WO2016098343A1 - Composition de résine thermoplastique, article moulé en résine thermoplastique ainsi que procédé de fabrication de celui-ci, et stratifié - Google Patents

Composition de résine thermoplastique, article moulé en résine thermoplastique ainsi que procédé de fabrication de celui-ci, et stratifié Download PDF

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Publication number
WO2016098343A1
WO2016098343A1 PCT/JP2015/006230 JP2015006230W WO2016098343A1 WO 2016098343 A1 WO2016098343 A1 WO 2016098343A1 JP 2015006230 W JP2015006230 W JP 2015006230W WO 2016098343 A1 WO2016098343 A1 WO 2016098343A1
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thermoplastic resin
resin composition
vinyl chloride
mass
acid
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PCT/JP2015/006230
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English (en)
Japanese (ja)
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崇倫 藤原
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日本ゼオン株式会社
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Priority to JP2016564686A priority Critical patent/JP6760078B2/ja
Publication of WO2016098343A1 publication Critical patent/WO2016098343A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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
    • C08L27/04—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 chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride

Definitions

  • the present invention provides a thermoplastic resin composition that gives a powder molded body having a low pinhole generation rate when forming a fake stitch, a thermoplastic resin molded body obtained by powder molding the thermoplastic resin composition, and the heat
  • the present invention relates to a laminate having a plastic resin molded body and a polyurethane foam molded body, and a method for producing the thermoplastic resin molded body.
  • Automotive interior materials such as instrument panels, door trims, center consoles, door panels and seats are installed in passenger compartments of vehicles such as passenger cars.
  • the automobile interior material usually has a structure in which a skin material is provided on the outer surface of the base material.
  • the skin material is often formed of a synthetic resin from the viewpoint of moldability, cost, durability, and the like.
  • the synthetic resin skin material is provided with a stitch pattern (real stitch) formed by sewing threads.
  • Various methods for forming such a real stitch have been studied conventionally (see, for example, Patent Documents 1 and 2).
  • a synthetic resin skin material having a stitch pattern (fake stitch) formed integrally with the skin material on the surface is manufactured by powder molding of a thermoplastic resin composition.
  • the problem to be solved by the present invention is to provide a thermoplastic resin composition that gives a powder molded body having a low pinhole generation rate during fake stitch formation.
  • Another problem to be solved by the present invention is a thermoplastic resin molded body obtained by powder-molding the thermoplastic resin composition, and a laminate having the thermoplastic resin molded body and a foamed polyurethane molded body. Is an offer.
  • another subject which this invention tends to solve is provision of the manufacturing method of the said thermoplastic resin molding.
  • thermoplastic resin composition in which the average particle diameter of the contained particles is in a specific range has a pinhole generation ratio during fake stitch formation.
  • present inventors have found that a low-powder compact can be obtained and have completed the present invention.
  • the present invention is a thermoplastic resin composition containing a thermoplastic resin, wherein the average particle size of particles contained in the thermoplastic resin composition is 80 ⁇ m or more and 150 ⁇ m or less.
  • thermoplastic resin composition of the present invention is preferably for an epidermis having a fake stitch.
  • thermoplastic resin composition of the present invention further contains a plasticizer, and that the thermoplastic resin is a vinyl chloride resin.
  • thermoplastic resin composition of the present invention preferably contains 30 to 190 parts by mass of the plasticizer with respect to 100 parts by mass of the vinyl chloride resin.
  • the (a) vinyl chloride resin is 70 mass% or more and 100 mass% or less (a) vinyl chloride resin particles, and 0 mass% or more and 30 mass% or less ( b) It is preferable to consist only of vinyl chloride resin fine particles.
  • “resin particles” refers to particles having a particle size of 30 ⁇ m or more, and “resin particles” refers to particles having a particle size of less than 30 ⁇ m.
  • the average polymerization degree of the (a) vinyl chloride resin particles is 800 or more and 5000 or less, and the average polymerization degree of the (b) vinyl chloride resin particles is 500 or more and 5000 or less. It is preferable that
  • thermoplastic resin composition of the present invention is powder molding, and a more preferred use is powder slush molding.
  • the present invention is a thermoplastic resin molded body obtained by powder molding any one of the above thermoplastic resin compositions.
  • thermoplastic resin molded article of the present invention is preferably formed by powder slush molding of any of the thermoplastic resin compositions described above.
  • thermoplastic resin molded article of the present invention is preferably for a skin having a fake stitch.
  • thermoplastic resin molded article of the present invention is preferably for an automotive instrument panel skin.
  • the present invention is a laminate having a foamed polyurethane molded body and any one of the thermoplastic resin molded bodies.
  • the laminate of the present invention is preferably for an automotive instrument panel.
  • the present invention is a method for producing a thermoplastic resin molded article, characterized by powder molding any one of the above thermoplastic resin compositions.
  • thermoplastic resin composition of the present invention gives a powder molded body with a low pinhole generation rate during fake stitch formation.
  • thermoplastic resin composition contains a thermoplastic resin and optionally contains a plasticizer and an additive.
  • the thermoplastic resin composition of the present invention is usually an aggregate (powder composition) of particles composed of a plurality of particles, and the average particle diameter of these particles is 80 ⁇ m or more and 150 ⁇ m or less.
  • thermoplastic resin functions as a matrix resin in the thermoplastic resin composition.
  • the thermoplastic resin contained in the thermoplastic resin composition of the present invention is not limited to a specific resin.
  • the thermoplastic resin include vinyl chloride resin, thermoplastic polyurethane, polyolefin resin, polyolefin rubber, ABS (acrylonitrile-butadiene-styrene copolymer) resin, polystyrene, polyamide, and the like.
  • thermoplastic resins may be used individually by 1 type, and may use 2 or more types together. Among them, vinyl chloride resin is preferable from the viewpoint of reducing the pinhole generation ratio in forming the fake stitch.
  • These thermoplastic resins are usually present in the form of resin particles or resin fine particles (thermoplastic resin particles or thermoplastic resin fine particles) in the thermoplastic resin composition of the present invention.
  • vinyl chloride resin examples include (a) vinyl chloride resin particles and (b) vinyl chloride resin fine particles.
  • Specific examples of comonomers of the vinyl chloride copolymer include olefins such as ethylene and propylene; halogenated olefins such as allyl chloride, vinylidene chloride, vinyl fluoride, and ethylene trifluoride; vinyl acetate and propionic acid.
  • Carboxylic acid vinyl esters such as vinyl; vinyl ethers such as isobutyl vinyl ether and cetyl vinyl ether; allyl ethers such as allyl-3-chloro-2-oxypropyl ether and allyl glycidyl ether; acrylic acid, maleic acid, itaconic acid, acrylic 2-hydroxyethyl acid, methyl methacrylate, monomethyl maleate, diethyl maleate, maleic anhydride and other unsaturated carboxylic acids, their esters or acid anhydrides; acrylonitrile, methacrylonitrile and other unsaturated nitriles; Acrylamide, N- methylol acrylamide, acrylamido-2-methylpropanesulfonic acid, (meth) acrylamides such as acrylamide propyl trimethyl ammonium chloride; allyl amine benzoates, allylamine and its derivatives such as diallyl dimethyl ammonium chloride; and the like.
  • the monomer exemplified above is only a part of the monomer (comonomer) copolymerizable with vinyl chloride.
  • “polyvinyl chloride” edited by Kinki Chemical Association Vinyl Division
  • the various monomers exemplified in Nikkan Kogyo Shimbun (1988), pages 75-104 may be used.
  • One or more of these monomers can be used.
  • the vinyl chloride resin constituting the above (a) vinyl chloride resin particles and (b) vinyl chloride resin fine particles include ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, and ethylene-ethyl acrylate copolymer.
  • resins obtained by graft polymerization of (1) vinyl chloride or (2) vinyl chloride and the above-mentioned comonomer to a resin such as chlorinated polyethylene are also included.
  • (meth) acryl means acryl and / or methacryl.
  • the vinyl chloride resin constituting the above (a) vinyl chloride resin particles and (b) vinyl chloride resin fine particles may be any of conventionally known methods such as suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization. It can also be manufactured by a manufacturing method.
  • the average particle diameter of the vinyl chloride resin particles (a) is preferably 50 ⁇ m or more and 250 ⁇ m or less, more preferably 100 ⁇ m or more and 200 ⁇ m or less, and further preferably 110 ⁇ m or more and 130 ⁇ m or less. If (a) vinyl chloride resin particles having an average particle size in the above range are used, the average particle size of the particles contained in the resulting thermoplastic resin composition can be easily adjusted within a predetermined range, and when forming a fake stitch The pinhole generation rate can be reduced. “(A) Average particle diameter of vinyl chloride resin particles” refers to a volume average particle diameter measured by, for example, a laser diffraction method in accordance with JIS Z8825.
  • the average degree of polymerization of the vinyl chloride resin constituting the (a) vinyl chloride resin particles is preferably 800 or more and 5000 or less, more preferably 800 or more and 3000 or less, and still more preferably 800 or more and 2000 or less.
  • the “average polymerization degree” is measured according to JIS K 6720-2.
  • thermoplastic resin composition of the present invention can also use (b) vinyl chloride resin fine particles as the vinyl chloride resin.
  • the (b) vinyl chloride resin fine particles function as a dusting agent that improves the powder fluidity of the thermoplastic resin composition while functioning as a matrix resin.
  • the preferable average particle diameter of the vinyl chloride resin fine particles (b) is 0.1 ⁇ m or more and 10 ⁇ m or less. This is because if (b) vinyl chloride resin fine particles having an average particle diameter in the above range are used, the powder fluidity of the thermoplastic resin composition is improved.
  • “(b) Average particle diameter of vinyl chloride resin fine particles” refers to a volume average particle diameter measured by, for example, a laser diffraction method in accordance with JIS Z8825.
  • the preferable average polymerization degree of the vinyl chloride resin constituting the vinyl chloride resin fine particles is preferably 500 or more and 5000 or less, more preferably 600 or more and 3000 or less, and further preferably 700 or more and 2500 or less.
  • B When the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin fine particles is within the above range, the powder flowability of the thermoplastic resin composition is good, and pinholes are formed during fake stitch formation. The generation rate can be reduced.
  • the vinyl chloride resin constituting the vinyl chloride resin fine particles (b) it is preferable to use a vinyl chloride resin produced by an emulsion polymerization method.
  • the vinyl chloride resin preferably contains at least (a) vinyl chloride resin particles, and optionally (b) vinyl chloride resin fine particles.
  • 100% by mass of the vinyl chloride resin consists only of (a) vinyl chloride resin particles of 70% by mass to 100% by mass and (b) vinyl chloride resin fine particles of 0% by mass to 30% by mass. . If a vinyl chloride resin having such a composition is used, the pinhole generation rate at the time of forming the fake stitch can be reduced.
  • 100% by mass of the vinyl chloride resin comprises only 70% by mass to 99% by mass of (a) vinyl chloride resin particles and 1% by mass to 30% by mass of (b) vinyl chloride resin fine particles. It is more preferable that it consists only of 75% by mass to 95% by mass of (a) vinyl chloride resin particles and 5% by mass to 25% by mass of (b) vinyl chloride resin fine particles, more preferably 80% by mass to 92% by mass. It is particularly preferable that the film comprises only the following (a) vinyl chloride resin particles and (b) vinyl chloride resin fine particles of 8% by mass or more and 20% by mass or less. When the content of the above (a) vinyl chloride resin particles and (b) vinyl chloride resin fine particles is within the above range, the powder fluidity of the thermoplastic resin composition is good, and the pin at the time of fake stitch formation The hole generation rate can be reduced.
  • Thermoplastic polyurethanes are generally prepared using polyols, diisocyanates, and chain extenders.
  • thermoplastic polyurethane examples include polyester polyol, polyester ether polyol, polycarbonate polyol, and polyether polyol.
  • the polyester polyol is, for example, a dehydration condensation reaction product of a dicarboxylic acid and a polyhydric alcohol having no ether bond.
  • the dicarboxylic acid include aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid; hexahydrophthalic acid, hexa Examples thereof include alicyclic dicarboxylic acids such as hydroterephthalic acid and hexahydroisophthalic acid; acid esters thereof; acid anhydrides thereof; and mixtures thereof.
  • polyhydric alcohol having no ether bond examples include ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentane.
  • examples thereof include diol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, and mixtures thereof.
  • Polyester polyols can also be obtained as polylactone diols by ring-opening polymerization of lactone monomers such as ⁇ -caprolactone.
  • the polyester ether polyol is, for example, a dehydration condensation reaction product of a dicarboxylic acid and a polyhydric alcohol having an ether bond.
  • the dicarboxylic acid include aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid; hexahydrophthalic acid, hexa Examples thereof include alicyclic dicarboxylic acids such as hydroterephthalic acid and hexahydroisophthalic acid; acid esters thereof; acid anhydrides thereof; and mixtures thereof.
  • the polyhydric alcohol having an ether bond include diethylene glycol, propylene oxide adducts of various molecules, and mixtures thereof.
  • the polycarbonate polyol is, for example, a reaction product of a polyhydric alcohol and a carbonate compound.
  • the polyhydric alcohol include ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- Examples include hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene glycol, and mixtures thereof.
  • the carbonate compound include diethylene carbonate, dimethyl carbonate, diethyl carbonate, and mixtures thereof.
  • the polyether polyol is, for example, a ring-opening polymer of a cyclic ether.
  • the cyclic ether include ethylene oxide, propylene oxide, tetrahydrofuran, and a mixture thereof.
  • Specific polyether polyols include polyethylene glycol obtained by ring-opening polymerization of ethylene oxide, polypropylene glycol obtained by ring-opening polymerization of propylene oxide, and polytetramethylene ether obtained by ring-opening polymerization of tetrahydrofuran. Examples include glycols and copolyethers obtained by ring-opening polymerization of plural kinds of cyclic ethers.
  • polystyrene resin may be used alone or in combination of two or more.
  • polyether polyols are preferred from the viewpoint of hydrolysis resistance as the polyols used for preparing the thermoplastic polyurethane.
  • Diisocyanates used in the preparation of thermoplastic polyurethanes include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate, tolidine diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate.
  • MDI 4,4'-diphenylmethane diisocyanate
  • MDI 4,4'-diphenylmethane diisocyanate
  • 1,5-naphthylene diisocyanate 1,5-naphthylene diisocyanate
  • tolidine diisocyanate 1,6-hexamethylene diisocyanate
  • isophorone diisocyanate isophorone diisocyanate.
  • Xylylene diisocyanate (XDI), hydrogenated xylylene diisocyanate (hydrogenated XDI), triisocyanate, tetramethylxylene diisocyanate (TMXDI), 1,6,11-undecane triisocyanate, 1,8-diisocyanate methyloctane, lysine ester
  • TMXDI tetramethylxylene diisocyanate
  • 1,6,11-undecane triisocyanate 1,8-diisocyanate methyloctane
  • lysine ester examples thereof include triisocyanate, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate.
  • MDI 4,4′-diphenylmethane diisocyanate
  • Examples of the chain extender used for preparing the thermoplastic polyurethane include a low molecular weight polyol.
  • the low molecular weight polyol include ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6 -Aliphatic polyols such as hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene glycol, 1,4-cyclohexanedimethanol, glycerin; Aromatic glycols such as 1,4-dimethylolbenzene, bisphenol A, ethylene oxide adduct of bisphenol A, and propylene oxide adduct of bisphenol A.
  • polyolefin resin refers to a repeating unit derived from one or more monoolefins having 2 to 10 carbon atoms, such as ethylene, propylene, 1-butene and 1-hexene, of 50% by mass or more. And a polymer having an A hardness of JIS K-6253 (1997) exceeding 98.
  • the polyolefin resin may contain a repeating unit derived from a monomer other than the monoolefin described above.
  • Examples of monomers other than the above monoolefin include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like.
  • Conjugated dienes having 4 to 8 carbon atoms having 4 to 8 carbon atoms; carbon numbers such as dicyclopentadiene, 5-ethylidene-2-norbornene, 1,4-hexadiene, 1,5-dicyclooctadiene, 7-methyl-1,6-octadiene 5 to 15 non-conjugated dienes; vinyl ester compounds such as vinyl acetate; unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate; acrylic acid, methacrylic acid, etc. Of unsaturated carboxylic acids.
  • polystyrene resin examples include ethylene homopolymer, propylene homopolymer, 1-butene homopolymer, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-1-hexene copolymer. , Ethylene-1-octene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer, ethylene-propylene-1-butene copolymer, ethylene- And propylene-1-hexene copolymer and ethylene-propylene-1-octene copolymer. These polyolefin resins may be used individually by 1 type, and may use 2 or more types together.
  • polyolefin rubber means one or two monoolefins having 2 to 10 carbon atoms, such as ethylene, propylene, 1-butene, 2-methylpropylene, 3-methyl-1-butene, 1-hexene and the like. It is a polymer containing 50% by mass or more of repeating units derived from seeds and having a hardness A of 98 or less in JIS K-6253 (1997).
  • the polyolefin rubber may contain a repeating unit derived from a monomer other than the monoolefin described above.
  • Examples of monomers other than the above monoolefin include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like.
  • polystyrene resin examples include propylene homopolymer, 1-butene homopolymer, 2-methylpropene homopolymer, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-3-methyl-1 -Butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer Ethylene-propylene-5-ethylidene-2-norbornene copolymer, ethylene-propylene-1-butene copolymer, ethylene-propylene-1-hexene copolymer, ethylene-propylene-1-octene copolymer, etc. is there. These polyolefin rubbers may be used alone or in combination of two or more.
  • the thermoplastic resin composition of the present invention preferably contains a plasticizer.
  • a preferable plasticizer is trimellitic acid ester plasticizer.
  • the trimellitic acid ester plasticizer is an ester compound of trimellitic acid and a monohydric alcohol.
  • monohydric alcohol examples include, but are not limited to, 1-hexanol, 1-heptanol, 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, etc. Is mentioned.
  • a trimellitic acid ester plasticizer preferable as a plasticizer is a triesterized product obtained by esterifying substantially all the carboxy groups of trimellitic acid with the above-described monohydric alcohol.
  • the alcohol residue part in the triesterized product may be derived from the same alcohol or may be derived from different alcohols.
  • the trimellitic acid ester plasticizer may be composed of a single compound or a mixture of different compounds.
  • trimellitic acid ester plasticizers are trimellitic acid tri-n-hexyl, trimellitic acid tri-n-heptyl, trimellitic acid tri-n-octyl, trimellitic acid tri- (2-ethylhexyl) , Trimellitic acid tri-n-nonyl, trimellitic acid tri-n-decyl, trimellitic acid triisodecyl, trimellitic acid tri-n-undecyl, trimellitic acid tri-n-dodecyl, trimellitic acid tri-n-alkyl Esters (esters having two or more kinds of alkyl groups having different carbon numbers [however, having 6 to 12 carbon atoms] in the molecule), trimellitic acid trialkyl esters (alkyl groups having different carbon numbers [however, Is an ester having 2 or more types in the molecule), and mixtures thereof.
  • trimellitic acid ester plasticizers include tri-n-octyl trimellitic acid, tri- (2-ethylhexyl) trimellitic acid, tri-n-nonyl trimellitic acid, and tri-n-decyl trimellitic acid.
  • Trimellitic acid tri-n-alkyl esters esters having two or more kinds of alkyl groups having different carbon numbers (wherein the carbon number is 8 to 10) in the molecule), and mixtures thereof.
  • plasticizer other than trimellitic acid ester plasticizer that can be used as the plasticizer contained in the thermoplastic resin composition of the present invention include the following primary plasticizer and secondary plasticizer.
  • primary plasticizers Pyromellitic acid tetra-n-hexyl, pyromellitic acid tetra-n-heptyl, pyromellitic acid tetra-n-octyl, pyromellitic acid tetra- (2-ethylhexyl), pyromellitic acid tetra-n-nonyl, pyromellitic acid Tetra-n-decyl, pyromellitic acid tetraisodecyl, pyromellitic acid tetra-n-undecyl, pyromellitic acid tetra-n-dodecyl, pyromellitic acid tetra-n-alkyl ester (an alkyl group having a different carbon number [however, Pyromellitic ester plasticizers such as esters having 2 or more carbon atoms in the molecule; Dimethyl phthalate, diethyl
  • a glycol derivative of Glycerol derivatives such as glycerol monoacetate, glycerol triacetate, glycerol tributyrate; Epoxy derivatives such as epoxyhexahydrophthalate diisodecyl, epoxy triglyceride, epoxidized octyl oleate, epoxidized decyl oleate; Examples thereof include polyester plasticizers such as adipic acid-based polyester, sebacic acid-based polyester, and phthalic acid-based polyester.
  • secondary plasticizers include epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil; fatty acid esters of glycols such as chlorinated paraffin and triethylene glycol dicaprylate, butyl epoxy stearate, phenyl oleate And methyl dihydroabietic acid.
  • plasticizers other than the trimellitic acid ester plasticizer epoxidized vegetable oil is preferable.
  • one or more plasticizers other than the trimellitic acid ester plasticizer can be used.
  • a secondary plasticizer it is preferable to use together the said secondary plasticizer and the primary plasticizer of equal mass or more.
  • the total content of the plasticizer is preferably 30 to 190 parts by mass, more preferably 60 to 170 parts by mass, and still more preferably 100 parts by mass of the thermoplastic resin. Is 90 parts by mass or more and 160 parts by mass or less. If content of the said plasticizer is in the said range, the pinhole generation
  • thermoplastic resin composition of the present invention may contain perchloric acid-treated hydrotalcite.
  • Perchloric acid-treated hydrotalcite for example, by adding hydrotalcite to a dilute aqueous solution of perchloric acid, stirring, and then filtering, dehydrating or drying as necessary, thereby allowing carbonate anions in hydrotalcite It can be easily produced by replacing at least a part of (CO 3 2 ⁇ ) with a perchlorate anion (ClO 4 ⁇ ) (2 mol of perchlorate anion is substituted for 1 mol of carbonate anion).
  • the molar ratio of the hydrotalcite to the perchloric acid can be arbitrarily set, but is generally 0.1 to 2 moles of perchloric acid per mole of hydrotalcite.
  • the substitution rate of the carbonate anion to the perchlorate anion in the untreated (unsubstituted) hydrotalcite is preferably 50 mol% or more, more preferably 70 mol% or more, and still more preferably 85 mol% or more. Further, the substitution rate of the carbonate anion to the perchlorate anion in the untreated (unsubstituted) hydrotalcite is preferably 95 mol% or less. If the substitution rate of the carbonate anion to the perchlorate anion in the untreated (unsubstituted) hydrotalcite is within the above range, the pinhole generation rate at the time of forming the fake stitch can be reduced.
  • Hydrotalcite is a non - stoichiometric compound represented by the general formula [Mg 1-x Al x (OH) 2 ] x + [(CO 3 ) x / 2 ⁇ mH 2 O] x- , and is a positively charged basic layer It is an inorganic substance having a layered crystal structure composed of [Mg 1-x Al x (OH) 2 ] x + and a negatively charged intermediate layer [(CO 3 ) x / 2 ⁇ mH 2 O] x ⁇ .
  • x is a number in the range of greater than 0 and less than or equal to 0.33.
  • the natural hydrotalcite is Mg 6 Al 2 (OH) 16 CO 3 .4H 2 O.
  • the synthetic hydrotalcite, Mg 4.5 Al 2 (OH) 13 CO 3 ⁇ 3.5H 2 O are commercially available. A method for synthesizing synthetic hydrotalcite is described in, for example, Japanese Patent Publication No. 61-174270.
  • the preferable content of perchloric acid-treated hydrotalcite with respect to 100 parts by mass of the thermoplastic resin is 0.5 parts by mass or more and 7 parts by mass or less, and the more preferable content is 1 part by mass or more and 6 parts by mass or less. A more preferable content is 1.5 parts by mass or more and 5.5 parts by mass or less. If the content of the perchloric acid-treated hydrotalcite is within the above range, the pinhole generation ratio at the time of forming the fake stitch can be reduced.
  • the thermoplastic resin composition of the present invention may contain zeolite as a stabilizer.
  • Zeolite has the general formula: M x / n ⁇ [(AlO 2 ) x ⁇ (SiO 2 ) y ] ⁇ zH 2 O (wherein M is a metal ion of valence n, and x + y is a tetrahedron per unit cell) Number, z is the number of moles of water).
  • M in the general formula include monovalent or divalent metals such as Na, Li, Ca, Mg, and Zn, and mixed types thereof.
  • Zeolite content is not limited to a specific range.
  • a preferable content of zeolite is 0.1 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin.
  • the thermoplastic resin composition of the present invention may contain a fatty acid metal salt.
  • Preferred fatty acid metal salts are monovalent fatty acid metal salts, more preferred fatty acid metal salts are monovalent fatty acid metal salts having 12 to 24 carbon atoms, and more preferred fatty acid metal salts having 15 to 21 carbon atoms. It is a monovalent fatty acid metal salt.
  • Specific examples of the fatty acid metal salt include lithium stearate, magnesium stearate, aluminum stearate, calcium stearate, strontium stearate, barium stearate, zinc stearate, calcium laurate, barium laurate, zinc laurate, 2-ethylhexane.
  • the metal constituting the fatty acid metal salt is preferably a metal capable of generating a polyvalent cation, more preferably a metal capable of generating a divalent cation, and a divalent cation of the third to sixth periods of the periodic table. Is more preferable, and a metal capable of generating a divalent cation in the fourth period of the periodic table is particularly preferable.
  • the most preferred fatty acid metal salt is zinc stearate.
  • the preferable content of the fatty acid metal salt with respect to 100 parts by mass of the thermoplastic resin is 0.05 part by mass or more and 5 parts by mass or less, more preferably 0.1 part by mass or more and 1 part by mass or less, and further preferably 0. .1 to 0.5 parts by mass.
  • the content of the fatty acid metal salt is in the above range, the value of the color difference after the thermoforming of the thermoplastic resin composition can be reduced.
  • the thermoplastic resin composition of the present invention may contain a dusting agent other than the above (b) vinyl chloride resin fine particles (hereinafter sometimes referred to as “other dusting agents”).
  • Other dusting agents include inorganic fine particles such as calcium carbonate, talc, and aluminum oxide; polyacrylonitrile resin fine particles, poly (meth) acrylate resin fine particles, polystyrene resin fine particles, polyethylene resin fine particles, polypropylene resin fine particles, polyester resin fine particles, polyamide Organic fine particles such as resin fine particles may be mentioned.
  • inorganic fine particles having an average particle size of 10 nm to 100 nm are preferable.
  • the content of other dusting agents is not limited to a specific range.
  • the content of other dusting agents is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, with respect to 100 parts by mass of the thermoplastic resin.
  • the thermoplastic resin composition of the present invention includes a colorant, a perchloric acid compound other than perchloric acid-treated hydrotalcite (sodium perchlorate, potassium perchlorate, etc.), an antioxidant, a fungicide, a flame retardant, It may contain other additives such as antistatic agents, fillers, light stabilizers (including UV absorbers), foaming agents, ⁇ -diketones, and lubricants.
  • the colorant are quinacridone pigments, perylene pigments, polyazo condensation pigments, isoindolinone pigments, copper phthalocyanine pigments, titanium white, and carbon black.
  • the thermoplastic resin composition of the present invention one or more pigments are used.
  • the quinacridone pigment is obtained by treating p-phenylene dianthranilic acid with concentrated sulfuric acid and exhibits a yellowish red to reddish purple hue.
  • Specific examples of the quinacridone pigment are quinacridone red, quinacridone magenta, and quinacridone violet.
  • the perylene pigment is obtained by a condensation reaction of perylene-3,4,9,10-tetracarboxylic anhydride and an aromatic primary amine, and exhibits a hue from red to magenta and brown.
  • Specific examples of the perylene pigment are perylene red, perylene orange, perylene maroon, perylene vermilion, and perylene bordeaux.
  • the polyazo condensation pigment is obtained by condensing an azo dye in a solvent to obtain a high molecular weight, and exhibits a hue of a yellow or red pigment.
  • Specific examples of the polyazo condensation pigment are polyazo red, polyazo yellow, chromophthal orange, chromophthal red, and chromophthal scarlet.
  • the isoindolinone pigment is obtained by a condensation reaction of 4,5,6,7-tetrachloroisoindolinone and an aromatic primary diamine, and exhibits a hue of greenish yellow to red and brown.
  • a specific example of the isoindolinone pigment is isoindolinone yellow.
  • the copper phthalocyanine pigment is a pigment in which copper is coordinated to phthalocyanines, and exhibits a hue of yellowish green to vivid blue.
  • Specific examples of the copper phthalocyanine pigment are phthalocyanine green and phthalocyanine blue.
  • Titanium white is a white pigment made of titanium dioxide and has a large hiding power, and there are anatase type and rutile type.
  • Carbon black is a black pigment containing carbon as a main component and containing oxygen, hydrogen, and nitrogen. Specific examples of carbon black are thermal black, acetylene black, channel black, furnace black, lamp black, and bone black.
  • antioxidants include phenolic antioxidants, sulfur antioxidants, phosphorus antioxidants, and the like.
  • fungicide examples include aliphatic ester fungicides, hydrocarbon fungicides, organic nitrogen fungicides, organic nitrogen sulfur fungicides, and the like.
  • flame retardants are halogen flame retardants such as chlorinated paraffin; phosphorus flame retardants such as phosphate esters; inorganic hydroxides such as magnesium hydroxide and aluminum hydroxide;
  • antistatic agent examples include anionic antistatic agents such as fatty acid salts, higher alcohol sulfates and sulfonates; cationic antistatic agents such as aliphatic amine salts and quaternary ammonium salts; polyoxyethylene alkyl ethers And nonionic antistatic agents such as polyoxyethylene alkylphenol ethers.
  • filler examples include silica, talc, mica, calcium carbonate, clay and the like.
  • light stabilizers include benzotriazole-based, benzophenone-based, nickel chelate-based ultraviolet absorbers, hindered amine-based light stabilizers, and the like.
  • blowing agent examples include azo compounds such as azodicarbonamide and azobisisobutyronitrile, nitroso compounds such as N, N′-dinitrosopentamethylenetetramine, p-toluenesulfonyl hydrazide, p, p-oxybis (benzene)
  • Organic foaming agents such as sulfonyl hydrazide compounds such as sulfonyl hydrazide; volatile hydrocarbon compounds such as chlorofluorocarbon gas, carbon dioxide gas, water and pentane; gas-based foaming agents such as microcapsules enclosing these.
  • ⁇ -diketones are used to more effectively suppress fluctuations in the initial color tone of a thermoplastic resin molded product obtained by powder molding of the thermoplastic resin composition of the present invention.
  • Specific examples of ⁇ -diketones are dibenzoylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, and the like.
  • One of these ⁇ -diketones may be used alone, or two or more thereof may be used in combination.
  • the content of ⁇ -diketones is not limited to a specific range.
  • a preferable content of ⁇ -diketones is 0.1 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin.
  • a specific example of the lubricant is 12-hydroxystearic acid oligomer.
  • thermoplastic resin composition of the present invention can be produced by mixing the components described above.
  • a method for producing a thermoplastic resin composition containing a thermoplastic resin and a plasticizer includes mixing at least the thermoplastic resin and the plasticizer.
  • an additive may be mixed arbitrarily.
  • the mixing method of a thermoplastic resin, a plasticizer, and an additive is not limited.
  • a preferred mixing method is to dry dry blend the components except the plasticizer and the dusting agent (including the above-mentioned (b) vinyl chloride resin fine particles and other dusting agent added if necessary), and then In this method, a plasticizer and a dusting agent are sequentially mixed.
  • the Henschel mixer is preferably used for dry blending.
  • the temperature during dry blending is preferably 50 ° C. or higher and 100 ° C. or lower, more preferably 70 ° C. or higher and 80 ° C. or lower.
  • thermoplastic resin composition of the present invention obtained as described above is usually an aggregate (powder composition) of particles composed of a plurality of particles.
  • grains contained in the thermoplastic resin composition of this invention needs to be 80 micrometers or more and 150 micrometers or less, Preferably they are 100 micrometers or more and 150 micrometers or less, More preferably, they are 110 micrometers or more and 150 micrometers or less. More preferably, they are 110 micrometers or more and 140 micrometers or less. If the average particle diameter of the particles contained in the thermoplastic resin composition is within the above range, the pinhole generation rate during fake stitch formation can be reduced.
  • grains contained in a thermoplastic resin composition points out the median diameter measured by the following method.
  • Method for measuring average particle diameter of particles contained in thermoplastic resin composition A combination sieve in which the openings are 355 ⁇ m, 250 ⁇ m, 180 ⁇ m, 150 ⁇ m, 125 ⁇ m, 106 ⁇ m, and 75 ⁇ m, respectively, and a sonic automatic sieving measuring device (manufactured by Seishin Co., Ltd., Robot Shifter RPS-105) Is used to screen the thermoplastic resin composition, and the median diameter is determined according to JIS Z 8815.
  • the average particle size of the particles contained in the thermoplastic resin composition changes the type and particle size of the material used for preparing the thermoplastic resin composition, and the mixing conditions when preparing the thermoplastic resin composition. It can be adjusted by doing.
  • thermoplastic resin molding The thermoplastic resin molded article of the present invention is obtained by powder molding, preferably powder slush molding, of the above-described thermoplastic resin composition of the present invention. Moreover, the thermoplastic resin molding of the present invention can be suitably used as a skin having a fake stitch by simultaneously obtaining a fake stitch portion during powder molding (preferably powder slush molding). And as a suitable use of the thermoplastic resin molding of this invention, skins, such as an automotive interior material, for example, an instrument panel, a door trim, etc. are mentioned.
  • thermoplastic resin molded article of the present invention can be produced using the above-described thermoplastic resin composition. That is, the method for producing a thermoplastic resin molded article of the present invention is characterized in that at least one of the above-mentioned thermoplastic resin compositions is powder-molded, preferably powder slush molded.
  • the mold temperature at the time of powder slush molding is preferably 200 ° C. or higher and 300 ° C. or lower, more preferably 220 ° C. or higher and 280 ° C. or lower.
  • thermoplastic resin composition of the present invention When producing the thermoplastic resin molded article of the present invention, the thermoplastic resin composition of the present invention is sprinkled on a mold in the above temperature range and allowed to stand for 5 seconds to 30 seconds, and then excess thermoplasticity is produced. The resin composition is shaken off and allowed to stand for 30 seconds or more and 3 minutes or less, and then the mold is cooled to 10 ° C. or more and 60 ° C. or less, and the obtained thermoplastic resin molded article of the present invention is removed from the mold. To do.
  • the die for fake stitch has a digging portion for imparting a fake stitch portion to the thermoplastic resin molded body, preferably a digging portion having a thread shape.
  • the groove width of the thread-shaped digging part is preferably 0.2 mm or more and 0.7 mm or less, more preferably 0.3 mm or more and 0.5 mm or less, and the width of the convex part of the thread-shaped digging part is , Preferably 0.02 mm to 0.1 mm, more preferably 0.03 mm to 0.08 mm.
  • the number of thread-shaped digging portions for imparting a fake stitch portion to the thermoplastic resin molded body of the fake stitch mold is usually a plurality, preferably 10 or more per mold. It is 10,000 or less, more preferably 30 or more and 1,000 or less.
  • the laminated body of the present invention can be obtained by laminating the thermoplastic resin molded body of the present invention and the foamed polyurethane molded body.
  • Lamination method is a method in which a thermoplastic resin molded body and a foamed polyurethane molded body are separately manufactured, and then bonded together by using heat fusion or thermal bonding or a known adhesive; on the thermoplastic resin molded body, Polymerization by reacting isocyanates and polyols, which are raw materials for foamed polyurethane moldings, and foaming polyurethane by a known method to directly form foamed polyurethane moldings on thermoplastic resin moldings Etc.
  • the latter is more preferable because the process is simple and the thermoplastic resin molded body and the foamed polyurethane molded body can be securely bonded even when obtaining laminates of various shapes. .
  • the laminated body of this invention is used suitably as a vehicle interior material, for example, an instrument panel, a door trim, etc.
  • the average particle diameter (volume average particle diameter) of (a) vinyl chloride resin particles and (b) vinyl chloride resin fine particles used in the thermoplastic resin composition is vinyl chloride resin particles and vinyl chloride resin.
  • the fine particles were dispersed in a water tank, and the light diffraction / scattering intensity distribution was measured and analyzed using the apparatus shown below, and the particle diameter and volume-based particle diameter distribution were measured.
  • ⁇ Apparatus Laser diffraction particle size distribution analyzer (manufactured by Shimadzu Corporation, model number “SALD-2300”) ⁇ Measuring method: Laser diffraction and scattering ⁇ Measuring range: 0.017 ⁇ m to 2500 ⁇ m
  • Light source Semiconductor laser (wavelength 680 nm, output 3 mW)
  • thermoplastic resin composition ⁇ Average degree of polymerization of (a) vinyl chloride resin particles and (b) vinyl chloride resin particles>
  • the average degree of polymerization of (a) vinyl chloride resin particles and (b) vinyl chloride resin fine particles used in the thermoplastic resin composition is in accordance with JIS K6720-2.
  • Each of the vinyl resin fine particles was calculated by dissolving each of the vinyl resin fine particles in cyclohexanone and measuring the viscosity.
  • thermoplastic resin composition ⁇ Average particle diameter of particles contained in thermoplastic resin composition> A set screen in which sieves with openings of 355 ⁇ m, 250 ⁇ m, 180 ⁇ m, 150 ⁇ m, 125 ⁇ m, 106 ⁇ m, and 75 ⁇ m are stacked in order from the top, and an automatic sound sieving measuring device (manufactured by Seishin Co., Ltd., Robot Shifter RPS-105) ) was used to screen the thermoplastic resin composition, and the median diameter was determined according to JIS Z 8815.
  • Example 1 and Comparative Examples 1 and 2 Of the blending components shown in Table 1, components except for plasticizers (trimellitic acid ester plasticizer and epoxidized soybean oil) and dusting agent vinyl chloride resin fine particles were placed in a Henschel mixer and mixed. Then, when the temperature of the mixture rose to 80 ° C., the plasticizer was added and dried up (referred to a state in which the plasticizer was absorbed into the vinyl chloride resin particles and the mixture was further improved). Thereafter, when the dried-up mixture was cooled to 70 ° C. or less, vinyl chloride resin fine particles as a dusting agent were added to produce a thermoplastic resin composition (vinyl chloride resin composition).
  • plasticizers trimellitic acid ester plasticizer and epoxidized soybean oil
  • dusting agent vinyl chloride resin fine particles were placed in a Henschel mixer and mixed. Then, when the temperature of the mixture rose to 80 ° C. Then, the plasticizer was added and dried up (referred to a state in which the plasticizer
  • thermoplastic resin composition was heated in an oven at 250 ° C. with a nickel electroforming mold (having 56 thread-shaped digging portions with a groove width of 0.4 mm and a convex width of 0.05 mm)
  • the thermoplastic resin molded sheet was allowed to melt for a period of time (specifically, 14 to 17 seconds) adjusted so that the thickness of the thermoplastic resin molded sheet became 1 mm, and then the excess thermoplastic composition was shaken off. After that, the mold was left in an oven set at 200 ° C., and after 60 seconds from standing, the mold was cooled with cooling water.
  • thermoplastic resin molding thermoplastic resin molding
  • production ratio was computed by the method mentioned above. The results are shown in Table 1. Cut the obtained thermoplastic resin molded sheet to 100 mm x 100 mm, lay the two cut vinyl chloride resin molded sheets so that they do not overlap in a 200 mm x 300 mm x 10 mm mold, and place the wrinkled face down placed.
  • a polyol mixture composed of parts by mass and a polymethylene polyphenylene polyisocyanate (polymeric MDI)) are mixed in a ratio such that the index is 98. The mixture was prepared.
  • the prepared liquid mixture was each poured on 2 sheets of thermoplastic resin molding sheets spread
  • ZEST 1300S manufactured by Shin Daiichi PVC Co., Ltd. (vinyl chloride resin particles obtained by suspension polymerization, average degree of polymerization 1300, average particle size 120 ⁇ m) 2) New 1st PVC Co., Ltd., ZEST 1300Z (vinyl chloride resin particles obtained by suspension polymerization, average polymerization degree 1300, average particle diameter 145 ⁇ m) 3) ZEST 1700Z (Vinyl chloride resin particles obtained by suspension polymerization, average degree of polymerization 1700, average particle size 145 ⁇ m), manufactured by Shin Daiichi Vinyl Co., Ltd.
  • thermoplastic resin composition of the present invention is suitably used as a molding material for the skin of automobile interior materials such as instrument panels and door trims.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Moulding By Coating Moulds (AREA)

Abstract

L'invention a pour objet de fournir une composition de résine thermoplastique destinée à obtenir un article moulé à partir de poudre présentant un faible risque d'apparition de piqûre lors de la formation de fausse maille. La composition de résine thermoplastique de l'invention contient une résine thermoplastique, et présente un diamètre particulaire moyen de particules qu'elle comprend supérieur ou égal à 80μｍ et inférieur ou égal à 150μｍ.
PCT/JP2015/006230 2014-12-17 2015-12-14 Composition de résine thermoplastique, article moulé en résine thermoplastique ainsi que procédé de fabrication de celui-ci, et stratifié WO2016098343A1 (fr)

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CN109370104A (zh) * 2018-09-29 2019-02-22 句容峰岭科技有限公司 一种聚氯乙烯搪塑复合粉料及其制备方法
WO2020090556A1 (fr) * 2018-10-31 2020-05-07 日本ゼオン株式会社 Composition de résine de chlorure de vinyle pour moulage à partir de poudres, article moulé en résine de chlorure de vinyle, et stratifié
WO2021261162A1 (fr) * 2020-06-26 2021-12-30 日本ゼオン株式会社 Composition de résine de chlorure de vinyle, composition de résine de chlorure de vinyle pour la formation de poudre, corps formé d'une composition de résine de chlorure de vinyle et procédé de fabrication de corps stratifié

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JPH0494908A (ja) * 1990-08-10 1992-03-27 Kanegafuchi Chem Ind Co Ltd 粉末成形用樹脂組成物
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CN109370104A (zh) * 2018-09-29 2019-02-22 句容峰岭科技有限公司 一种聚氯乙烯搪塑复合粉料及其制备方法
WO2020090556A1 (fr) * 2018-10-31 2020-05-07 日本ゼオン株式会社 Composition de résine de chlorure de vinyle pour moulage à partir de poudres, article moulé en résine de chlorure de vinyle, et stratifié
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JPWO2020090556A1 (ja) * 2018-10-31 2021-09-30 日本ゼオン株式会社 粉体成形用塩化ビニル樹脂組成物、塩化ビニル樹脂成形体および積層体
JP7367693B2 (ja) 2018-10-31 2023-10-24 日本ゼオン株式会社 粉体成形用塩化ビニル樹脂組成物、塩化ビニル樹脂成形体および積層体
WO2021261162A1 (fr) * 2020-06-26 2021-12-30 日本ゼオン株式会社 Composition de résine de chlorure de vinyle, composition de résine de chlorure de vinyle pour la formation de poudre, corps formé d'une composition de résine de chlorure de vinyle et procédé de fabrication de corps stratifié

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