WO2012173111A1 - Composition de résine de polycarbonate et moulage obtenu à l'aide de celle-ci - Google Patents

Composition de résine de polycarbonate et moulage obtenu à l'aide de celle-ci Download PDF

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WO2012173111A1
WO2012173111A1 PCT/JP2012/065005 JP2012065005W WO2012173111A1 WO 2012173111 A1 WO2012173111 A1 WO 2012173111A1 JP 2012065005 W JP2012065005 W JP 2012065005W WO 2012173111 A1 WO2012173111 A1 WO 2012173111A1
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polycarbonate resin
resin composition
mass
group
carbon atoms
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PCT/JP2012/065005
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English (en)
Japanese (ja)
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野寺　明夫
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出光興産株式会社
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Priority to JP2013520555A priority Critical patent/JP5988971B2/ja
Priority to CN201280029564.7A priority patent/CN103608404B/zh
Priority to KR1020137033336A priority patent/KR101903214B1/ko
Publication of WO2012173111A1 publication Critical patent/WO2012173111A1/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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • 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
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2383/10—Block- or graft-copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2427/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2427/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Definitions

  • the present invention relates to a polycarbonate resin composition and a molded body using the same. More specifically, a polycarbonate resin composition that gives a molded article excellent in flame retardancy, rigidity, impact resistance, electrical conductivity and molded appearance, and further in thermal conductivity, and the resin composition, The present invention relates to a molded article having properties.
  • a conductive polymer material in which a conductive filler or the like is blended with a low-conductivity polymer material has been widely used.
  • the conductive filler metal fiber, metal powder, carbon black, carbon fiber and the like are generally used.
  • the metal fiber and metal powder are used as the conductive filler, there is an excellent conductivity imparting effect, but the corrosion resistance. There is a disadvantage that the mechanical strength is difficult to obtain.
  • carbon black is used as a conductive filler, conductive carbon black such as ketjen black, Vulcan XC72, and acetylene black, which can obtain high conductivity with a small amount of addition, is used. Is bad.
  • Patent Document 1 discloses a technique for improving conductivity and flame retardancy by blending a carbon nanotube with a polycarbonate-polyorganosiloxane copolymer (may be abbreviated as PC-PDMS).
  • PC-PDMS polycarbonate-polyorganosiloxane copolymer
  • Patent Document 3 disclose a technique for blending functional graphene with a resin.
  • Patent Document 2 is a technique of blending graphite with polycarbonate to impart thermal conductivity. However, unless it is used in combination with a flame retardant, flame retardancy is not manifested, and description of conductivity and rigidity is provided. There is no. In Patent Document 2, there is no description of graphene having a nano-order thickness, and dispersion of graphene having a nano-order thickness is difficult to produce using an ordinary extruder. The performance has not been fully developed.
  • patent document 3 is a technique which mix
  • the present invention has been made under such circumstances, and a polycarbonate resin composition that gives a molded article excellent in flame retardancy, rigidity, impact resistance, conductivity and molded appearance, and further in thermal conductivity and the like, and It is an object of the present invention to provide a molded article having the above-mentioned properties formed by molding the resin composition.
  • the present inventor has obtained a polycarbonate organosiloxane copolymer containing a polyorganosiloxane block composed of a specific structural unit at a predetermined ratio, and other aromatic polycarbonates. It has been found that a resin composition containing a predetermined amount of a graphene sheet can be adapted to the purpose with respect to a polycarbonate-based resin contained at a specific ratio. The present invention has been completed based on such findings.
  • the present invention provides the following (1) to (8).
  • a polycarbonate resin composition comprising (A) 70 to 99.5% by mass and graphene sheet (B) 30 to 0.5% by mass.
  • the polycarbonate-polyorganosiloxane copolymer (A-1) includes a structural unit having a main chain represented by the general formula (I) and a structural unit represented by the general formula (II),
  • R 1 and R 2 are each independently an alkyl or alkoxy group having 1 to 6 carbon atoms
  • X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, carbon A cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, —S—, —SO—, —SO 2 —, —O— or —CO—
  • R 3 to R 6 are each independently Represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms
  • Y represents an organic residue containing an aliphatic group or an aromatic group.
  • N is an average number of repetitions and represents an integer of 1 to 600, and a and b represent integers of 0 to 4.
  • Y is an organic residue from allylphenol or eugenol.
  • the structural unit represented by the general formula (I) is a structural unit derived from bisphenol A.
  • R 3 and R 4 in the structural unit represented by the general formula (II) are both methyl groups.
  • the polytetrafluoroethylene (C) is further contained in an amount of 0.01 to 1 part by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B).
  • a polycarbonate resin composition that gives a molded article excellent in flame retardancy, rigidity, impact resistance, electrical conductivity and molded appearance, as well as thermal conductivity, and the above-mentioned molded resin composition.
  • a molded body having properties can be provided.
  • the molded body of the present invention has the above-mentioned properties and does not cause contamination of semiconductors and the like due to the dropping of carbon. Therefore, the housing of electrical / electronic equipment such as OA equipment, information equipment, home appliances, The application fields such as parts, films, and automobile parts are expected to expand.
  • the polycarbonate resin composition of the present invention will be described.
  • the mass ratio of the polycarbonate-polyorganosiloxane copolymer (A-1) to the aromatic polycarbonate (A-2) other than (A-1) is 5:95 to 100: It comprises 70 to 99.5% by mass of a polycarbonate resin (A) consisting of 0 and 30 to 0.5% by mass of a graphene sheet (B).
  • A polycarbonate resin
  • B graphene sheet
  • the polycarbonate-polyorganosiloxane copolymer (A-1) used in the present invention includes a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II) in the main chain, Further, those containing 2 to 40% by mass of a polyorganosiloxane block composed of the structural unit represented by the general formula (II) are preferable.
  • the polycarbonate-polyorganosiloxane copolymer is sometimes referred to as “PC-PDMS copolymer”.
  • R 1 and R 2 are each independently an alkyl group or alkoxy group having 1 to 6 carbon atoms
  • X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, or a carbon number
  • R 3 to R 6 are each independently A hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms
  • Y represents an organic residue containing aliphatic or aromatic
  • n is an average number of repetitions and represents an integer of 1 to 600
  • a and b represent integers of 0 to 4.
  • Y is
  • the content of the polyorganosiloxane block is preferably 2 to 40% by mass from the viewpoint of flame retardancy and impact resistance. More preferably, it is 25 mass%.
  • the structural unit represented by the general formula (I) is preferably a structural unit derived from bisphenol A, and represented by the general formula (II).
  • R 3 and R 4 are preferably both methyl groups.
  • the viscosity average molecular weight of the PC-PDMS copolymer (A-1) is large.
  • the viscosity average molecular weight of the PC-PDMS copolymer (A-1) is preferably 15000 to 24000, more preferably 16000 to 22500, and further preferably 17000 to 21000.
  • the viscosity average molecular weight is 15000 or more, the strength of the molded product is sufficient.
  • the viscosity average molecular weight is 24000 or less, the viscosity of the copolymer becomes small, so that the productivity during production is good and the thin-wall molding is also good. .
  • the PC-PDMS copolymer (A-1) includes a dihydric phenol represented by the following general formula (1), a polyorganosiloxane represented by the following general formula (2), phosgene, carbonate, or chloro It is obtained by using a formate and a molecular weight regulator used as necessary.
  • R 1 and R 2 , X, a and b are the same as those in the general formula (I).
  • R 3 to R 6 , Y, n Is the same as in the general formula (II)
  • m is 0 or 1
  • Z is halogen, —R 7 OH, —R 7 COOH, —R 7 NH 2 , —COOH or —SH
  • 7 represents a linear, branched or cyclic alkylene group, an aryl-substituted alkylene group, an aryl-substituted alkylene group which may have an alkoxy group on the ring, or an arylene group.
  • the dihydric phenol represented by the general formula (1) used as a raw material for the PC-PDMS copolymer (A-1) is not particularly limited, but 2,2-bis (4-Hydroxyphenyl) propane (common name: bisphenol A) is preferred.
  • bisphenol A 2,2-bis (4-Hydroxyphenyl) propane
  • dihydric phenols other than bisphenol A include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2 -Bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4- Hydroxyphenyl) naphthylmethane, 1,1-bis (4-hydroxy-t-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-) 3,5-tetramethylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorofe) Bis (hydroxyaryl) alkanes such as propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-d
  • the polyorganosiloxane represented by the general formula (2) is a phenol having an olefinically unsaturated carbon-carbon bond, preferably vinylphenol, allylphenol, eugenol, isopropenylphenol or the like having a predetermined polymerization degree n. It can be easily produced by hydrosilation reaction at the end of the polyorganosiloxane chain.
  • the phenols are more preferably allylphenol or eugenol.
  • Y in the general formula (II) of the component (A-1) is an organic residue derived from allylphenol or eugenol.
  • R 3 to R 6 are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms, 6 represents an alkoxy group having 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and n represents an average number of repeating units of the organosiloxane constituent unit and represents a number of 1 to 600.
  • R 8 represents an alkyl, alkenyl, aryl or aralkyl group, c represents a positive integer, and is usually an integer of 1 to 6.
  • a phenol-modified polyorganosiloxane represented by the general formula (3) is preferable.
  • ⁇ , ⁇ -bis [3- (o-hydroxyphenyl) propyl] polydimethylsiloxane which is one of the compounds represented by the general formula (4), is represented by the general formula (5): ⁇ , ⁇ -bis [3- (4-hydroxy-2-methoxyphenyl) propyl] polydimethylsiloxane, which is one of the compounds shown, is preferred.
  • the phenol-modified polyorganosiloxane can be produced by a known method. As a manufacturing method, the method shown below is mentioned, for example. First, cyclotrisiloxane and disiloxane are reacted in the presence of an acidic catalyst to synthesize ⁇ , ⁇ -dihydrogenorganopolysiloxane. At this time, ⁇ , ⁇ -dihydrogenorganopolysiloxane having a desired average repeating unit can be synthesized by changing the charging ratio of cyclotrisiloxane and disiloxane.
  • this ⁇ , ⁇ -dihydrogenorganopolysiloxane is subjected to an addition reaction with a phenol compound having an unsaturated aliphatic hydrocarbon group such as allylphenol or eugenol, to thereby obtain a desired compound.
  • a phenol compound having an unsaturated aliphatic hydrocarbon group such as allylphenol or eugenol
  • a phenol-modified polyorganosiloxane having an average repeating unit can be produced.
  • the component (A-2) which is an aromatic polycarbonate other than the above (A-1) is a dihydric phenol compound and an organic solvent inert to the reaction, in the presence of an alkaline aqueous solution.
  • interfacial polymerization method in which polymerization catalyst such as tertiary amine or quaternary ammonium salt is added to polymerize, or dihydric phenol compound is dissolved in pyridine or mixed solution of pyridine and inert solvent
  • polymerization catalyst such as tertiary amine or quaternary ammonium salt
  • dihydric phenol compound is dissolved in pyridine or mixed solution of pyridine and inert solvent
  • the dihydric phenol compound used in the production of the component (A-2) aromatic polycarbonate is 2,2-bis (4-hydroxyphenyl) propane (common name: bisphenol A), bis (4-hydroxyphenyl). Methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane Bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) naphthylmethane, 1,1-bis (4-hydroxy-3-t -Butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2 , 2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlor
  • a molecular weight regulator In the production of the aromatic polycarbonate component (A-2), a molecular weight regulator, a terminal terminator, and the like may be used as necessary. Any of these can be used as long as they are usually used for polymerization of polycarbonate resin.
  • Specific molecular weight regulators include monohydric phenols such as phenol, on-butylphenol, mn-butylphenol, pn-butylphenol, o-isobutylphenol, m-isobutylphenol, and p-isobutylphenol.
  • monovalent carboxylic acid and derivatives thereof, and monovalent phenol can be used.
  • a branched polycarbonate can be obtained by using a branching agent for the above dihydric phenol compound.
  • the amount of the branching agent added is preferably 0.01 to 3 mol%, more preferably 0.1 to 1.0 mol%, based on the dihydric phenol compound.
  • branching agent examples include 1,1,1-tris (4-hydroxyphenyl) ethane, 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl ] Ethylidene] bisphenol, ⁇ , ⁇ ′, ⁇ ′′ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, 1- [ ⁇ -methyl- ⁇ - (4′-hydroxyphenyl) ethyl]- Examples thereof include compounds having three or more functional groups such as 4- [ ⁇ ′, ⁇ ′-bis (4 ′′ -hydroxyphenyl) ethyl] benzene, phloroglysin, trimellitic acid, and isatin bis (o-cresol).
  • the content of (A-1) is 5 to 100% by mass, preferably 70 to 100% by mass, The content is preferably 50 to 100% by mass, and the content of (A-2) is 95 to 0% by mass, preferably 30 to 0% by mass, and more preferably 50 to 0% by mass.
  • the content of (A-1) is 5% by mass or more, or the content of (A-2) is 95% by mass or less, the content of the polyorganosiloxane block portion in the polycarbonate resin (A) is increased.
  • the content of the polyorganosiloxane block portion having the structural unit of the general formula (II) is preferably 0.1 to 40 in the polycarbonate resin (A) comprising the components (A-1) and (A-2).
  • % By mass, more preferably 0.5 to 25% by mass, still more preferably 0.5 to 15% by mass, and still more preferably 0.5 to 10% by mass. If it is 0.1 mass% or more, the effect of improving impact strength is sufficient, while if it is 40 mass% or less, it has sufficient flame retardancy and heat resistance.
  • Graphene sheet (B) In the polycarbonate resin composition of the present invention, in order to impart properties such as flame retardancy, conductivity, rigidity, molded appearance, and thermal conductivity to the molded body, it is necessary to contain a graphene sheet as the component (B). Cost.
  • a graphene sheet is a graphene plate having one or more layers of graphene surfaces, and is usually sliced using ultrasonic energy, and the level of flaking is to adjust the sound generation time (sonification) time Can be controlled by.
  • the graphene sheet used in the present invention preferably has a thickness of 5 to 10 nm and a size of 3 ⁇ m or more.
  • the thickness of the graphene sheet used in the present invention is 5 to 10 nm and the size is 3 ⁇ m or more, the dispersibility of the graphene sheet is improved, and it is easy to be combined with the resin, flame retardancy, conductivity, rigidity, molded appearance, Furthermore, a molded body having excellent thermal conductivity can be obtained.
  • the thickness of the graphene sheet is preferably 6 to 8 nm, and the size of the graphene sheet is preferably 3 to 30 ⁇ m, more preferably 5 to 25 ⁇ m, still more preferably 5 to 20 ⁇ m.
  • the size of the graphene sheet is preferably 5 to 30 ⁇ m, and more preferably 5 to 20 ⁇ m.
  • the graphene sheet has a plate-like shape, and its thickness is the size in the thickness direction formed by overlapping the graphene sheets.
  • the size is the size of the graphene structure itself. It can be measured by the method described in 1. Products include “xGnP” (graphene nanoplatelet) manufactured by XG Sciences. In contrast to carbon nanotubes, it has an open and flat shape, so it is possible to introduce functional groups at the peripheral edges and to apply an interfacial treatment to the surface.
  • the above-mentioned polycarbonate resin (A) is added in an amount of 70 to 99.5% by mass and the graphene in order to impart properties such as conductivity, rigidity, flame retardancy, and thermal conductivity. It is necessary to contain the sheet (B) in a proportion of 30 to 0.5% by mass. When the content of the graphene sheet (B) is less than 0.5% by mass, the effect of imparting the properties is difficult to be exhibited. From the above viewpoint, the preferable content of the graphene sheet (B) is 1 to 30% by mass, and more preferably 1 to 20% by mass with respect to the total amount with the polycarbonate resin (A).
  • Polytetrafluoroethylene (C) In the polycarbonate resin composition of the present invention, it is preferable to contain polytetrafluoroethylene as the component (C) in order to have a melt dripping preventing effect and to impart high flame retardancy.
  • the polytetrafluoroethylene (C) is polytetrafluoroethylene (hereinafter abbreviated as PTFE) having a fibril forming ability and an average molecular weight of 500,000 or more, and has an effect of preventing melt dripping and has high flame retardancy. Can be granted.
  • the average molecular weight must be 500,000 or more, preferably 500,000 to 10,000,000, more preferably 1,000,000 to 10,000,000.
  • PTFE having fibril-forming ability is not particularly limited, and specifically, “Teflon (registered trademark)” 6-J (manufactured by Mitsui DuPont Fluorochemical Co., Ltd.), Polyflon D-1, Polyflon F-103, Polyflon F201, Polyflon MPA FA-100 (manufactured by Daikin Industries), CD076 (manufactured by Asahi Glass Fluoropolymers), Argoflon F5 (manufactured by Montefluos), and the like.
  • Teflon registered trademark
  • 6-J manufactured by Mitsui DuPont Fluorochemical Co., Ltd.
  • Polyflon D-1 Polyflon F-103
  • Polyflon F201 Polyflon MPA FA-100
  • CD076 manufactured by Asahi Glass Fluoropolymers
  • Argoflon F5 manufactured by Montefluos
  • PTFE having the fibril-forming ability as described above is, for example, tetrafluoroethylene in an aqueous solvent in the presence of sodium, potassium or ammonium peroxydisulfide, at a pressure of 7 to 700 kPa, at a temperature of 0 to 200 ° C., preferably Can be obtained by polymerization at 20 to 100 ° C.
  • the content of PTFE is usually 0.01 to 1 part by mass, preferably 0.05 to 1 part by mass with respect to 100 parts by mass of the total amount of the polycarbonate resin (A) and the graphene sheet (B). 0.9 parts by mass, more preferably 0.1 to 0.8 parts by mass. When the content of the PTFE is within the above range, the melt dripping prevention property in the intended flame retardancy is sufficient.
  • a mixed powder composed of polytetrafluoroethylene particles and organic polymer particles can be contained instead of the PTFE.
  • the polytetrafluoroethylene particles in the mixed powder usually have a particle size of 10 ⁇ m or less, preferably 0.05 to 1.0 ⁇ m.
  • the polytetrafluoroethylene particles are prepared, for example, as an aqueous dispersion dispersed in water containing an emulsifier and the like. This aqueous dispersion of polytetrafluoroethylene particles is obtained by emulsion polymerization of a tetrafluoroethylene monomer using a fluorine-containing surfactant.
  • Fluorine-containing olefins such as hexafluoropropylene, chlorotrifluoroethylene, fluoroalkylethylene and perfluoroalkyl vinyl ether as copolymerization components, as long as the properties of polytetrafluoroethylene are not impaired during the emulsion polymerization of polytetrafluoroethylene particles, Fluorine-containing alkyl (meth) acrylates such as perfluoroalkyl (meth) acrylate can be used.
  • the content of the copolymer component is preferably 10% by mass or less with respect to tetrafluoroethylene in the polytetrafluoroethylene particles.
  • the organic polymer particles in the mixed powder are not particularly limited, but are compatible with the polycarbonate resin from the viewpoint of dispersibility of the polytetrafluoroethylene particles when blended with the polycarbonate resin (A). It is preferable that it has.
  • the content of the mixed powder composed of the polytetrafluoroethylene particles and the organic polymer particles is usually 0.1 to 1 with respect to 100 parts by mass of the total amount of the polycarbonate resin (A) and the graphene sheet (B). Parts by mass, preferably 0.1 to 0.9 parts by mass, more preferably 0.2 to 0.8 parts by mass. When the content of the mixed powder is 0.1 parts by mass or more, drip performance is good and flame retardancy can be achieved. On the other hand, if it is 1 mass part or less, the ratio of the organic polymer in a composition does not increase too much, and a flame retardance can be achieved.
  • additives include phosphorus antioxidants, alkali (earth) metal salts of organic sulfonic acids as flame retardants, reinforcing materials, fillers, hindered amine light stabilizers, and oxidations other than phosphorus. Inhibitors, ultraviolet absorbers, antistatic agents, lubricants, mold release agents, dyes, pigments, elastomers for improving impact resistance, and the like.
  • phosphorus antioxidant there is no restriction
  • Representative examples include tris (nonylphenyl) phosphite, 2-ethylhexidiphenyl phosphite, trimethyl phosphite, triethyl phosphite, tributyl phosphite, trioctyl phosphite, trinonyl phosphite, tridecyl Trialkyl phosphites such as phosphite, trioctadecyl phosphite, distearyl pentaerythryl diphosphite, tris (2-chloroethyl) phosphite, tris (2,3-dichloropropyl) phosphite, and tricyclohexyl phosphite Tricycloalkyl phosphite, triphenyl phosphite,
  • these phosphorus antioxidants may be used alone or in combination of two or more.
  • the content of the phosphorus antioxidant in the polycarbonate resin composition is preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the polycarbonate resin (A). By containing the phosphorus antioxidant in the above range, a sufficient antioxidant effect can be obtained.
  • Alkali (earth) metal salt of organic sulfonic acid In the polycarbonate resin composition of the present invention, in order to improve flame retardancy, an alkali metal salt and / or alkaline earth metal salt of organic sulfonic acid (hereinafter also referred to as alkali (earth) metal salt of organic sulfonate). ) Can be contained.
  • the organic sulfonic acid include perfluoroalkane sulfonic acid and polystyrene sulfonic acid.
  • Various organic sulfonic acid alkali (earth) metal salts include organic sulfonic acid alkali metal salts and alkaline earth metal salts having at least one carbon atom.
  • alkali metal examples include sodium, potassium, lithium and cesium
  • alkaline earth metal examples include magnesium, calcium, strontium and barium. Of these, sodium, potassium and cesium salts are preferred.
  • component (C) an alkali metal salt and / or an alkaline earth metal salt of perfluoroalkanesulfonic acid or polystyrenesulfonic acid is preferable.
  • alkali (earth) metal salt of perfluoroalkanesulfonic acid examples include those represented by the following general formula (12). (C d F 2d + 1 SO 3 ) e M (12)
  • d represents an integer of 1 to 10
  • M represents an alkaline metal such as lithium, sodium, potassium and cesium, or an alkaline earth metal such as magnesium, calcium, strontium and barium
  • e represents M The valence of is shown.
  • these metal salts for example, those described in Japanese Patent Publication No. 47-40445 are applicable.
  • examples of perfluoroalkanesulfonic acid include perfluoromethanesulfonic acid, perfluoroethanesulfonic acid, perfluoropropanesulfonic acid, perfluorobutanesulfonic acid, perfluoromethylbutanesulfonic acid, perfluoro Examples include hexanesulfonic acid, perfluoroheptanesulfonic acid, and perfluorooctanesulfonic acid. In particular, these potassium salts are preferably used.
  • alkylsulfonic acid alkylsulfonic acid, benzenesulfonic acid, alkylbenzenesulfonic acid, diphenylsulfonic acid, naphthalenesulfonic acid, 2,5-dichlorobenzenesulfonic acid, 2,4,5-trichlorobenzenesulfonic acid, diphenylsulfone-3-sulfonic acid
  • examples thereof include diphenylsulfone-3,3′-disulfonic acid, naphthalenetrisulfonic acid and their fluorine-substituted products, and alkali metal salts and alkaline earth metal salts of organic sulfonic acids such as polystyrene sulfonic acid.
  • perfluoroalkanesulfonic acid and diphenylsulfonic acid are particularly preferable as the organic sulfonic acid.
  • alkali (earth) metal salt of polystyrene sulfonic acid examples include an alkali (earth) metal salt of a sulfonate group-containing aromatic vinyl resin represented by the following general formula (13).
  • Q represents a sulfonate group
  • R 9 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
  • s represents an integer of 1 to 5
  • t represents a mole fraction
  • the sulfonate group of Q is an alkali metal salt and / or alkaline earth metal salt of sulfonic acid, and the metals include sodium, potassium, lithium, rubidium, cesium, beryllium, magnesium, calcium, strontium and barium.
  • R 9 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrogen atom or a methyl group.
  • s is an integer of 1 to 5, and t has a relationship of 0 ⁇ t ⁇ 1. Therefore, the sulfonate group (Q) may include a fully substituted or partially substituted aromatic ring.
  • the content of the alkali (earth) metal salt of the organic sulfonic acid is preferably 0.01 to 0.15 parts by mass, more preferably 100 parts by mass of the polycarbonate resin (A).
  • the amount is 0.02 to 0.13 parts by mass, more preferably 0.03 to 0.12 parts by mass.
  • the flame retardancy can be sufficiently improved.
  • the polycarbonate resin composition of the present invention does not substantially contain any of an organic halogen flame retardant and an organic phosphate ester flame retardant. For this reason, there is no fear of generation of harmful gas, contamination of the molding machine, burning of the resin, and deterioration of heat resistance.
  • the polycarbonate resin composition of the present invention comprises the above-mentioned components (A) [(A-1) and (A-2)], (B) component and (C) component or mixed powder used as necessary, Can be prepared by blending various components at a predetermined ratio and kneading.
  • blending 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 screw. It can be carried out by a method using an extruder, a kneader or the like.
  • the heating temperature at the time of kneading is usually appropriately selected within the range of 240 to 300 ° C.
  • the components other than the polycarbonate-based resin can be added in advance as a master batch with melt-kneading with the polycarbonate-based resin.
  • the polycarbonate resin composition of the present invention uses the above-mentioned melt-kneading molding machine, or using the obtained pellets as a raw material, an injection molding method, an injection compression molding method, an extrusion molding method, a blow molding method, a press molding method, a vacuum
  • Various molded articles can be produced by a molding method, a foam molding method, or the like.
  • a pellet-shaped molding raw material can be produced by the melt kneading method, and then the pellet can be used suitably for production of an injection molded product by injection molding or injection compression molding.
  • a gas injection molding method for preventing the appearance of sink marks or for reducing the weight can be adopted.
  • the molded article of the present invention produced in this way is excellent in flame retardancy, rigidity, impact resistance, conductivity, molded appearance, thermal conductivity, and the like, and may cause contamination of semiconductors and the like due to carbon falling off. Therefore, it is suitably used for housings, parts, films, and automobile parts of electrical / electronic equipment such as OA equipment, information equipment, and home appliances.
  • PC composition ⁇ Performance evaluation of polycarbonate resin composition (hereinafter sometimes abbreviated as PC composition)> (Test piece preparation method)
  • PC composition polycarbonate resin composition
  • Tables 1 to 3 supplied to an extruder (model name: VS40, manufactured by Tanabe Plastic Machine Co., Ltd.), melt-kneaded at 240 ° C., and pelletized.
  • Irganox 1076 manufactured by BASF Japan Ltd.
  • the obtained pellets were dried at 120 ° C. for 12 hours, and then injection molded under the conditions of an injection molding machine (manufactured by Toshiba Machine Co., Ltd., model: IS100N) cylinder temperature 260 ° C. and mold temperature 80 ° C. Obtained.
  • an injection molding machine manufactured by Toshiba Machine Co., Ltd., model: IS100N
  • IZOD Izod impact strength
  • Flexural modulus conforms to ASTM D-790 (test conditions, etc .: 23 ° C., 4 mm)
  • Volume resistivity value Conforms to JIS K6911 (test plate: 80 ⁇ 80 ⁇ 3 mm)
  • Molding appearance Evaluated according to the following criteria. ⁇ : Good, ⁇ : Defect appearance such as bumps on the surface
  • ⁇ Thickness and size of graphene sheet> The thickness and size of the graphene sheet were measured by observation with an electron microscope.
  • the tubular reactor used here was a double tube, and the discharge temperature of the reaction solution was maintained at 25 ° C. through the jacket portion through cooling water.
  • the pH of the effluent was adjusted to 10-11.
  • the reaction solution thus obtained was allowed to stand to separate and remove the aqueous phase, and the methylene chloride phase (220 liters) was collected to obtain a PC oligomer (concentration 317 g / liter).
  • the degree of polymerization of the PC oligomer obtained here was 2 to 4, and the concentration of the chloroformate group was 0.7 mol / L.
  • Production Example 3 [Production of PC-PDMS copolymer] 182 g of reactive PDMS obtained in Production Example 2 was dissolved in 2 liters of methylene chloride, and 10 liters of PC oligomer obtained in Production Example 1 were mixed. Thereto, 26 g of sodium hydroxide dissolved in 1 liter of water and 5.7 cm 3 of triethylamine were added, and the mixture was stirred and reacted at room temperature at 500 rpm for 1 hour.
  • the PDMS content is determined based on the intensity ratio between the isopropyl methyl group peak of bisphenol A found at 1.7 ppm by 1 H-NMR and the methyl group peak of dimethylsiloxane found at 0.2 ppm. It was.
  • the polycarbonate resin composition belonging to the present invention contains a graphene sheet at a specific ratio, so that high flame retardancy is obtained and a reduction in impact strength is reduced. It is also excellent in rigidity, conductivity and molded appearance.
  • the impact strength and flame retardancy are excellent.
  • the flame retardance of a thin wall is attained.
  • the carbon nanotubes used in the comparative examples are inferior in rigidity and flame retardancy compared with the graphene sheet, and the micro-order graphite not only significantly reduces the impact strength but also reduces the flame retardancy. End up.
  • the polycarbonate resin composition of the present invention can give a molded article excellent in flame retardancy, rigidity, impact resistance, conductivity, molded appearance, and thermal conductivity.
  • This molded body is expected to expand its application fields such as housings, parts, films, and automobile parts of electrical / electronic equipment such as OA equipment, information equipment, and home appliances.

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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)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention porte sur : une composition de résine de polycarbonate caractérisée en ce qu'elle comprend 70-99,5 % en masse d'une résine de polycarbonate (A) et 30-0,5 % en masse d'une feuille de graphène (B), la résine de polycarbonate (A) comprenant un copolymère polycarbonate-polyorganosiloxane (A-1) et un polycarbonate aromatique (A-2) autre que le composant (A-1) à un rapport de 5:95 à 100:0 en masse ; et un moulage obtenu par moulage de la composition de résine. La présente invention concerne : une composition de résine de polycarbonate qui permet la fabrication d'un moulage ayant une excellente capacité de retard de flamme, une excellente raideur, une excellente résistance aux chocs, une excellente conductivité électrique, un excellente aspect de moulage, une excellente conductivité de chaleur, etc. ; et un moulage qui est obtenu par moulage de la composition de résine et qui présente les propriétés mentionnées ci-dessus.
PCT/JP2012/065005 2011-06-17 2012-06-12 Composition de résine de polycarbonate et moulage obtenu à l'aide de celle-ci WO2012173111A1 (fr)

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CN201280029564.7A CN103608404B (zh) 2011-06-17 2012-06-12 聚碳酸酯树脂组合物及使用其的成形体
KR1020137033336A KR101903214B1 (ko) 2011-06-17 2012-06-12 폴리카보네이트 수지 조성물 및 그것을 사용한 성형체

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WO2013141058A1 (fr) * 2012-03-22 2013-09-26 出光興産株式会社 Composition de résine de polycarbonate et corps moulé à base de celle-ci
CN104990022A (zh) * 2015-05-27 2015-10-21 安徽博昌电子科技股份有限公司 吸附式应急指示灯
CN105829447A (zh) * 2013-12-26 2016-08-03 出光兴产株式会社 屋外设置用成形体
WO2023017131A3 (fr) * 2021-08-13 2023-04-06 Jt International Sa Dispositif à fumer électronique doté d'un boîtier de batterie

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CN105038285A (zh) * 2014-04-18 2015-11-11 台湾奈米碳管股份有限公司 含碳的高分子复合颗粒的制造方法
CN104693772A (zh) * 2015-03-04 2015-06-10 安徽科聚新材料有限公司 一种玻纤云母混合增强聚碳酸酯材料及其制备方法
CN106800765B (zh) * 2017-01-21 2018-06-08 郑州人造金刚石及制品工程技术研究中心有限公司 一种用于智能手机外壳的聚碳酸酯材料及其制备方法和应用
CN111621133B (zh) * 2020-06-30 2022-11-08 万华化学集团股份有限公司 一种高介电低损耗的聚碳酸酯组合物及其制备方法与用途
CN115286915A (zh) * 2022-08-31 2022-11-04 河南德利新能源材料有限公司 一种聚碳酸酯组合物制备方法

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CN105829447A (zh) * 2013-12-26 2016-08-03 出光兴产株式会社 屋外设置用成形体
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WO2023017131A3 (fr) * 2021-08-13 2023-04-06 Jt International Sa Dispositif à fumer électronique doté d'un boîtier de batterie

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KR101903214B1 (ko) 2018-10-01
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