled structure so as not to be separated, Hitoshi particles
• a composite rubber-based copolymer obtained by graft-polymerizing at least one type of butyl monomer on a composite rubber having a diameter of about 0.01 to 1 ⁇ .
• This copolymer has a higher impact resistance improving effect than the graft copolymer of each rubber alone.
• This composite rubber-based graft copolymer can be obtained as a commercially available product, such as Metablen S-201, manufactured by Mitsubishi Rayon Co., Ltd.
• the content of (F) the rubber-like elastic material in the polycarbonate resin composition of the present invention is from 0 to 10 parts by mass based on 100 parts by mass of the total amount of (A) the polycarbonate resin and (B) the styrene-based resin. And preferably 3 to 8 parts by mass.
• the content of the rubber-like elastic body is determined by comprehensively considering impact resistance, heat resistance, rigidity, and the like required for a target molded product.
• Examples of the inorganic filler of the (G) component in the polycarbonate resin composition of the present invention include talc, My power, kaolin, diatomaceous earth, calcium carbonate, sulfate power, barium sulfate, glass fiber, carbon fiber, and potassium titanate fiber. Can be mentioned.
• plate-like talc, my strength, and fibrous fillers are preferred.
• Talc is a hydrous silicate of magnesium, and commercially available talc can be used.
• Talc may contain trace amounts of aluminum oxide, calcium oxide, and iron oxide in addition to the main components of caicic acid and magnesium oxide. In order to produce the resin composition of the present invention, these are included. You can go out.
• the average particle size of the inorganic filler such as talc is usually 0.1 to 50 ⁇ , preferably 0.2 to 20 ⁇ .
• the rigidity can be improved and the amount of the halogen-free phosphoric acid ester as a flame retardant can be reduced.
• the inorganic filler (G) in the polycarbonate resin composition of the present invention is added to further improve the rigidity of the molded article and further the flame retardancy, and the content thereof is ( ⁇ ) the polycarbonate resin and ( ⁇ ) The amount is 0 to 20 parts by mass, preferably 3 to 15 parts by mass, based on 100 parts by mass of the total amount of the styrene resin.
• the polycarbonate resin composition of the present invention comprises an essential component consisting of the above ( ⁇ ) to (D) for the purpose of improving appearance, antistatic, improving weather resistance, improving rigidity, and the like.
• an additive component commonly used in polycarbonate resins can be added as necessary.
• antistatic agents for example, antistatic agents, polyamide polyether block copolymers (permanent Benzotriazole and benzophenone ultraviolet absorbers, hinderdamine light stabilizers (weatherproofing agents), antibacterial agents, compatibilizers, coloring agents (dyes and pigments).
• polyamide polyether block copolymers permanent Benzotriazole and benzophenone ultraviolet absorbers, hinderdamine light stabilizers (weatherproofing agents), antibacterial agents, compatibilizers, coloring agents (dyes and pigments).
• the amount of the optional component is not particularly limited as long as the properties of the polycarbonate resin composition of the present invention are maintained.
• thermoplastic resin composition of the present invention the above-mentioned components (A) to (E) are used in the above proportions, and various optional components (F) to (G) used as necessary, and further other components are used. It can be obtained by mixing and kneading general components in an appropriate ratio.
• the compounding and kneading at this time are preliminarily mixed with a device usually used, for example, a rib blender, a drum tumbler, etc., and a Henschel mixer, a Banbury mixer, a single screw extruder, a twin screw screw are used. It can be carried out by a method using an extruder, a multi-screw extruder, a kneader or the like.
• the heating temperature at the time of kneading is appropriately selected usually in the range of 240 to 300 ° C.
• the components other than the polycarbonate resin and the styrene-based resin can be previously melt-kneaded with the polycarbonate resin, the styrene-based resin, and the like, that is, added as a master batch.
• the polycarbonate resin composition of the present invention is obtained by using the above-described melt-kneading molding machine or the obtained pellets as a raw material, and then performing injection molding, injection compression molding, extrusion molding, blow molding, press molding, and vacuum molding. Also, various molded articles can be manufactured by a foam molding method or the like.
• a pellet-shaped molding raw material is produced by the above-described melt-kneading method, and then, using this pellet, production of an injection-molded product by injection molding or injection compression molding where release properties are the most problematic. Especially suitable for it can.
• a gas injection molding method for preventing sink marks on the appearance or reducing the weight can be adopted.
• Injection molded articles obtained from the polycarbonate resin composition of the present invention include copying machines, fax machines, televisions, radios, tape recorders, VCRs, personal computers, printers, telephones, and information terminals. , Refrigerators, OA equipment such as microwave ovens, home appliances, electrics, housing for electronic equipment, and various parts.
• each component was blended in the proportions shown in Tables 1 and 2 [(A) and (B) components were in mass%, and the other components were in parts by mass with respect to 100 parts by mass of resin (A) and (B) Show. Then, it was supplied to a vent-type twin-screw extruder (model name: TEM35, manufactured by Toshiba Machine Co., Ltd.), melt-kneaded at 260 ° C, and pelletized.
• a vent-type twin-screw extruder model name: TEM35, manufactured by Toshiba Machine Co., Ltd.
• Irganox 11076 manufactured by Ciba's Specialty Chemicals Co., Ltd.
• ADK STAB C manufactured by Asahi Denka Kogyo Co., Ltd.
• the obtained pellets were dried at 120 ° C for 12 hours, and then injection molded at a molding temperature of 260 ° C and a mold temperature of 80 ° C to obtain test pieces.
• the performance evaluation method is shown below.
• PC A 190 (made by Idemitsu Petrochemical Co., Ltd.); polycarbonate resin
• HIPS impact-resistant polystyrene
• IDEMISTSUPSIT44 manufactured by Idemitsu Petrochemical Co., Ltd.
• MI 8 g / 10 minutes (200 ° C, 5 kg load)
• AB S Atarilonitrile-butadiene-styrene copolymer (AB S); AT-05 (manufactured by A & L)
• PTF E mixed powder A380 (manufactured by Mitsubishi Rayon Co.); PTF E content 50% by mass
• Release agent 1 pentaerythritol toltrastearate; EW-440A
• Release agent 2 Glycerin monostearate; S-100, A (manufactured by RIKEN Vitamin Co., Ltd.)
• Release agent 3 polyethylene wax; 400 P (Mitsui Chemicals)
• Rubber-like elastic body core-shell type S2001 (Mitsubishi Rayon Co., Ltd.)
• Tensile strength test pieces were molded with a two-point gate using a mold, and the tensile strength (MPa) was measured.
• the surface impact strengths of the polycarbonate resin composition of the present invention are all ductile fractures, stable and high strength can be maintained, the molding appearance and weld strength are excellent, and a flame retardant is added. Then 1.5 mm V-1 0.
• Comparative Examples 1-2 the use of powder of polytetramethylene full O B Ethylene 1 0 0 mass 0/0, surface impact strength, to include the brittle fracture or brittle fracture, molding appearance ⁇ Pi Uerudo strength Decreases.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=29996806

Family Applications (1)

Country Status (3)

Cited By (3)

Families Citing this family (11)

Citations (1)

• 2002
  • 2002-06-27 JP JP2002188002A patent/JP4146175B2/ja not_active Expired - Lifetime
• 2003
  • 2003-05-30 WO PCT/JP2003/006838 patent/WO2004003078A1/ja active Application Filing
  • 2003-06-05 TW TW92115272A patent/TW200400228A/zh unknown

Patent Citations (1)

Also Published As

Similar Documents

Legal Events