WO2012056971A1 - Composition de résine de polycarbonate aromatique et corps moulé obtenu par moulage par injection de la composition - Google Patents

Composition de résine de polycarbonate aromatique et corps moulé obtenu par moulage par injection de la composition Download PDF

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Publication number
WO2012056971A1
WO2012056971A1 PCT/JP2011/074059 JP2011074059W WO2012056971A1 WO 2012056971 A1 WO2012056971 A1 WO 2012056971A1 JP 2011074059 W JP2011074059 W JP 2011074059W WO 2012056971 A1 WO2012056971 A1 WO 2012056971A1
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polycarbonate resin
aromatic polycarbonate
mass
resin composition
parts
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PCT/JP2011/074059
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English (en)
Japanese (ja)
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敬直 竹内
誠一 前場
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出光興産株式会社
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Priority to KR1020137013189A priority Critical patent/KR20130132819A/ko
Priority to CN201180057565.8A priority patent/CN103261322B/zh
Publication of WO2012056971A1 publication Critical patent/WO2012056971A1/fr

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    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

Definitions

  • the present invention relates to an aromatic polycarbonate resin composition and a molded article formed by injection molding the same, and more particularly, electronic or electric equipment (liquid crystal projector, personal computer, communication equipment, digital camera, video camera, television, electromagnetic Suitable for heat dissipation parts, heat transfer parts, heat dissipation parts, heat dissipation parts for LED application products (LED lighting, LED display boards, image sensors, etc.), heat transfer parts, and case with heat dissipation functions
  • the present invention relates to an aromatic polycarbonate resin composition that can be used in the present invention and a molded article obtained by injection molding the same.
  • Polycarbonate resins especially aromatic polycarbonate resins, have excellent heat resistance and impact resistance, and are used in electronic and electrical equipment casings.
  • digital cameras Thermal measures to avoid adverse effects from the heat generated from the inside due to high pixel count and high speed processing in digital video cameras, miniaturization of projectors, high speed processing in personal computers and mobile devices, and the use of LEDs for various light sources The emphasis is on. Therefore, there is a demand for a polycarbonate resin material having excellent thermal conductivity, but in addition to thermal conductivity, insulation is often required.
  • metal nitrides such as boron nitride and aluminum nitride are blended in aromatic polycarbonate resin as a heat conductive filler having high thermal conductivity and insulating properties.
  • metal nitride is expensive.
  • the resin cost is high, and it is difficult to spread.
  • Patent Document 1 and Patent Document 1 disclose that thermal conductivity is improved by blending aromatic polycarbonate resin with talc, mica, wollastonite, kaolin, calcium carbonate, titanium oxide or the like as a cheaper inorganic filler. It is known at 2 mag.
  • Patent Document 1 discloses a light-reflective multilayer comprising a light-reflective resin layer (A) and a resin base layer (B) containing 30% by mass or more of an inorganic filler and having a flexural modulus of 5 GPa or more. A sheet is described.
  • the thermal conductivity of the resin base material layer (B) is specified to be 1 W / m ⁇ ° C.
  • the resin base material layer (B) It is described that kaolin, calcium carbonate, aluminum oxide, graphite, boron nitride, titanium oxide, glass fiber, carbon fiber, etc. are used, and that heat conductivity is improved by containing a high amount of inorganic filler. Has been. However, this resin base material layer (B) is obtained by sheet molding, and specifically, only a combination of talc and mica and talc and graphite is disclosed for inorganic fillers. .
  • Patent Document 2 describes a flame retardant resin composition comprising an aromatic polycarbonate resin, a white pigment containing titanium oxide, and talc, and further describes the addition of alkoxysilicone.
  • This resin composition describes that a molded product having good light reflectivity, light shielding properties, thermal conductivity, mechanical properties (rigidity), and dimensional stability can be obtained.
  • titanium oxide and talc is contained in the aromatic polycarbonate resin, there is a problem that although the thermal conductivity is improved, mechanical properties such as impact resistance are lowered.
  • this composition provides a composition suitable for a reflector for a backlight used in an illuminating device such as an LCD, and is used for the purpose of increasing the size, reducing the thickness, and reducing the weight of the aromatic polycarbonate.
  • a high fluidity copolymer PC obtained by copolymerization using a specific copolymerization monomer, or to ensure fluidity It is difficult to improve impact resistance because an aromatic polycarbonate resin having a relatively low molecular weight is used.
  • the present invention provides a balance of thermal conductivity, insulation, impact resistance, heat distortion resistance, fluidity, etc. required for electronic or electrical equipment parts by using a specific inorganic filler and a silicone additive in combination. It is an object of the present invention to obtain an aromatic polycarbonate resin composition that can be applied as a design member and can be imparted with a colorability, and a molded product obtained by injection molding the same.
  • the present inventors have blended a specific amount of an aromatic polycarbonate resin with titanium oxide or a mixture of titanium oxide and talc and an organopolysiloxane containing an alkoxy group.
  • the aromatic polycarbonate resin composition obtained and the molded article obtained by injection molding the resin composition are excellent in thermal conductivity and insulation, and can impart colorability applicable as a design member.
  • the headline and the present invention were completed.
  • the present invention (1) (A) 40-220 parts by mass of titanium oxide coated with polyol, (B-2) 0-70 parts by mass of talc, and (C) alkoxy for 100 parts by mass of aromatic polycarbonate resin Aromatics characterized in that 3 to 15 parts by mass of a group-containing organopolysiloxane is blended, and the total amount of component (B-1) and component (B-2) is 70 to 220 parts by mass Polycarbonate resin composition, (2) The aromatic polycarbonate resin composition according to the above (1), further comprising (D) 1 to 7 parts by mass of polytetrafluoroethylene, (3) The aromatic polycarbonate resin composition according to (1) or (2), further comprising (E) 0.1 to 1 part by mass of a phosphorus stabilizer.
  • Polycarbonate resin composition (6) The aromatic polycarbonate resin composition according to any one of the above (1) to (5), wherein (A) the aromatic polycarbonate resin has a viscosity average molecular weight of 16,500 to 30,000, (7) The above (1) to (A) (A) wherein the aromatic polycarbonate resin is a polycarbonate-polyorganosiloxane copolymer or a mixture of a polycarbonate-polyorganosiloxane copolymer and another aromatic polycarbonate resin.
  • the aromatic polycarbonate resin composition according to any one of (8) A molded body obtained by injection molding the aromatic polycarbonate resin composition according to any one of (1) to (7) above, and (9) a molded body is a heat radiating part of an electric device, an electronic device or a lighting device. Or the molded object as described in said (8) which is a heat transfer component is provided.
  • the molded product obtained from the aromatic polycarbonate resin composition of the present invention has a balance of thermal conductivity, insulating heat, impact resistance, heat distortion resistance, fluidity and the like required for electric parts.
  • the obtained molded body is white, it is possible to obtain a molded body having excellent design properties by adding a favorite colorant.
  • it can be suitably used as a heat dissipating part or heat transfer part for electrical / electronic equipment or lighting equipment by injection molding.
  • the aromatic polycarbonate resin composition of the present invention comprises (A) an aromatic polycarbonate resin, (B-1) titanium oxide coated with a polyol, or (B-1) titanium oxide coated with a polyol and (B-2). ) Talc and (C) Organopolysiloxane containing an alkoxy group as an essential component.
  • the aromatic polycarbonate resin used as the component (A) in the present invention (hereinafter sometimes simply referred to as “polycarbonate resin”) is not particularly limited and includes various types. Usually, a dihydric phenol and a carbonate precursor. Polycarbonate resin produced by the reaction with can be used. For example, a dihydric phenol and a carbonate precursor are used by a solution method or a melting method, specifically, a reaction of a dihydric phenol and phosgene, or a transesterification reaction of a dihydric phenol and diphenyl carbonate or the like. be able to.
  • dihydric phenols can be mentioned.
  • various dihydric phenols can be used.
  • dihydric phenols bis (hydroxyphenyl) alkane, particularly 2,2-bis (4-hydroxyphenyl) propane [bisphenol A] is preferable.
  • these dihydric phenols may each be used independently, and 2 or more types may be mixed and used for them.
  • the carbonate precursor include carbonyl halide, carbonyl ester, and haloformate. Specific examples include phosgene, dihaloformate of dihydric phenol, diphenyl carbonate, dimethyl carbonate, and diethyl carbonate.
  • this polycarbonate resin what the molecular chain has a linear structure, a cyclic structure, or a branched structure can be used.
  • the polycarbonate resin having a branched structure 1,1,1-tris (4-hydroxyphenyl) ethane, ⁇ , ⁇ ′, ⁇ ′′ -tris (4-bidoxyphenyl) -1, Those produced using 3,5-triisopropylbenzene, phloroglucin, trimellitic acid, isatin bis (o-cresol), etc.
  • this polycarbonate resin a bifunctional carboxylic acid such as terephthalic acid, or Polyester-carbonate resins produced using ester precursors such as ester-forming derivatives can also be used, and mixtures of polycarbonate resins having various chemical structures can also be used.
  • the viscosity average molecular weight of these polycarbonate resins is usually 10,000 to 50,000, but in the present invention, it is 16,500 to 30,000, preferably 19,000 to 25,000. When the viscosity average molecular weight is 19000 or more, sufficient strength is obtained, and when it is 30,000 or less, productivity is prevented from being lowered.
  • a known molecular weight regulator such as phenol, p-tert-butylphenol, p-dodecylphenol, p-tert-octylphenol or p-cumylphenol is used.
  • a polycarbonate-polyorganosiloxane copolymer (hereinafter sometimes referred to as a PC-POS copolymer) may be used.
  • This copolymer is prepared by, for example, dissolving a polycarbonate oligomer and a polyorganosiloxane having a reactive group at a terminal in a solvent such as methylene chloride, adding a sodium hydroxide aqueous solution of dihydric phenol to this, and adding triethylamine or the like. It can be produced by interfacial polycondensation reaction using a catalyst.
  • polyorganosiloxane structure portion in this case, those having a polydimethylsiloxane structure, a polydiethylenesiloxane structure, a polymethylphenylsiloxane structure, or a polydiphenylsiloxane structure are preferably used.
  • the PC-POS copolymer those having a polymerization degree of 3 to 100 for the polycarbonate portion and a polymerization degree of about 2 to 500 for the polyorganosiloxane portion are preferably used.
  • the content of the polyorganosiloxane moiety in this PC-POS copolymer is 0.5 to 30% by mass, preferably 1 to 20% by mass, and more preferably 1 to 10% by mass.
  • the content of the polyorganosiloxane block part By setting the content of the polyorganosiloxane block part to 0.5% by mass or more, impact resistance can be improved, and by setting the content to 30% by mass or less, a decrease in heat resistance can be prevented.
  • this PC-POS copolymer flame retardancy is imparted to the resin composition.
  • the viscosity average molecular weight of this PC-POS copolymer is usually 5,000 to 100,000, but in the present invention, it is preferably 16,500 to 30,000. By setting the viscosity average molecular weight of the PC-POS copolymer to 16,500 or more, the strength of the molded product is sufficiently maintained, and by setting the viscosity to 30,000 or less, the productivity is prevented from decreasing.
  • the PC-POS copolymer is preferably a polycarbonate-polydimethylsiloxane copolymer (PC-PDMS copolymer) in which the polyorganosiloxane has a polydimethylsiloxane structure from the viewpoint of heat resistance, impact resistance and flame retardancy.
  • PC-PDMS copolymer polycarbonate-polydimethylsiloxane copolymer
  • the PC-POS copolymer / PC mass ratio
  • the mixing is preferably performed so that the content of the siloxane block portion is 0.5 to 30% by mass, preferably 1 to 20% by mass, and more preferably 1 to 10% by mass.
  • the aromatic polycarbonate resin composition of the present invention is blended with titanium oxide whose surface is coated with a polyol as the component (B-1) in order to mainly impart thermal conductivity.
  • the titanium oxide used in the present invention is particularly preferably titanium dioxide.
  • the average particle diameter of titanium oxide is preferably 0.05 to 0.5 ⁇ m, more preferably 0.1 to 0.4 ⁇ m, and still more preferably 0.15 to 0.3 ⁇ m.
  • the surface of the titanium oxide used in the present invention is coated with a polyol, so that the dispersibility of the titanium oxide in the aromatic polycarbonate composition can be improved and the molecular weight of the polycarbonate can be prevented from being lowered.
  • titanium oxide used in the present invention is a hydrated oxide of at least one element containing an element such as aluminum, silicon, magnesium, zirconia titanium, tin and / or the titanium oxide surface before coating the surface with a polyol.
  • An oxide may be coated.
  • Examples of the polyol used when coating titanium oxide with a polyol include trimethylolpropane, trimethylolethane, ditrimethylolpropane, trimethylolpropane ethoxylate, pentaerythritol and the like. Among these, trimethylolpropane and trimethylolethane are used. Is preferred.
  • Examples of the method of coating the surface with a polyol include a wet method and a dry method. In the wet method, titanium oxide is added to a mixture of a polyol and a low-boiling solvent, and after stirring, the low-boiling solvent is removed.
  • the polyol and titanium oxide are mixed in a mixer such as a Henschel mixer or a tumbler, or the polyol is dissolved in a solvent or the dispersed mixed solution is sprayed onto the titanium oxide.
  • a mixer such as a Henschel mixer or a tumbler
  • the polyol is dissolved in a solvent or the dispersed mixed solution is sprayed onto the titanium oxide.
  • the crystal structure of titanium oxide can be either a rutile type or an anatase type, but the rutile type is more preferable from the viewpoint of the thermal stability, light resistance, etc. of the aromatic polycarbonate resin composition.
  • the blending amount of titanium oxide as the component (B-1) is 40 to 220 parts by mass, preferably 50 to 180 parts by mass with respect to 100 parts by mass of the component (A).
  • the thermal conductivity of the resulting molded article is obtained by using together 0 to 70 parts by mass, preferably 0 to 60 parts by mass of talc as the component (B-2) together with titanium oxide as the component (B-1). And the heat resistance of the molded product can be further improved.
  • the total amount of the component (B-1) and the component (B-2) is 70 to 220 parts by mass, preferably 80 to 180 parts by mass. When the total amount is 70 parts by mass or more, the thermal conductivity is prevented from being reduced, and when the total amount is 220 parts by mass or less, the moldability is prevented from being deteriorated.
  • talc when using a talc, it can prevent that the uniform kneading
  • talc of the component (B-2) used at this time those commercially available as additives for thermoplastic resins can be arbitrarily used.
  • Talc is a hydrated silicate of magnesium, and may contain trace amounts of aluminum oxide, calcium oxide, and iron oxide in addition to the main components of silicic acid and magnesium oxide, but is used in the resin composition of the present invention. Things may contain these.
  • the average particle size is in the range of 0.5 to 50 ⁇ m, preferably 1 to 20 ⁇ m.
  • the aspect ratio is usually in the range of 2-20.
  • average particle diameters and aspect ratios are determined by comprehensively considering other components depending on the fluidity at the time of molding, impact resistance required for the molded product, rigidity, and the like.
  • talc what was surface-treated with a fatty acid etc., the talc etc. which were grind
  • an organopolysiloxane containing an alkoxy group is blended as the component (C).
  • component titanium oxide is blended at a high concentration by blending (C) component alkoxy group-containing organopolysiloxane (hereinafter simply referred to as organopolysiloxane). While suppressing the molecular weight fall of the polycarbonate resin which is (A) component of this, it has the effect of improving the smoothness of the surface of the obtained molded object.
  • organopolysiloxane there are various types.
  • the organopolysiloxane contains an organoxysilyl group in which an alkoxy group is bonded to a silicon atom directly or via a divalent hydrocarbon group, and is linear, cyclic, Examples thereof include linear organopolysiloxanes having a network shape and a partial branch. In particular, linear organopolysiloxane is preferred.
  • organopolysiloxane containing an organoxysilyl group in which such an alkoxy group is bonded to a silicon atom directly or via a divalent hydrocarbon group include, for example, the general formula (IV)
  • R 1 represents a monovalent hydrocarbon group
  • A represents a monovalent hydrocarbon group, an alkoxy group (—OR 4 ), or the following general formula (V).
  • R 2 represents a divalent hydrocarbon group
  • R 3 and R 4 represent a monovalent hydrocarbon group
  • X is an integer of 0 to 2).
  • at least one of A in one molecule is an alkoxy group or an organoxysilyl group-containing monovalent hydrocarbon group.
  • m is an integer of 1 to 300
  • n is an integer of 0 to 300
  • m + n is an integer of 1 to 300].
  • the monovalent hydrocarbon group represented by R 1 is specifically an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, or a hexyl group, Examples thereof include alkenyl groups such as vinyl group, allyl group, butenyl group, pentenyl group and hexenyl group, aryl groups such as phenyl group, tolyl group and xylyl group, and aralkyl groups such as benzyl group and phenethyl group.
  • a specific example of the monovalent hydrocarbon group represented by A is the same as in the case of R 1 .
  • specific examples of the divalent hydrocarbon group represented by R 2 include alkylene groups such as a methylene group, an ethylene group, a propylene group, and a butylene group.
  • the monovalent hydrocarbon groups represented by R 3 and R 4 are the same as described above.
  • Specific examples of the monovalent hydrocarbon group containing an organoxysilyl group include a trimethoxysilylethylene group, a triethoxysilyl group.
  • organopolysiloxane of component (C) examples include an ethylene group, dimethoxyphenoxysilylpropylene group, trimethoxysilylpropylene group, trimethoxysilylbutylene group, methyldimethoxysilylpropylene group, dimethylmethoxysilylpropylene group and the like.
  • This organopolysiloxane of component (C) may be used singly or in combination of two or more. Since organopolysiloxane having no alkoxy group cannot suppress a decrease in molecular weight, sufficient impact strength cannot be obtained.
  • the compounding amount of the organopolysiloxane of component (C) requires 3 to 15 parts by mass, preferably 4 to 10 parts by mass, per 100 parts by mass of the (A) aromatic polycarbonate resin.
  • the blending amount By setting the blending amount to 3 parts by mass or more, it is possible to prevent the decrease in the molecular weight of the polycarbonate resin from being inferior in impact resistance, and by setting it to 15 parts by mass or less, a molded product at the time of molding. Is prevented from adhering to the mold, and uniform kneading during the production of pellets and molded products is prevented.
  • polytetrafluoroethylene can be mix
  • polytetrafluoroethylene (PTFE) [hereinafter sometimes simply referred to as “(D) component”] preferably has a fibril-forming ability.
  • fibril forming ability means that resins tend to be bonded and become fibrous due to an external action such as shearing force.
  • Examples of the component (D) in the aromatic polycarbonate resin composition of the present invention include polytetrafluoroethylene, a tetrafluoroethylene copolymer (for example, a tetrafluoroethylene / hexafluoropropylene copolymer), and the like.
  • PTFE having fibril-forming ability has a very high molecular weight, and the number average molecular weight determined from the standard specific gravity is usually 500,000 or more, preferably 500,000 to 15 million, more preferably 1,000,000 to 10 million.
  • tetrafluoroethylene is polymerized in an aqueous solvent in the presence of sodium, potassium or ammonium peroxydisulfide at a pressure of about 7 to 700 kPa and a temperature of about 0 to 200 ° C., preferably 20 to 100 ° C. Can be obtained.
  • those in the form of an aqueous dispersion can also be used, and those classified as type 3 according to the ASTM standard can be used.
  • Commercially available products classified as Type 3 include, for example, “Teflon 6-J” (trade name, manufactured by Mitsui Dupont Fluoro Chemical Co., Ltd.), “Polyflon D-1” and “Polyflon F-103” [trade name.
  • PTFE Polytetrafluoroethylene from which impurities such as perfluorooctanoic acid have been removed by environmental regulations can also be used without problems.
  • the PTFE may be used alone or in combination of two or more.
  • the polytetrafluoroethylene of component (D) is preferably added in a range of up to 7 parts by mass, and impact characteristics can be improved by adding in this range, but if it exceeds 7 parts by mass, the pellets This is not preferable because the kneading stability at the time of manufacture is lowered, and kneading failure may be caused and impact characteristics are lowered.
  • the polytetrafluoroethylene of (D) component can provide the aromatic polycarbonate resin composition of this invention with the melt dripping prevention effect, and can improve a flame retardance.
  • a phosphorus stabilizer can be added as the component (E).
  • Titanium oxide and talc are used in the aromatic polycarbonate resin composition of the present invention, but when these inorganic compounds are added to the polycarbonate resin, they have an undesirable effect of decomposing the polycarbonate resin and reducing its molecular weight. .
  • the titanium oxide used in the present invention prevents such undesired effects by treating the surface with a polyol. In order to suppress these unfavorable effects as much as possible, a phosphorus stabilizer is further added. It is preferable to mix.
  • Examples of the phosphorus stabilizer used in the present invention include an aromatic phosphine compound and / or a phosphoric acid compound.
  • the aromatic phosphine compound acts as a stabilizer for the polycarbonate resin when the component (B-1) titanium oxide is used, and the phosphoric acid compound uses the component (B-2) talc. When used, it acts as a stabilizer for the polycarbonate resin.
  • aromatic phosphine compound for example, the following formula (P) P- (X) 3 . . . . . . . (P) (Wherein, X is a hydrocarbon group, at least one of which is an aryl group having 6 to 18 carbon atoms which may have a substituent).
  • Examples of the arylphosphine compound of the formula (P) include triphenylphosphine, diphenylbutylphosphine, diphenyloctadecylphosphine, tris- (p-tolyl) phosphine, tris- (p-nonylphenyl) phosphine, and tris- (naphthyl) phosphine.
  • Diphenyl- (hydroxymethyl) -phosphine diphenyl- (acetoxymethyl) -phosphine, diphenyl- ( ⁇ -ethylcarboxyethyl) -phosphine, tris- (p-chlorophenyl) phosphine, tris- (p-fluorophenyl) phosphine, Diphenylbenzylphosphine, diphenyl- ⁇ -cyanoethylphosphine, diphenyl- (p-hydroxyphenyl) -phosphine, diphenyl-1,4-dihydroxyphenyl-2-phosphine, phenyl And naphthylbenzylphosphine.
  • triphenylphosphine can be particularly preferably used.
  • Examples of phosphoric acid compounds include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specific examples include triphenyl phosphite, tris (nonylphenyl) phosphite, tris.
  • the aromatic phosphine compound is preferably blended in an amount of 0.1 to 1 part by mass with respect to 100 parts by mass of the (A) aromatic polycarbonate resin. ) It is preferable to blend 0.2 to 1 part by mass with respect to 100 parts by mass of the aromatic polycarbonate resin.
  • Component flame retardants include halogen flame retardants, nitrogen flame retardants, metal hydroxides, phosphorus flame retardants, organic metal salt flame retardants (organic alkali metal salts, organic alkaline earth metal salts), Known materials such as silicone-based flame retardants and expandable graphite can be used depending on the purpose.
  • halogen flame retardants include tetrabromobisphenol A (TBA), halogenated polycarbonates and (co) polymers of halogenated polycarbonates, oligomers thereof (TBA carbonate oligomers), decabromodiphenyl ether, TBA epoxy oligomers, halogenated polystyrene, Examples thereof include halogenated polyolefins.
  • TAA tetrabromobisphenol A
  • halogenated polycarbonates and (co) polymers of halogenated polycarbonates, oligomers thereof (TBA carbonate oligomers), decabromodiphenyl ether, TBA epoxy oligomers, halogenated polystyrene, Examples thereof include halogenated polyolefins.
  • Examples of the nitrogen-based flame retardant include melamine, an alkyl group, or an aromatic group-substituted melamine.
  • Examples of the metal hydroxide include magnesium hydroxide and aluminum hydroxide.
  • Examples of phosphorus flame retardants include halogen-free organic phosphorus flame retardants.
  • As the halogen-free machine phosphorus-based flame retardant any organic compound having a phosphorus atom and not containing a halogen can be used without particular limitation.
  • phosphate ester compounds having one or more ester oxygen atoms directly bonded to the phosphorus atom are preferably used.
  • the phosphate ester compound may be a monomer, dimer, oligomer, polymer, or a mixture thereof.
  • trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, tri (2-ethylhexyl) phosphate, diisopropyl Phenyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) phosphate, trinaphthyl phosphate, bisphenol A bisphosphate, hydroquinone bisphosphate, resorcin bisphosphate, resorcinol-diphenyl phosphate, trioxybenzene triphosphate, or a substitution product thereof, condensation Thing etc. are mentioned.
  • halogen-free phosphorus-based flame retardants other than organic phosphorus-based flame retardants include red phosphoric acid
  • organic alkali metal salts and organic alkaline earth metal salts that are organic metal salt flame retardants include alkali metal salts and alkaline earths of organic acids or organic acid esters having at least one carbon atom.
  • a metal salt is preferably used.
  • organic sulfonic acid, organic carboxylic acid, etc. are mentioned as an organic acid or organic acid ester.
  • the alkali metal salt include salts such as sodium, potassium, lithium, and cesium.
  • the alkaline earth metal salt include salts such as magnesium, calcium, strontium, and barium. Among these, sodium, potassium, and cesium salts are preferable.
  • the salt of the organic acid may be substituted with a halogen such as fluorine, chlorine or bromine.
  • perfluoromethanesulfonic acid perfluoroethanesulfonic acid, perfluorobutanesulfonic acid potassium salt and the like can be mentioned.
  • these organometallic salt flame retardants flame retardancy can be obtained even if the amount of brominated flame retardant and phosphorus flame retardant added is reduced.
  • impact strength improves by addition of an organic metal salt flame retardant, flame retardance is reduced when too much is added.
  • the organometallic salt flame retardant is added, the range of 0.01 to 0.5 parts by mass is preferable. Further, by adding these organometallic salt flame retardants, an improvement in the heat distortion temperature is observed, although slightly, compared with the case where only the brominated flame retardant is added.
  • silicone flame retardant examples include silicone oil and silicone resin.
  • silicone flame retardant examples include (poly) organosiloxanes having a functional group. Examples of this functional group include an alkoxy group, aryloxy, polyoxyalkylene group, hydrogen group, hydroxyl group, carboxyl group, cyano group, amino group, mercapto group, and epoxy group.
  • the above flame retardants may be used alone or in combination of two or more.
  • the blending amount of the flame retardant (F) is in the range of 0.01 to 30 parts by mass, preferably 0.05 to 30 parts by mass with respect to 100 parts by mass of the component (A). If it exists in this range, sufficient flame retardance will be acquired, without impairing the other physical property of the molded object obtained.
  • ⁇ Component (G)> In the aromatic polycarbonate resin composition of the present invention, as the component (G), a release agent, an antistatic agent, a fluorescent brightening agent, a flame retardant other than the component (F), or a coloring agent that is usually used as necessary. Various additives such as a light stabilizer such as an agent, a hindered amine, and an inorganic filler other than the component (B) can be used.
  • the compounding amount of the component (G) is not particularly limited as long as the characteristics of the aromatic polycarbonate resin composition of the present invention are maintained.
  • the manufacturing method of the molded object formed by injection-molding the aromatic polycarbonate resin composition of this invention is demonstrated.
  • the molded product formed by injection molding of the aromatic polycarbonate resin composition of the present invention further requires the above components (A) to (C), and if necessary, the components (D) to (G) in the above proportions. It is obtained by blending various resin components used in accordance with the ratio at an appropriate ratio, pelletizing an aromatic polycarbonate resin composition obtained by kneading, and injection molding.
  • Various resin components include fluidity improvers such as acrylonitrile-styrene copolymer resin and terpene resin, and core / shell such as graft copolymer (MAS resin) of n-butyl acrylate, styrene and methyl methacrylate.
  • fluidity improvers such as acrylonitrile-styrene copolymer resin and terpene resin
  • core / shell such as graft copolymer (MAS resin) of n-butyl acrylate, styrene and methyl methacrylate.
  • MAS resin graft copolymer
  • thermoplastic resins used as impact resistance improvers such as mold elastomers and / or rubber component-containing styrene resins (HIPS, ABS, etc.).
  • the compounding and kneading are premixed with commonly used equipment such as a ribbon blender, a drum tumbler, etc., and then a Henschel mixer, a Banbury mixer, a single screw extruder, a twin screw extruder, a multi screw extruder, and It can be performed by a method using a conida or the like.
  • the heating temperature at the time of kneading is appropriately selected in the range of usually 240 to 330 ° C, preferably 250 to 320 ° C.
  • an extrusion molding machine particularly a vent type extrusion molding machine.
  • the components other than the aromatic polycarbonate resin can be added in advance as a master batch with melt kneading with the aromatic polycarbonate resin or other thermoplastic resin.
  • a method of injection molding using the pellets thus obtained as a raw material a general injection molding method or an injection compression molding method, and a special molding method such as a gas assist molding method can be used to manufacture various molded products. can do. Since the molded article of the present invention has an excellent thermal conductivity of 3 to 6 W / m / K, it is useful as a heat radiating component in a casing of an electric / electronic device having an internal heat source or an LED lighting device.
  • the heat dissipation is excellent, so that the internal temperature is not greatly increased.
  • the molded body made of the resin composition of the present invention is more likely to form a sealed structure by joining with other resin parts than the molded body made of a metal member, it is dustproof and waterproof for products used outdoors or in water. This is useful in that the property can be improved.
  • molding technique which improves external appearance such as a heat cycle shaping
  • flame retarding is calculated
  • molding techniques such as lamination molding with the resin material which has a flame retardance, and two-color molding.
  • partial compression molding For molding a molded product having a partial thin-walled portion, partial compression molding or the like should be used. You can also. Since the molded body made of the aromatic polycarbonate resin composition of the present invention contains titanium oxide and, if necessary, talc at a high content, the color tone has a high whiteness and is arbitrarily colored. By adding the agent, a molded article having high design properties can be obtained. Therefore, it can be suitably used for a casing, a chassis, a reflecting member, and the like, which are various parts of an electronic device or an electric device. In addition, the aromatic polycarbonate resin composition of the present invention can be formed into a molded article using a molding method other than injection molding.
  • a sheet molded body having high light reflectance can be obtained by extrusion molding. It can also be used as a component such as a liquid crystal display backlight. And a sheet molded object can also be made into a molded article by pressure forming etc., such as vacuum forming.
  • the sheet molded body can be applied to a commonly used sheet such as a laminated sheet made of a material having flame retardancy as well as a laminated sheet made of a material having transparency.
  • the reflectance of the prepared sample was evaluated by the Y value using an LCM spectrophotometer MS2020 plus (manufactured by Macbeth).
  • Flow characteristics flow value
  • the raw material pellets were measured according to JIS-K7210 at a temperature of 320 ° C. and a load of 160 kg.
  • Izod impact strength kJ / m 2
  • the test piece was prepared with an injection molding machine (Toshiba Machine Co., Ltd., IS-100EN, molding temperature 320 ° C., mold temperature 80 ° C.).
  • Use raw material pellets dried at 120 ° C for 5 hours.
  • ASTM D256 measurement was performed with a notch at 23 ° C.
  • the test was conducted with 5 pieces of 1/8 inch wall thickness, and the average value was shown (unit: kJ / m 2 ).
  • (6) Thermal deformation temperature (° C) In accordance with ASTM D648, the test was conducted with a test piece having a thickness of 1/8 inch. The test piece was made of raw material pellets that had been dried at 120 ° C. for 5 hours, and using an injection molding machine (IS-100EN, manufactured by Toshiba Machine Co., Ltd.), a molding temperature of 320 ° C. and a mold temperature of 80 ° C. It was manufactured under the following molding conditions.
  • test pieces (length 12.7 mm, width 12.7 mm, thickness 3.2 mm, 1.5 mm) prepared according to UL standard 94. It was.
  • the UL standard 94 is a method for evaluating the flame retardancy from the afterflame time after the burner flame is indirectly fired for 10 seconds on a test piece of a predetermined size held vertically.
  • the tubular reactor had a jacket portion, and the temperature of the reaction solution was kept at 40 ° C. or lower by passing cooling water through the jacket.
  • the reaction solution exiting the tubular reactor was continuously introduced into a 40-liter baffled tank reactor equipped with a receding blade, and further 2.8 liters / hour of an aqueous sodium hydroxide solution of bisphenol A, The reaction was carried out by adding 0.07 liter / hour of 25% by weight aqueous sodium hydroxide solution, 17 liter / hour of water and 0.64 liter / hour of 1% by weight aqueous triethylamine solution.
  • the reaction liquid overflowing from the tank reactor was continuously extracted and allowed to stand to separate and remove the aqueous phase, and the methylene chloride phase was collected.
  • the polycarbonate oligomer thus obtained had a concentration of 318 g / liter and a chloroformate group concentration of 0.75 mol / liter.
  • the weight average molecular weight (Mw) was 1190.
  • the weight average molecular weight (Mw) was measured using GPC [column: TOSOH TSK-GEL MULTIPIORE HXL-M (2) + Shodex KF801 (1)], temperature 40 ° C., flow rate 1. It was measured as a standard polystyrene equivalent molecular weight (weight average molecular weight: Mw) at 0 ml / min, detector: RI].
  • methylene chloride solution of pt-butylphenol (PTBP) 140 g of PTBP dissolved in 2.0 liters of methylene chloride
  • BPA sodium hydroxide aqueous solution 577 g of NaOH and sodium dithionite 2
  • a solution in which 1012 g of BPA was dissolved in an aqueous solution in which 0.0 g was dissolved in 8.4 liters of water was added, and the polymerization reaction was carried out for 50 minutes.
  • the methylene chloride solution of the PC-PDMS copolymer obtained by washing was concentrated and pulverized, and the obtained flakes were dried at 120 ° C. under reduced pressure.
  • PDMS residue amount (PDMS copolymerization amount) determined by nuclear magnetic resonance (NMR) of the obtained PC-PDMS copolymer was 5.4% by mass, viscosity number measured according to ISO 1628-4 (1999) Was 47.0, and the viscosity average molecular weight Mv was 17,500.
  • This PC-PDMS copolymer was designated as A-4.
  • B-1-3 Titanium oxide coated with polyol (described as “prepared product” in the table) Rutile titanium dioxide particles having an average particle diameter of 0.2 ⁇ m were made into an aqueous slurry of 200 g / liter, and aluminum sulfate and sodium hydroxide were added to coat the surface of titanium dioxide with hydrous aluminum oxide.
  • the surface treatment amount was 5.0% by mass with respect to titanium dioxide in terms of Al 2 O 3 .
  • the washed cake obtained by filtering and washing the slurry was dried at 120 ° C. all day and night, and pulverized with a jet mill. This was baked at 800 ° C. for 2 hours in an electric furnace, and the hydrous aluminum oxide on the titanium dioxide surface was modified to alumina.
  • Titanium oxide for comparison titanium oxide not coated with polyol
  • Titanium oxide for comparison 1 whose surface is coated with alumina [Ishihara Sangyo Co., Ltd., “CR-60”, average particle size 0.21 ⁇ m]
  • Titanium oxide 2 for comparison whose surface is coated with silica / alumina [manufactured by Ishihara Sangyo Co., Ltd., “PF726” average particle size 0.21 ⁇ m]
  • Comparative titanium oxide 3 in which CR-60 is coated with dimethylpolysiloxane Titanium oxide B-1-2 prepared by using dimethylpolysiloxane in place of trimethylolpropane
  • C-1 Methoxy-modified silicone (manufactured by Toray Dow Corning Co., Ltd., “BY16-161”, viscosity 27 mm 2 / s at 25 ° C.)
  • C-2 Methoxy-modified silicone (“KR-511” manufactured by Shin-Etsu Chemical Co., Ltd.)
  • D Polytetrafluoroethylene
  • D-1 Polytetrafluoroethylene (Asahi Glass Co., Ltd., “Algoflon F5”)
  • D-2) Polytetrafluoroethylene [manufactured by Solvay Solexis, “CD076”]
  • E component Phosphorus stabilizer (antioxidant)
  • E-1 Phosphorous antioxidant: triphenylphosphine [manufactured by Johoku Chemical Industry Co., Ltd., “JC263”]
  • E-2) Phosphorous antioxidant: diphenylisooctyl phosphite [manufactured by ADEKA Corporation, “ADK Stab C”]
  • E-3) Phosphorous antioxidant: 2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite [manufactured by ADEKA, “PEP-36]]
  • G Component (G): Other additives
  • G-1 Octadecyl-3- (3,5-di-t-butyl-hydroxyphenyl) propionate [manufactured by Ciba Japan, “Irganox 1076”]
  • G-2 Glycerol monostearate [manufactured by Riken Vitamin Co., Ltd., “S-100A”]
  • G-3 Pentaerystole tetrastearate [Riken Vitamin Co., Ltd., “EW-440A”]
  • Examples 1 to 37 and Comparative Examples 1 to 10 Each component was mixed in the proportions shown in Tables 1 to 4 using a high-speed levitation mixer (KFC, SFC-50) and supplied to a vent type twin screw extruder (Toshiki Machine Co., Ltd., TEM35). Then, it was melt-kneaded at a barrel temperature of 260 to 300 ° C., a screw rotation speed of 150 to 250 rpm, and a discharge rate of 10 to 25 kg / hour to obtain a pellet sample for evaluation.
  • KFC high-speed levitation mixer
  • SFC-50 vent type twin screw extruder
  • Tables 1 to 4 revealed the following.
  • Examples 1 to 37 an aromatic polycarbonate resin composition and a molded article excellent in the balance of evaluation items are obtained.
  • Comparative Example 1 since the blending amount of the polyol-coated titanium oxide of the component (B) is less than the range of the present invention, the thermal conductivity is lower than that in Example 1.
  • Comparative Example 2 since the blending amount of the titanium oxide coated with the polyol of the component (B) is larger than the upper limit (220 parts by mass) of the range of the present invention, the impact resistance is lowered as compared with Example 4. .
  • Comparative Example 3 since the compounding amount of the organopolysiloxane containing the alkoxy group as the component (C) is less than the lower limit (3 parts by mass) of the range of the present invention, the impact resistance is reduced as compared with Example 9. ing.
  • Comparative Example 4 since the compounding amount of the organopolysiloxane containing the alkoxy group as the component (C) is larger than the upper limit (15 parts by mass) of the range of the present invention, the impact resistance is reduced as compared with Example 10. ing.
  • Comparative Example 5 since titanium oxide coated with dimethylpolysiloxane is used as the component (B), compared with Example 13 using titanium oxide coated with polyol, impact resistance and heat distortion temperature are higher. It is falling.
  • Comparative Example 6 since dimethylpolysiloxane is used as the component (C), the impact resistance is lowered as compared with Example 2 using an organopolysiloxane containing an alkoxy group. In Comparative Examples 7 to 10, since the titanium oxide coated with polyol is not used as the component (B), the impact resistance is lower than that of Example 2.
  • a molded product formed by injection molding of the aromatic polycarbonate resin composition of the present invention is a heat-radiating component for electronic or electric equipment, a heat-transfer component, a housing having a heat-dissipating function, in particular, a heat-radiating component for LED application products, and a heat-transfer component. It is extremely useful in the field of a housing having a heat dissipation function.

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  • 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)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

La présente invention a pour but de proposer : une composition de résine de polycarbonate aromatique, qui a une excellente conductivité thermique et d'excellentes propriétés isolantes qui sont requises pour des composants de dispositifs électroniques/électriques, et qui est apte à fournir une capacité de coloration qui permet des applications en tant qu'éléments de conception ; et un corps moulé qui est obtenu par moulage par injection de la composition de résine de polycarbonate aromatique. Le but est atteint par une composition de résine de polycarbonate aromatique qui est obtenue par mélange de 40-220 parties en masse d'oxyde de titane (B-1) qui est recouvert par un polyol, de 0-70 parties en masse de talc (B-2) et de 3-10 parties en masse d'un organopolysiloxane (C) qui contient un groupe alcoxy pour 100 parties en masse d'une résine de polycarbonate aromatique (A), le total du composant (B-1) et du composant (B-2) étant de 70-220 parties en masse.
PCT/JP2011/074059 2010-10-26 2011-10-19 Composition de résine de polycarbonate aromatique et corps moulé obtenu par moulage par injection de la composition WO2012056971A1 (fr)

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WO2013115182A1 (fr) * 2012-01-30 2013-08-08 出光興産株式会社 Composition de résine de polycarbonate et article moulé
JP2014028896A (ja) * 2012-07-31 2014-02-13 Teijin Ltd 遮熱性屋外設置用ポリカーボネート系樹脂筐体
WO2015036941A1 (fr) * 2013-09-10 2015-03-19 Sabic Global Technologies B.V. Compositions polymères conductrices de chaleur, ductiles et à base de polycarbonate, et utilisation de celles-ci
JP2016204520A (ja) * 2015-04-22 2016-12-08 三菱化学株式会社 ポリカーボネート樹脂組成物
JP2020059863A (ja) * 2020-01-23 2020-04-16 三菱ケミカル株式会社 ポリカーボネート樹脂組成物
JP6941209B1 (ja) * 2020-08-18 2021-09-29 三菱瓦斯化学株式会社 樹脂シート、多層体、および、カード

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KR102118422B1 (ko) * 2018-11-05 2020-06-05 정준석 고내열성 및 투명성을 가진 대전방지 마스터배치 조성물 및 이를 포함하는 대전방지 수지 조성물

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WO2013115182A1 (fr) * 2012-01-30 2013-08-08 出光興産株式会社 Composition de résine de polycarbonate et article moulé
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JP2014028896A (ja) * 2012-07-31 2014-02-13 Teijin Ltd 遮熱性屋外設置用ポリカーボネート系樹脂筐体
WO2015036941A1 (fr) * 2013-09-10 2015-03-19 Sabic Global Technologies B.V. Compositions polymères conductrices de chaleur, ductiles et à base de polycarbonate, et utilisation de celles-ci
JP2016204520A (ja) * 2015-04-22 2016-12-08 三菱化学株式会社 ポリカーボネート樹脂組成物
JP2020059863A (ja) * 2020-01-23 2020-04-16 三菱ケミカル株式会社 ポリカーボネート樹脂組成物
JP6941209B1 (ja) * 2020-08-18 2021-09-29 三菱瓦斯化学株式会社 樹脂シート、多層体、および、カード
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JP2022034561A (ja) * 2020-08-18 2022-03-03 三菱瓦斯化学株式会社 樹脂シート、多層体、および、カード
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