WO2013069782A1 - Procédé de fabrication d'une composition de résine thermoplastique et article moulé - Google Patents

Procédé de fabrication d'une composition de résine thermoplastique et article moulé Download PDF

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Publication number
WO2013069782A1
WO2013069782A1 PCT/JP2012/079164 JP2012079164W WO2013069782A1 WO 2013069782 A1 WO2013069782 A1 WO 2013069782A1 JP 2012079164 W JP2012079164 W JP 2012079164W WO 2013069782 A1 WO2013069782 A1 WO 2013069782A1
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Prior art keywords
thermoplastic resin
component
resin composition
group
acid
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PCT/JP2012/079164
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English (en)
Japanese (ja)
Inventor
晋太郎 小松
英浩 古▲高▼
原田　博史
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住友化学株式会社
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    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/203—Solid polymers with solid and/or liquid additives
    • 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
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
    • 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
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/045—Reinforcing macromolecular compounds with loose or coherent fibrous material with vegetable or animal fibrous material
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/12—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of short lengths, e.g. chopped filaments, staple fibres or bristles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/16—Fillers
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08J2367/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the hydroxy and the carboxyl groups directly linked to aromatic rings
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08K2201/006—Additives being defined by their surface area

Definitions

  • the present invention relates to a molded article excellent in thermal conductivity and a method for producing a thermoplastic resin composition for obtaining the molded article.
  • JP-A-62-100577 Japanese Patent Laid-Open No. 4-178421 JP-A-5-86246
  • a molded body having a relatively complicated shape such as used for electric / electronic parts is generally manufactured by injection molding.
  • injection molding the thermal conductivity in the resin flow direction can be improved relatively easily, but it is very difficult to improve the thermal conductivity in the thickness direction of the molded product perpendicular to the flow direction. There was a problem that it was difficult.
  • the filler has to be highly filled, so that there is a problem that the strength of the molded body is lowered.
  • the present invention has been made in view of the above circumstances, and has a molded body excellent in electrical conductivity and strength in the thickness direction, having excellent electrical insulation as an electrical / electronic component, and the molded body It is an object of the present invention to provide a method for producing a thermoplastic resin composition for obtaining the above.
  • the present invention has the following aspects.
  • the first aspect of the present invention is: [1] Using a melt-kneading extruder provided with a nozzle, a cylinder and a screw installed in the cylinder, from the supply port provided in the cylinder, the following component (A), the following component (B) and the following component ( C) is supplied to the cylinder to melt and knead the component (A), the component (B) and the component (C) to obtain a kneaded product, and the kneaded product is fed from the nozzle to the melt kneading extruder.
  • the present invention relates to a method for producing a thermoplastic resin composition, comprising extruding to the outside and cooling the kneaded product at a cooling rate of 35 ° C./second or less.
  • thermoplastic resin composition according to [1], wherein the component (B) has a BET specific surface area of 1.0 to 5.0 m 2 / g.
  • thermoplastic resin composition according to [1] or [2], wherein the particle size distribution obtained by laser diffraction scattering measurement of the component (B) is bimodal.
  • the particle size distribution obtained by laser diffraction scattering measurement of the component (B) is maximum in the range of the volume average particle size of 1 to 5 ⁇ m and in the range of the volume average particle size of 0.1 to 1 ⁇ m, respectively.
  • the component (C) is at least one substance selected from the group consisting of carbon fiber, glass fiber, wollastonite whisker, aluminum borate whisker, and potassium titanate whisker.
  • the manufacturing method of the thermoplastic resin composition as described in any one.
  • thermoplastic resin composition according to any one of [1] to [5], wherein the component (A) is a liquid crystal polyester.
  • the liquid crystalline polyester comprises a repeating unit derived from at least one aromatic hydroxycarboxylic acid selected from the group consisting of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, hydroquinone and 4,4 ′
  • the total supply amount of the components (B) and (C) is 100 parts by mass or more with respect to 100 parts by mass of the component (A).
  • a method for producing a thermoplastic resin composition is 100 parts by mass or more with respect to 100 parts by mass of the component (A).
  • the second aspect of the present invention is: [9] relates to a molded article obtained by molding the thermoplastic resin composition obtained by the production method according to any one of [1] to [8].
  • the electrical / electronic component is at least one component selected from the group consisting of a sealing material for electronic elements, an insulator, a reflector for display device, a housing for storing electronic elements, and a surface-mounted component.
  • a sealing material for electronic elements for electronic elements
  • an insulator for electronic elements
  • a reflector for display device for display device
  • a housing for storing electronic elements
  • a surface-mounted component for storing electronic elements.
  • a third aspect of the present invention uses a melt kneading extruder provided with a cylinder and a screw installed in the cylinder, and from the supply port provided in the cylinder, the following components (A), (B) and ( C) is supplied to the cylinder and melt-kneaded to produce a thermoplastic resin composition, in which the kneaded product extruded from the nozzle of the melt-kneading extruder is cooled at a cooling rate of 35 ° C / Provided is a method for producing a thermoplastic resin composition characterized by cooling in seconds or less.
  • thermoplastic resin composition (A) Thermoplastic resin (B) Alumina fine particles (C) Fibrous filler
  • BET specific surface area of the component (B) is 1.0. It is preferably ⁇ 5.0 m 2 / g.
  • the particle size distribution obtained by laser diffraction scattering measurement of the component (B) is preferably bimodal.
  • the particle size distribution obtained by laser diffraction scattering measurement of the component (B) is in the range of 1-5 ⁇ m in volume average particle size, and the volume Bimodality having maximum values in the average particle size range of 0.1 to 1 ⁇ m is preferable.
  • the component (C) is made of the group consisting of carbon fiber, glass fiber, wollastonite whisker, aluminum borate whisker, and potassium titanate whisker. It is preferably one or more selected.
  • the component (A) is preferably a liquid crystal polyester.
  • the liquid crystal polyester is a repeating product derived from an aromatic hydroxycarboxylic acid of p-hydroxybenzoic acid and / or 6-hydroxy-2-naphthoic acid.
  • the total supply amount of the components (B) and (C) is 100 parts by mass or more with respect to 100 parts by mass of the component (A).
  • the 4th aspect of this invention provides the molded object formed by shape
  • the molded body of the fourth aspect of the present invention preferably has a volume resistivity value at 23 ° C. of 1 ⁇ 10 10 ⁇ m or more.
  • the molded body of the fourth aspect of the present invention is preferably for electric / electronic parts.
  • the electrical / electronic component is composed of a group consisting of an electronic element sealing material, an insulator, a display device reflector, a housing for electronic element storage, and a surface mount component. It is preferably one or more selected.
  • the molded object which has the electrical insulation suitable as an electrical / electronic component, and was excellent in the thermal conductivity of thickness direction, and intensity
  • the method for producing a thermoplastic resin composition according to the first aspect of the present invention uses a melt-kneading extruder provided with a nozzle, a cylinder, and a screw installed in the cylinder, from a supply port provided in the cylinder.
  • the following component (A), the following component (B) and the following component (C) are supplied to the cylinder, and the component (A), the component (B) and the component (C) are melt-kneaded to obtain a kneaded product.
  • thermoplastic resin composition capable of producing a molded article excellent in electrical insulation, thermal conductivity in the thickness direction, and strength can be obtained.
  • thermal conductivity means “thermal conductivity in the thickness direction of the molded body”.
  • the “thickness direction” means a direction perpendicular to the MD direction and the TD direction of the molded product (molded plate).
  • MD direction means the injection direction of the molded product (molded plate), and “TD direction” means the width direction of the molded product (molded plate) perpendicular to the injection direction.
  • the method for producing a thermoplastic resin composition according to the third aspect of the present invention uses a melt-kneading extruder provided with a cylinder and a screw installed in the cylinder, and from the supply port provided in the cylinder, the following A method for producing a thermoplastic resin composition by supplying components (A), (B) and (C) to the cylinder and melt-kneading them, and is extruded from the nozzle of the melt-kneading extruder.
  • the kneaded product is cooled at a cooling rate of 35 ° C./second or less.
  • thermoplastic resin (B) Alumina fine particles (C) Fibrous filler
  • the cooling rate of the extruded kneaded product is set to 35 ° C./sec or less, which is lower than the conventional one, so A thermoplastic resin composition capable of producing a molded article having excellent properties, thermal conductivity in the thickness direction, and strength is obtained.
  • thermal conductivity means “thermal conductivity in the thickness direction of the molded body”.
  • the thermoplastic resin (component (A)) is preferably one that can be molded at a molding temperature of 200 to 450 ° C.
  • examples thereof include polyolefin, polystyrene, polyamide, halogenated vinyl resin, polyacetal, saturated polyester, polycarbonate, poly
  • examples thereof include aryl sulfone, polyaryl ketone, polyphenylene ether, polyphenylene sulfide, polyaryl ether ketone, polyether sulfone, polyphenylene sulfide sulfone, polyarylate, polyamide, liquid crystal polyester, and fluororesin.
  • a thermoplastic resin may be used individually by 1 type, and may use 2 or more types together as a polymer alloy.
  • the thermoplastic resin is preferably liquid crystal polyester, polyethersulfone, polyarylate, polyphenylene sulfide, polyamide 4/6 or polyamide 6T, and more preferably polyphenylene sulfide or liquid crystal polyester because of excellent heat resistance and electrical insulation. . And since it is excellent also in the thin-wall moldability in addition to the point which is excellent in heat resistance and electrical insulation, liquid crystalline polyester is especially preferable. As described above, when the liquid crystalline polyester having excellent thin-wall moldability is used as the thermoplastic resin, the moldability at the time of molding a relatively complicated shape of electric / electronic parts becomes particularly good.
  • Polyphenylene sulfide is typically a resin mainly containing a repeating unit represented by the following formula (10).
  • Such polyphenylene sulfide can be produced by a reaction of a halogen-substituted aromatic compound and an alkali sulfide disclosed in “US Pat. No. 2,513,188” and “Japanese Examined Patent Publication No. 44-27671”, “US Pat. No. 3,274,165”.
  • Examples include a method of performing a condensation reaction with sulfur chloride under a Lewis acid catalyst. Moreover, you may use the commercially available polyphenylene sulfide (for example, polyphenylene sulfide by Dainippon Ink & Chemicals, Inc.) which can be obtained easily.
  • polyphenylene sulfide for example, polyphenylene sulfide by Dainippon Ink & Chemicals, Inc.
  • the liquid crystalline polyester is a liquid crystalline polyester that exhibits liquid crystallinity in a molten state, and is preferably melted at a temperature of 450 ° C. or lower.
  • the liquid crystal polyester may be a liquid crystal polyester amide, a liquid crystal polyester ether, a liquid crystal polyester carbonate, or a liquid crystal polyester imide.
  • the “liquid crystal polyester amide” has an ester bond (—O—CO—) and an amide bond (—NH—CO—) in the polymer skeleton.
  • “Liquid crystal polyester ether” has an ester bond and an ether bond (—O—) in the polymer skeleton.
  • the “liquid crystal polyester carbonate” has an ester bond and a carbonate bond (—O—CO—O—) in the polymer skeleton.
  • the “liquid crystal polyester imide” has an ester bond and an imide structure represented by the following chemical formula in a polymer skeleton.
  • the liquid crystal polyester is preferably a wholly aromatic liquid crystal polyester using only an aromatic compound as a raw material monomer.
  • the “fully aromatic liquid crystal polyester” is, for example, a polyester called a thermotropic liquid crystal polymer, (1) Composed of a combination of aromatic dicarboxylic acid, aromatic diol and aromatic hydroxycarboxylic acid (2) Consisting of different types of aromatic hydroxycarboxylic acid (3) Combination of aromatic dicarboxylic acid and aromatic diol The thing which consists of etc. is mentioned.
  • aromatic dicarboxylic acids aromatic diols and aromatic hydroxycarboxylic acids, their ester-forming derivatives may be used as raw materials.
  • “Aromatic” is a group of cyclic unsaturated organic compounds represented by benzene.
  • liquid crystal polyester As a typical example of liquid crystal polyester, (I) An aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid, and at least one compound selected from the group consisting of an aromatic diol, an aromatic hydroxyamine, and an aromatic diamine are polymerized (polycondensed). thing, (II) a polymer obtained by polymerizing plural kinds of aromatic hydroxycarboxylic acids, (III) A polymer obtained by polymerizing an aromatic dicarboxylic acid and at least one compound selected from the group consisting of an aromatic diol, an aromatic hydroxyamine and an aromatic diamine, (IV) What polymerizes polyester, such as a polyethylene terephthalate, and aromatic hydroxycarboxylic acid is mentioned.
  • aromatic hydroxycarboxylic acid is a compound represented by the following general formula (a).
  • the aromatic dicarboxylic acid is a compound represented by the following general formula (b).
  • the aromatic diol is a compound represented by the following general formula (c).
  • the aromatic hydroxyamine is a compound represented by the following general formula (d).
  • An aromatic diamine is a compound represented by the following general formula (e).
  • Examples of polymerizable derivatives of a compound having a carboxyl group such as aromatic hydroxycarboxylic acid and aromatic dicarboxylic acid include those obtained by converting a carboxyl group into an alkoxycarbonyl group or an aryloxycarbonyl group (ester), carboxyl Examples include those obtained by converting a group into a haloformyl group (acid halide), and those obtained by converting a carboxyl group into an acyloxycarbonyl group (acid anhydride).
  • polymerizable derivatives of hydroxyl group-containing compounds such as aromatic hydroxycarboxylic acids, aromatic diols and aromatic hydroxyamines include those obtained by acylating hydroxyl groups and converting them to acyloxyl groups (acylated products) ).
  • polymerizable derivatives of amino group-containing compounds such as aromatic hydroxyamines and aromatic diamines include those obtained by acylating an amino group and converting it to an acylamino group (acylated product).
  • the liquid crystalline polyester preferably has a repeating unit represented by the following general formula (1) (hereinafter sometimes referred to as “repeating unit (1)”).
  • the repeating unit (1) and the following general formula (2) ) (Hereinafter sometimes referred to as “repeat unit (2)”) and a repeat unit represented by the following general formula (3) (hereinafter referred to as “repeat unit (3)”). More preferably).
  • Ar 1 is a phenylene group, a naphthylene group or a biphenylylene group
  • Ar 2 and Ar 3 are each independently a phenylene group, a naphthylene group, a biphenylylene group or a group represented by the following general formula (4): Yes
  • X and Y are each independently an oxygen atom or imino group
  • one or more hydrogen atoms in Ar 1 , Ar 2 and Ar 3 are each independently substituted with a halogen atom, an alkyl group or an aryl group May be.
  • Ar 4 and Ar 5 are each independently a phenylene group or a naphthylene group
  • Z is an oxygen atom, a sulfur atom, a carbonyl group, a sulfon
  • the alkyl group preferably has 1 to 10 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group Group, 2-ethylhexyl group, n-octyl group, n-nonyl group and n-decyl group.
  • the aryl group preferably has 6 to 20 carbon atoms.
  • Specific examples include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 1-naphthyl group, and a 2-naphthyl group.
  • the number is as follows for each group represented by Ar 1 , Ar 2, or Ar 3 , respectively. Independently, it is preferably 2 or less, more preferably 1.
  • the number of carbon atoms is preferably 1 to 10.
  • Specific examples include a methylene group, an ethylidene group, an isopropylidene group, an n-butylidene group, and a 2-ethylhexylidene group.
  • the repeating unit (1) is a repeating unit derived from a predetermined aromatic hydroxycarboxylic acid.
  • Ar 1 is a 1,4-phenylene group (repeating unit derived from p-hydroxybenzoic acid), and Ar 1 is a 2,6-naphthylene group (6-hydroxy Preferred is a repeating unit derived from -2-naphthoic acid.
  • the repeating unit (2) is a repeating unit derived from a predetermined aromatic dicarboxylic acid.
  • Ar 2 is a 1,4-phenylene group (repeating unit derived from terephthalic acid), Ar 2 is a 1,3-phenylene group (repeating unit derived from isophthalic acid) ), Ar 2 is a 2,6-naphthylene group (repeating unit derived from 2,6-naphthalenedicarboxylic acid), and Ar 2 is a diphenyl ether-4,4′-diyl group (diphenyl) Preferred is a repeating unit derived from ether-4,4′-dicarboxylic acid).
  • the repeating unit (3) is a repeating unit derived from a predetermined aromatic diol, aromatic hydroxylamine or aromatic diamine.
  • Ar 3 is a 1,4-phenylene group (a repeating unit derived from hydroquinone, p-aminophenol or p-phenylenediamine), and Ar 3 is a 4,4′-biphenylylene group. (Repeating units derived from 4,4′-dihydroxybiphenyl, 4-amino-4′-hydroxybiphenyl or 4,4′-diaminobiphenyl) are preferred.
  • the content of the repeating unit (1) is the total amount of all repeating units constituting the liquid crystal polyester (the substance of each repeating unit is obtained by dividing the mass of each repeating unit constituting the liquid crystal polyester by the formula weight of each repeating unit).
  • the equivalent amount (mole) is obtained and the total of these is preferably 30 mol% or more, more preferably 30 to 80 mol%, still more preferably 40 to 70 mol%, particularly preferably 45 to 65 mol%. Mol%.
  • the content of the repeating unit (2) is preferably 35 mol% or less, more preferably 10 to 35 mol%, still more preferably 15 to 30 mol%, based on the total amount of all repeating units constituting the liquid crystal polyester. Particularly preferred is 17.5 to 27.5 mol%.
  • the content of the repeating unit (3) is preferably 35 mol% or less, more preferably 10 to 35 mol%, still more preferably 15 to 30 mol%, based on the total amount of all repeating units constituting the liquid crystal polyester. Particularly preferred is 17.5 to 27.5 mol%.
  • the higher the content of the repeating unit (1) the easier it is to improve the melt flowability, heat resistance, strength and rigidity of the liquid crystalline polyester. However, if the content is too large, the melting temperature and melt viscosity tend to increase, and the temperature required for molding. Tends to be high.
  • the ratio between the content of the repeating unit (2) and the content of the repeating unit (3) is expressed as [content of repeating unit (2)] / [content of repeating unit (3)] (mol / mol).
  • the ratio is preferably 0.9 / 1 to 1 / 0.9, more preferably 0.95 / 1 to 1 / 0.95, and still more preferably 0.98 / 1 to 1 / 0.98.
  • the liquid crystal polyester may have two or more repeating units (1) to (3) independently.
  • the liquid crystal polyester may have a repeating unit other than the repeating units (1) to (3), but the content thereof is preferably 10 with respect to the total amount of all repeating units constituting the liquid crystal polyester.
  • the mol% or less more preferably 5 mol% or less.
  • the liquid crystal polyester preferably has, as the repeating unit (3), X and Y each having an oxygen atom, that is, a repeating unit derived from a predetermined aromatic diol.
  • X and Y each have only an oxygen atom.
  • the liquid crystalline polyester comprises a repeating unit derived from at least one aromatic hydroxycarboxylic acid selected from the group consisting of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid as the repeating unit (1), and a repeating unit ( 2) as a repeating unit derived from one or more aromatic dicarboxylic acids selected from the group consisting of terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid, and as repeating unit (3) hydroquinone and 4,4′-dihydroxy It is preferable to have a repeating unit derived from at least one aromatic diol selected from the group consisting of biphenyl, and it is more preferable to have only these repeating units.
  • Ar 1 is a 1,4-phenylene group (repeating unit derived from p-hydroxybenzoic acid);
  • Ar 2 is 1,4 A group having a phenylene group (repeating unit derived from terephthalic acid) and a group in which Ar 2 is a 1,3-phenylene group (repeating unit derived from isophthalic acid);
  • Ar 3 is 4 as the repeating unit (3) , 4′-biphenylylene groups (repeating units derived from 4,4′-dihydroxybiphenyl) are more preferred.
  • the liquid crystal polyester is preferably produced by melt polymerizing raw material monomers corresponding to the repeating units constituting the liquid crystal polyester and solid-phase polymerizing the obtained polymer (prepolymer). Thereby, high molecular weight liquid crystal polyester having high heat resistance, strength and rigidity can be produced with good operability.
  • Melt polymerization may be carried out in the presence of a catalyst.
  • the catalyst in this case include metals such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, and antimony trioxide.
  • nitrogen-containing heterocyclic compounds such as 4- (dimethylamino) pyridine and 1-methylimidazole, and nitrogen-containing heterocyclic compounds are preferably used.
  • the liquid crystal polyester has a flow initiation temperature of preferably 270 ° C. or higher, more preferably 270 ° C. to 400 ° C., and further preferably 280 ° C. to 380 ° C. As the flow start temperature is higher, the heat resistance, strength, and rigidity are more likely to be improved. However, if the flow start temperature is too high, the melting temperature and the melt viscosity are likely to be high, and the temperature required for molding is likely to be high. As described above, when solid phase polymerization is performed in the production of liquid crystal polyester, the flow start temperature of liquid crystal polyester can be set to 270 ° C. or higher in a relatively short time.
  • the flow start temperature is also called flow temperature or flow temperature, and the temperature is raised at a rate of 4 ° C./min under a load of 9.8 MPa (100 kg / cm 2 ) using a capillary rheometer while liquid crystal polyester is used.
  • the alumina fine particles are preferably fine particles made of ⁇ -alumina, and the content of aluminum oxide (Al 2 O 3 ) is 95% by mass or more based on the total mass of the alumina fine particles, Those having a volume average particle size of 0.1 to 50 ⁇ m are particularly suitable.
  • the volume average particle size of the alumina fine particles is preferably 0.1 to 30 ⁇ m, more preferably 0.1 to 20 ⁇ m, and particularly preferably 0.1 to 10 ⁇ m.
  • the “volume average particle diameter” of the alumina fine particles is measured using a microtrack particle size analyzer (for example, HRA manufactured by Nikkiso Co., Ltd.), and the alumina fine particles are 2% by mass aqueous sodium hexametaphosphate.
  • a microtrack particle size analyzer for example, HRA manufactured by Nikkiso Co., Ltd.
  • the alumina fine particles are 2% by mass aqueous sodium hexametaphosphate.
  • the laser beam is irradiated and the diffraction (scattering) is measured (particle size distribution measurement by laser diffraction scattering measurement).
  • the shape may be any of spherical, polyhedral and crushed particles.
  • the alumina fine particles preferably have a BET specific surface area of 1.0 to 5.0 m 2 / g, and the alumina fine particles are crushed particles in that the specific surface area tends to be relatively large. Particularly preferred.
  • the BET specific surface area of the alumina fine particles is in the range of 1.0 to 5.0 m 2 / g, when the thermoplastic resin composition obtained by the production method according to the present invention is melt-molded to obtain a molded body The damage of the mold used for molding can be further reduced, and the resulting molded product is more excellent in thermal conductivity.
  • the BET specific surface area of the alumina fine particles is more preferably 1.0 to 3.0 m 2 / g, and particularly preferably 1.0 to 2.5 m 2 / g. preferable.
  • commercially available alumina fine particles as described later may be selected from those having a BET specific surface area of 1.0 to 5.0 m 2 / g, Alumina particles having an appropriate volume average particle size (for example, about 40 to 70 ⁇ m) are prepared, crushed by various known means, and the specific surface area is increased, so that the BET specific surface area is 1.0 to 5
  • An alumina fine particle of 0.0 m 2 / g may be prepared. Examples of the crushing means at this time include a method using a pulverizer such as a jet mill, a micron mill, a ball mill, a vibration mill, and a media mill.
  • Examples of the method for measuring the BET specific surface area of alumina fine particles include the following nitrogen adsorption method. First, after the alumina fine particles are vacuum degassed at 120 ° C. for 8 hours, the adsorption isotherm by nitrogen is measured using a constant volume method. By using this adsorption isotherm, the specific surface area is calculated by the BET single point method. As an apparatus used at this time, for example, “BELSORP-mini” manufactured by Nippon BEL Co., Ltd. may be mentioned.
  • the alumina fine particles may be used as the alumina fine particles.
  • examples of commercially available products of alumina fine particles include alumina fine particles manufactured by Sumitomo Chemical Co., Ltd., Showa Denko Co., Ltd., and Nippon Light Metal Co., Ltd.
  • the BET specific surface area is preferably 1.0 to 5.0 m 2 / g, more preferably 1.0 to 3.0 m 2 / g as described above, and the volume average particle size is preferably May be selected from 0.1 to 50 ⁇ m.
  • the alumina fine particles preferably have a bimodal particle size distribution determined by laser diffraction scattering measurement.
  • the particle size distribution has a volume average particle size of 1 It is more preferable to have bimodality having local maximum values in the range of ⁇ 5 ⁇ m and the volume average particle size in the range of 0.1 to 1 ⁇ m.
  • Alumina fine particles having such a bimodal particle size distribution are commercially available.
  • alumina fine particles having a bimodal particle size distribution can be obtained by mixing two types of alumina fine particles having different particle sizes.
  • “bimodal” means that the particle size distribution has two maximum values.
  • “Maximum value” means the maximum value of intensity in one mountain-shaped waveform in a particle size distribution diagram (horizontal axis: particle size, vertical axis: intensity at the particle size) representing the distribution of the abundance ratio of particles. .
  • FIG. 1 and 2 are schematic views showing an outline of a bimodal particle distribution obtained by laser diffraction scattering measurement.
  • the horizontal axis represents the particle size
  • the right side represents the larger particle size.
  • the vertical axis represents the strength at the particle size.
  • FIG. 1 shows a typical bimodal particle size distribution, and the particle size distribution has two maximum values (a first maximum value and a second maximum value).
  • the bimodal particle size distribution is also used when the particle size distribution is such that the first maximum value appears like a shoulder peak with respect to the peak having the second maximum value.
  • the first maximum value is in the range of the volume average particle size of 0.1 to 1 ⁇ m
  • the second maximum value is in the range of the volume average particle size of 1 to 5 ⁇ m.
  • a certain alumina fine particle is more preferable.
  • the fibrous filler may be an inorganic filler or an organic filler.
  • the fibrous inorganic filler include glass fibers; carbon fibers such as pan-based carbon fibers and pitch-based carbon fibers; ceramic fibers such as silica fibers, alumina fibers and silica-alumina fibers; and metal fibers such as stainless fibers. It is done.
  • whiskers such as potassium titanate whisker, barium titanate whisker, wollastonite whisker, aluminum borate whisker, silicon nitride whisker, and silicon carbide whisker are also included.
  • the fibrous organic filler include polyester fibers and aramid fibers.
  • the fibrous filler is preferably carbon fiber, glass fiber, wollastonite whisker, aluminum borate whisker and potassium titanate whisker, and more preferably carbon fiber and glass fiber.
  • a fibrous filler may be used individually by 1 type, and may use 2 or more types together.
  • the fibrous filler preferably has a number average fiber diameter of 1 to 15 ⁇ m and a number average aspect ratio (number average fiber length / number average fiber diameter) of 10 or more.
  • the number average aspect ratio of the fibrous filler is more preferably 50 or more, and preferably 500 or less, more preferably 400 or less.
  • the number average fiber diameter and the number average fiber length of the fibrous filler can be measured by observing the fibrous filler with an electron microscope.
  • the fibrous filler for example, a commercially available product may be used as it is, or the surface is a coupling agent (silane coupling agent) in order to improve the dispersibility with respect to the thermoplastic resin and the adhesion to the thermoplastic resin.
  • a coupling agent silane coupling agent
  • Titanium coupling agents, etc. or surface treated with a surfactant or the like may be used.
  • silane coupling agent examples include methacryl silane, vinyl silane, epoxy silane, amino silane, and the like.
  • titanium coupling agent examples include titanic acid.
  • surfactant examples include higher fatty acids, higher fatty acid esters, higher fatty acid amides, higher fatty acid salts and the like.
  • thermoplastic resin other than the thermoplastic resin, the alumina fine particles, and the fibrous filler (components (A) to (C)) as long as they do not interfere with the effects of the present invention as necessary during melt-kneading.
  • Components may be supplied (blended), and the thermoplastic resin composition may contain these other components.
  • the other components include fillers and additives other than the alumina fine particles and the fibrous filler.
  • Examples of the filler other than the alumina fine particles and the fibrous filler include talc, glass flakes, silica particles, calcium carbonate and the like, and among these, talc is preferable.
  • examples of the additives include mold release improvers such as fluororesins; colorants such as dyes and pigments; antioxidants; thermal stabilizers; ultraviolet absorbers; antistatic agents; .
  • the supply amount of the alumina fine particles is larger than the supply amount of the fibrous filler by mass comparison.
  • W B mass%
  • W C mass%
  • W B / more preferably the value of W C is 2 or more, particularly preferably 3 or more.
  • the value of W B / W C is preferably 2 to 100, and more preferably 3 to 50.
  • the total supply amount of the alumina fine particles and the fibrous filler is preferably 100 parts by mass or more and more preferably 150 parts by mass or more with respect to 100 parts by mass of the thermoplastic resin supply.
  • the total supply amount of the alumina fine particles and the fibrous filler is preferably 100 to 500 parts by mass, and 150 to 400 parts by mass with respect to 100 parts by mass of the thermoplastic resin supply. Is more preferable.
  • thermoplastic resin composition is preferably obtained by extrusion melting and kneading the thermoplastic resin, alumina fine particles and fibrous filler (components (A) to (C)), and obtained by extrusion melting and kneading into pellets. .
  • a typical melt-kneading extruder used for extrusion melt-kneading includes a nozzle that is a small hole for extruding a heated melt, includes a cylinder having heating means, and supplies the raw material to be melt-kneaded to the cylinder
  • a single-screw melt kneading extruder provided with a supply port for pushing out the heated melt is preferably provided in the cylinder, and one screw is rotationally driven in the cylinder.
  • a twin-screw melt kneading extruder in which two screws are rotationally driven in different directions or in the same direction in the cylinder may be used, but a biaxial melt kneading extruder is preferable.
  • the ratio (L / D) of the effective length (L) of the screw to the diameter (D) of the screw is preferably 20 or more (where L and D are the same scale unit).
  • the kneaded product (thermoplastic resin composition) extruded from the nozzle of the melt-kneading extruder to the outside of the extruder is cooled at a cooling rate of 35 ° C./second or less.
  • the said cooling rate can be adjusted with the cooling method of the kneaded material extruded from the melt-kneading extruder, and the extrusion amount of a kneaded material, for example.
  • the cooling rate is, for example, the temperature a (° C.) of the kneaded product immediately after being extruded from the nozzle of the melt-kneading extruder, and the time after the kneaded product is extruded from the nozzle (after measuring the temperature a (° C.)).
  • the temperature of the kneaded product can be easily measured using, for example, an infrared radiation thermometer. By setting the time t to 3 to 10 seconds, for example, the cooling rate can be measured with higher accuracy.
  • the kneaded product extruded from the nozzle has a cooling rate of 35 ° C./second during cooling until it is heated again, such as until it is subjected to production of a molded body as a thermoplastic resin composition.
  • a cooling rate 35 ° C./second during cooling until it is heated again, such as until it is subjected to production of a molded body as a thermoplastic resin composition.
  • the cooling rate during this cooling operation is 35 ° C./second or less.
  • This cooling operation may be continued until at least the cooling rate does not exceed 35 ° C./second in a state where heat is naturally radiated. If the forced cooling operation is not performed on the kneaded material immediately after being extruded, the cooling rate is generally considered not to exceed 35 ° C./sec. Is.
  • the temperature b is preferably set to the temperature of the kneaded product immediately before the entrance of the cutting machine.
  • the time t is a time until the extruded kneaded material reaches the entrance of the cutting machine from the nozzle.
  • the forced cooling of the kneaded product is preferably performed by air cooling, water cooling, or the like.
  • the cooling rate of the kneaded product can be adjusted relatively easily by adjusting the conditions for spraying cooling shower water and blowing air.
  • Examples of such a strand cooling and taking device include those manufactured by Isuzu Chemical Industries and Tanaka.
  • the cooling rate during water cooling can be 35 ° C./second or less
  • the cooling rate during air cooling can be 30 ° C./second or less.
  • the extrusion rate of the kneaded product is preferably 5 to 300 kg / hour, more preferably 10 to 100 kg / hour. By setting it as such a range, the cooling rate of a kneaded material can be adjusted more easily.
  • the molded body according to the second aspect of the present invention is characterized by molding the thermoplastic resin composition obtained by the production method according to the first aspect of the present invention.
  • Such a molded article is excellent in electrical insulation, thermal conductivity and strength by using the thermoplastic resin composition.
  • the molded body according to the fourth aspect of the present invention is formed by molding a thermoplastic resin composition obtained by the production method according to the third aspect of the present invention.
  • a molded article is excellent in electrical insulation, thermal conductivity and strength by using the thermoplastic resin composition.
  • thermoplastic resin composition a suitable one can be appropriately selected depending on the shape of the target molded body, and among these, a melt molding method such as an injection molding method or an extrusion injection molding method is preferable, and an injection molding method is more preferable. preferable.
  • the injection molding method has an advantage that it is easy to mold a molded body having a complicated shape having a thin portion.
  • the molded body according to the present invention obtained by the injection molding method is useful as a part that requires heat conductivity, such as an electric / electronic part.
  • Injection molding is performed by melting the thermoplastic resin composition using an injection molding machine (for example, “Hydraulic Horizontal Molding Machine PS40E5ASE Model” manufactured by Nissei Plastic Industry Co., Ltd.) It can be performed by heating to a temperature and injecting it into a mold having the desired cavity shape.
  • the temperature at which the thermoplastic resin composition is heated and melted for injection is [Tp ′ + 10] ° C. or more and [Tp ′ + 50] ° C. or less based on the flow start temperature Tp ′ ° C. of the thermoplastic resin composition used. It is preferable to do.
  • the temperature of the mold is preferably selected from the range of room temperature (for example, 23 ° C.) to 180 ° C. from the viewpoint of the cooling rate and productivity of the thermoplastic resin composition.
  • the molded body can have a volume resistivity of 1 ⁇ 10 10 ⁇ m or more at 23 ° C.
  • the “volume specific resistance value” is a value measured according to “ASTM D257”.
  • the molded body can have a thermal conductivity of preferably 0.92 W / (m ⁇ K) or more and a bending strength of preferably 98 MPa or more, for example.
  • thermal conductivity is a value obtained from the product of thermal diffusivity, specific heat and specific gravity, and “bending strength” is a value measured according to “ASTM D790”.
  • the molded body can be applied to various uses, but is particularly suitable as an electric / electronic component because it is excellent in electrical insulation, thermal conductivity and mechanical strength.
  • the molded body is at least one selected from the group consisting of a sealing material for electronic elements, an insulator, a reflector for display device, a casing for storing electronic elements, a motor insulator for automobiles and industrial machines, and a surface mount component. It is preferable to use as a component. Further, as the surface mount component, a connector is suitable. In such electric / electronic parts, heat is generated by the operation of the electric / electronic equipment provided with these parts, and if the heat dissipation of these parts is insufficient, malfunctions occur and the reliability of the equipment decreases. Easy to do.
  • the molded body according to the present invention has a characteristic advantageous for heat dissipation in that the thermal conductivity becomes relatively isotropic as described above. Therefore, when the molded body according to the present invention is used as the electrical / electronic component, even if these components have a relatively complicated shape, the molded body according to the present invention efficiently dissipates heat due to the isotropic thermal conductivity. Realize stable operation of electrical and electronic equipment equipped with
  • the alumina fine particles and fibrous filler used in this example are as follows.
  • (Alumina fine particles) Fine low soda alumina AL-45-2 (manufactured by Showa Denko KK): volume average particle size 1.4 ⁇ m (in the particle size distribution, the volume average particle size is in the range of 1.0 to 2.0 ⁇ m and the volume average particle size It was bimodal, each having a maximum value in the range of 0.2 to 0.4 ⁇ m.), BET specific surface area 1.8 m 2 / g (Fibrous filler)
  • DIALEAD K223HE Mitsubishi Chemical Corporation
  • Carbon fiber Chopped glass fiber CS03JAPX-1 Carbon fiber Chopped glass fiber CS03JAPX-1 (Asahi Fiber Glass Co., Ltd.): Glass fiber (plate-like inorganic filler)
  • Talc X-50 Nahon Talc
  • Example 1 (Production of liquid crystal polyester composition)
  • the liquid crystal polyester obtained in Production Example 1 and the alumina fine particles and the fibrous filler were mixed in the same direction biaxial melt kneading extruder ("PCM-30HS" manufactured by Ikekai Tekko Co., Ltd.) in the ratio shown in Table 1.
  • PCM-30HS biaxial melt kneading extruder
  • the kneaded product is extruded in a strand form from the nozzle of the extruder and cooled, and then a strand cutter is used.
  • the pellet-like liquid crystal polyester composition was obtained by cutting and granulating.
  • the strand-like kneaded material was cooled by air cooling by blowing air using a strand cooling take-up device (manufactured by Isuzu Chemical Industries Ltd.).
  • the cooling rate is the time t from the nozzle to the strand cutter, which is the difference between the temperature a of the kneaded product immediately after being extruded from the nozzle of the extruder and the temperature b of the kneaded product immediately before the strand cutter entrance. The value was divided.
  • Example 2 Comparative Examples 1 and 2
  • a liquid crystal polyester composition and a molded body were produced in the same manner as in Example 1 except that the production conditions were as shown in Table 1.
  • the strand-shaped kneaded product was water-cooled by spraying cooling shower water.
  • thermo conductivity in the thickness direction A central part of the molded body (1) was cut out to obtain a sample for thermal conductivity evaluation.
  • the thermal diffusivity of this sample was measured using a laser flash method thermal constant measuring device (“TC-7000” manufactured by ULVAC-RIKO Inc.). Further, the specific heat of this sample was measured using DSC ("DSC7” manufactured by PERKIN ELMER), and the specific gravity of this sample was measured using an automatic specific gravity measuring device (“ASG-320K” manufactured by Kanto Major). .
  • the molded body (1) was measured at 23 ° C. by volume resistivity measurement in accordance with “ASTM D257” (using “Digital Super Insulation / Micro Ammeter DSM-8104” manufactured by Toa DK Corporation).
  • the molded products of Examples 1 and 2 in which the kneaded product extruded from the nozzle of the extruder was cooled at a cooling rate of 20 to 22 ° C./second were all thermal conductivity in the thickness direction. It was excellent in strength and insulation.
  • the molded product of Comparative Example 1 in which the kneaded product extruded from the nozzle of the extruder was cooled at a cooling rate of 42 ° C./second was inferior in thermal conductivity in the thickness direction.
  • the molded product of Comparative Example 2 in which the kneaded product was cooled at a cooling rate of 38 ° C./second was inferior in thermal conductivity and strength in the thickness direction.
  • the present invention can be used for manufacturing electrical / electronic components that require high heat dissipation.

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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)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

L'invention concerne un procédé de fabrication d'une composition de résine thermoplastique qui comprend : utiliser une machine d'extrusion de malaxage à l'état fondu dotée d'une buse, d'un cylindre et d'une vis positionnée à l'intérieur du cylindre ; obtenir un mélange en adressant (A) une résine thermoplastique, (B) des particules fines d'alumine et (C) une matière de charge fibreuse dans le cylindre par l'intermédiaire de l'orifice d'alimentation dans le cylindre, et malaxer à l'état fondu les composants (A, B, C) ; extruder le mélange par l'intermédiaire de la buse de la machine d'extrusion de malaxage à l'état fondu à l'extérieur de celle-ci ; et refroidir le mélange à une allure de refroidissement de 35°C ou moins par seconde. Egalement, un article moulé est obtenu par moulage de la composition de résine thermoplastique obtenue à l'aide de ce procédé de fabrication.
PCT/JP2012/079164 2011-11-11 2012-11-09 Procédé de fabrication d'une composition de résine thermoplastique et article moulé WO2013069782A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017089207A1 (fr) * 2015-11-26 2017-06-01 Robert Bosch Gmbh Dispositif électrique comprenant une matière d'enrobage
WO2018123745A1 (fr) * 2016-12-27 2018-07-05 日立化成株式会社 Composition de résine et dispositif à composant électronique
WO2021029268A1 (fr) * 2019-08-09 2021-02-18 住友化学株式会社 Granules de resine de polyester a cristaux liquides ainsi que corps moule de resine de polyester a cristaux liquides

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI814939B (zh) * 2018-11-09 2023-09-11 日商住友化學股份有限公司 液晶聚酯樹脂組成物及成形品

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4855242A (fr) * 1971-11-13 1973-08-03
JPS50119097A (fr) * 1974-03-05 1975-09-18
JPS5146350A (ja) * 1974-10-17 1976-04-20 Toray Industries Seikeiyokyokahoriamidojushisoseibutsuno seizohoho
JPH0776018A (ja) * 1993-09-08 1995-03-20 Mitsubishi Gas Chem Co Inc 樹脂成形材料の製法
JPH08192425A (ja) * 1995-01-18 1996-07-30 Polyplastics Co 紐状溶融熱可塑性樹脂または紐状溶融熱可塑性樹脂組成物の冷却方法
JP2001310323A (ja) * 2000-04-28 2001-11-06 Sumitomo Chem Co Ltd 熱可塑性樹脂組成物の製造方法
JP2006035677A (ja) * 2004-07-28 2006-02-09 Polyplastics Co 液晶性樹脂組成物の製造方法
JP2011037919A (ja) * 2009-08-06 2011-02-24 Teijin Ltd 熱伝導性棒状樹脂成形体
JP2011184681A (ja) * 2010-02-10 2011-09-22 Toyota Central R&D Labs Inc 樹脂組成物およびその製造方法
JP2011224924A (ja) * 2010-04-22 2011-11-10 Umg Abs Ltd ポリ乳酸系熱可塑性樹脂ペレットの製造方法
JP2012188624A (ja) * 2011-03-14 2012-10-04 Kaneka Corp 高熱伝導性樹脂組成物の製造方法および成形体の製造方法

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4855242A (fr) * 1971-11-13 1973-08-03
JPS50119097A (fr) * 1974-03-05 1975-09-18
JPS5146350A (ja) * 1974-10-17 1976-04-20 Toray Industries Seikeiyokyokahoriamidojushisoseibutsuno seizohoho
JPH0776018A (ja) * 1993-09-08 1995-03-20 Mitsubishi Gas Chem Co Inc 樹脂成形材料の製法
JPH08192425A (ja) * 1995-01-18 1996-07-30 Polyplastics Co 紐状溶融熱可塑性樹脂または紐状溶融熱可塑性樹脂組成物の冷却方法
JP2001310323A (ja) * 2000-04-28 2001-11-06 Sumitomo Chem Co Ltd 熱可塑性樹脂組成物の製造方法
JP2006035677A (ja) * 2004-07-28 2006-02-09 Polyplastics Co 液晶性樹脂組成物の製造方法
JP2011037919A (ja) * 2009-08-06 2011-02-24 Teijin Ltd 熱伝導性棒状樹脂成形体
JP2011184681A (ja) * 2010-02-10 2011-09-22 Toyota Central R&D Labs Inc 樹脂組成物およびその製造方法
JP2011224924A (ja) * 2010-04-22 2011-11-10 Umg Abs Ltd ポリ乳酸系熱可塑性樹脂ペレットの製造方法
JP2012188624A (ja) * 2011-03-14 2012-10-04 Kaneka Corp 高熱伝導性樹脂組成物の製造方法および成形体の製造方法

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017089207A1 (fr) * 2015-11-26 2017-06-01 Robert Bosch Gmbh Dispositif électrique comprenant une matière d'enrobage
US10937714B2 (en) 2015-11-26 2021-03-02 Robert Bosch Gmbh Electrical device having a covering material
WO2018123745A1 (fr) * 2016-12-27 2018-07-05 日立化成株式会社 Composition de résine et dispositif à composant électronique
JPWO2018123745A1 (ja) * 2016-12-27 2019-10-31 日立化成株式会社 樹脂組成物及び電子部品装置
JP2022125150A (ja) * 2016-12-27 2022-08-26 昭和電工マテリアルズ株式会社 樹脂組成物及び電子部品装置
WO2021029268A1 (fr) * 2019-08-09 2021-02-18 住友化学株式会社 Granules de resine de polyester a cristaux liquides ainsi que corps moule de resine de polyester a cristaux liquides
JP2021028383A (ja) * 2019-08-09 2021-02-25 住友化学株式会社 液晶ポリエステル樹脂ペレット、及び液晶ポリエステル樹脂成形体

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