WO2016098344A1 - Vinyl chloride resin composition, method for producing same, vinyl chloride resin molded article, method for producing same, and laminate - Google Patents

Vinyl chloride resin composition, method for producing same, vinyl chloride resin molded article, method for producing same, and laminate Download PDF

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Publication number
WO2016098344A1
WO2016098344A1 PCT/JP2015/006243 JP2015006243W WO2016098344A1 WO 2016098344 A1 WO2016098344 A1 WO 2016098344A1 JP 2015006243 W JP2015006243 W JP 2015006243W WO 2016098344 A1 WO2016098344 A1 WO 2016098344A1
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Prior art keywords
vinyl chloride
chloride resin
resin composition
mass
less
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PCT/JP2015/006243
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French (fr)
Japanese (ja)
Inventor
崇倫 藤原
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日本ゼオン株式会社
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Application filed by 日本ゼオン株式会社 filed Critical 日本ゼオン株式会社
Priority to JP2016564687A priority Critical patent/JP6720875B2/en
Priority to CN201580065408.XA priority patent/CN107001750A/en
Publication of WO2016098344A1 publication Critical patent/WO2016098344A1/en

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/18Slush casting, i.e. pouring moulding material into a hollow mould with excess material being poured off
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/40Layered products comprising a layer of synthetic resin comprising polyurethanes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered 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
    • B32B5/18Layered 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B60VEHICLES IN GENERAL
    • B60KARRANGEMENT OR MOUNTING OF PROPULSION UNITS OR OF TRANSMISSIONS IN VEHICLES; ARRANGEMENT OR MOUNTING OF PLURAL DIVERSE PRIME-MOVERS IN VEHICLES; AUXILIARY DRIVES FOR VEHICLES; INSTRUMENTATION OR DASHBOARDS FOR VEHICLES; ARRANGEMENTS IN CONNECTION WITH COOLING, AIR INTAKE, GAS EXHAUST OR FUEL SUPPLY OF PROPULSION UNITS IN VEHICLES
    • B60K37/00Dashboards
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00Compositions 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
    • C08L27/02Compositions 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
    • C08L27/04Compositions 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
    • C08L27/06Homopolymers or copolymers of vinyl chloride
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a vinyl chloride resin composition that gives a powder molded article having high adhesion to a foamed polyurethane molded article, a vinyl chloride resin molded article obtained by powder molding the vinyl chloride resin composition, and the vinyl chloride resin molded article.
  • the present invention relates to a laminate having a body and a polyurethane foam molded body, a method for producing the vinyl chloride resin composition, and a method for producing the vinyl chloride resin molded body.
  • the automobile instrument panel has a structure in which a polyurethane foam layer is provided between a skin made of resin and a base material.
  • the skin made of resin is produced mainly by powder molding a vinyl chloride resin composition.
  • the adhesiveness between the skin made of the powder molded body of the vinyl chloride resin composition and the polyurethane foam layer was low, and these two were easy to peel off. Therefore, in order to obtain a vinyl chloride resin composition that gives a powder molded body having high adhesion to the foamed polyurethane layer, powder molding containing vinyl chloride resin, plasticizer, perchloric acid-treated hydrotalcite, and white carbon
  • a vinyl chloride resin composition for use has been studied (for example, see Patent Document 1).
  • a vinyl chloride resin composition for powder molding containing a granular vinyl chloride resin, a fine vinyl chloride resin, a saccharide, a plasticizer, a stabilizer, a pigment, and the like has been studied (for example, see Patent Document 2). ).
  • the problem to be solved by the present invention is to provide a vinyl chloride resin composition that gives a powder molded body having high adhesion to a foamed polyurethane molded body.
  • Another problem to be solved by the present invention is a vinyl chloride resin molded article obtained by powder molding the vinyl chloride resin composition, and a laminate having the vinyl chloride resin molded article and a foamed polyurethane molded article. Is an offer.
  • another subject which this invention tends to solve is provision of the manufacturing method of the said vinyl chloride resin composition, and the manufacturing method of the said vinyl chloride resin molded object.
  • a vinyl chloride resin composition comprising (a) a vinyl chloride resin, (b) a plasticizer, and (c) a polyol compound having a molecular weight within a specific range.
  • the product has been found to give a powder molded product having high adhesion to the foamed polyurethane molded product, and the present invention has been completed.
  • the present invention includes (a) a vinyl chloride resin, (b) a plasticizer, and (c) a polyol compound having a molecular weight of 900 to 4000, and the polyol compound is at least one of a polyester polyol and a polyether polyol. It is a certain vinyl chloride resin composition.
  • a preferable blending amount of the (b) plasticizer is 30 parts by mass or more and 190 parts by mass or less with respect to 100 parts by mass of the (a) vinyl chloride resin.
  • the preferred compounding amount of the (c) polyol compound having a molecular weight of 900 or more and 4000 or less is 0.1 parts by mass or more with respect to 100 parts by mass of the (a) vinyl chloride resin. 30 parts by mass or less.
  • the vinyl chloride resin composition of the present invention comprises only 70% by mass to 100% by mass of (a1) vinyl chloride resin particles and 0% by mass to 30% by mass of (a2) vinyl chloride resin fine particles. Is preferred.
  • “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.
  • a preferable average particle size of the (a1) vinyl chloride resin particles is 50 ⁇ m or more and 500 ⁇ m or less, and a preferable average particle size of the (a2) vinyl chloride resin fine particles is 0.00. 1 ⁇ m or more and 10 ⁇ m or less.
  • the preferred use of the vinyl chloride resin composition of the present invention is powder molding, and the more preferred use is powder slush molding.
  • the present invention is a vinyl chloride resin molded body obtained by powder molding any one of the above vinyl chloride resin compositions.
  • the vinyl chloride resin molded article of the present invention is preferably formed by powder slush molding of any of the above vinyl chloride resin compositions.
  • the vinyl chloride resin molded product of the present invention is preferably for an automotive instrument panel skin.
  • the present invention is a laminate having a foamed polyurethane molded product and any one of the vinyl chloride resin molded products.
  • the laminate of the present invention is preferably for an automotive instrument panel.
  • the present invention also includes mixing (a) a vinyl chloride resin, (b) a plasticizer, and (c) a polyol compound having a molecular weight of 900 or more and 4000 or less.
  • the present invention is a method for producing a vinyl chloride resin molded article, which comprises powder molding any one of the vinyl chloride resin compositions or the vinyl chloride resin composition produced according to the production method. .
  • the vinyl chloride resin composition of the present invention gives a powder molded body having high adhesiveness to the foamed polyurethane molded body.
  • the vinyl chloride resin composition of the present invention contains (a) a vinyl chloride resin, (b) a plasticizer, and (c) a polyol compound having a molecular weight of 900 or more and 4000 or less, and optionally further contains an additive.
  • examples of (a) vinyl chloride resin include (a1) vinyl chloride resin particles that are resin particles and (a2) vinyl chloride resin particles that are resin fine particles.
  • the vinyl chloride resin constituting the (a1) vinyl chloride resin particles and the (a2) vinyl chloride resin fine particles, in addition to the vinyl chloride homopolymer, preferably has a vinyl chloride unit of 50% by mass or more, more preferably 70% by mass or more. Contains the containing copolymer.
  • 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 (a1) vinyl chloride resin particles and (a2) 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 (a1) vinyl chloride resin particles and (a2) 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.
  • vinyl chloride resin particles function as a matrix resin.
  • vinyl chloride resin fine particles function as a dusting agent (powder fluidity improver) described later while functioning as a matrix resin.
  • the average particle diameter of the (a1) vinyl chloride resin particles is preferably 50 ⁇ m to 500 ⁇ m, more preferably 50 ⁇ m to 250 ⁇ m, and still more preferably 100 ⁇ m to 200 ⁇ m.
  • the “average particle diameter” refers to the 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 (a1) vinyl chloride resin particles is preferably 800 or more and 5000 or less, and more preferably 800 or more and 3000 or less.
  • the vinyl chloride resin molded product obtained by powder molding the vinyl chloride resin composition is converted into a foamed polyurethane molded product. High adhesion can be imparted.
  • the “average polymerization degree” is measured according to JIS K 6720-2.
  • (A1) As the vinyl chloride resin constituting the vinyl chloride resin particles, it is preferable to use a vinyl chloride resin produced by a suspension polymerization method.
  • (a2) vinyl chloride resin fine particles can also be used as the (a) vinyl chloride resin.
  • the (a2) vinyl chloride resin fine particles function as a dusting agent that improves the powder fluidity of the vinyl chloride resin composition while functioning as a matrix resin.
  • the preferable average particle diameter of the (a2) vinyl chloride resin fine particles is 0.1 ⁇ m or more and 10 ⁇ m or less.
  • (A2) It is because the powder fluidity
  • the “average particle diameter” refers to a volume average particle diameter measured by, for example, a laser diffraction method in accordance with JIS Z8825.
  • the preferable average degree of polymerization of the vinyl chloride resin constituting the (a2) 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. (A2) If the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin fine particles is in the above range, the powder flowability of the vinyl chloride resin composition is good, and the vinyl chloride resin composition is powdered. The adhesion of the molded body of the vinyl chloride resin to the foamed polyurethane molded body is improved.
  • (A2) As the vinyl chloride resin constituting the vinyl chloride resin fine particles, it is preferable to use a vinyl chloride resin produced by an emulsion polymerization method.
  • the (a) vinyl chloride resin preferably contains at least (a1) vinyl chloride resin particles, and optionally (a2) vinyl chloride resin fine particles.
  • (a) 100% by mass of the vinyl chloride resin consists only of (a1) vinyl chloride resin particles of 70% by mass to 100% by mass and (a2) vinyl chloride resin fine particles of 0% by mass to 30% by mass. It is preferable. If (a) vinyl chloride resin of such a composition is used, the adhesiveness to the foaming polyurethane molding of the vinyl chloride resin molding formed by carrying out powder molding of the vinyl chloride resin composition will improve.
  • the vinyl chloride resin consists only of 70% to 99% by mass of (a1) vinyl chloride resin particles and 1% to 30% by mass of (a2) vinyl chloride resin fine particles. More preferably, it is composed of only 75% by mass to 95% by mass of (a1) vinyl chloride resin particles and 5% by mass to 25% by mass of (a2) vinyl chloride resin fine particles, and more preferably 80% by mass or more. It is particularly preferable that the composition consists of 92% by mass or less of (a1) vinyl chloride resin particles and 8% by mass or more and 20% by mass or less of (a2) vinyl chloride resin fine particles.
  • the powder flowability of the vinyl chloride resin composition is good, and the vinyl chloride resin composition is The adhesiveness of the vinyl chloride resin molded article formed by powder molding to the foamed polyurethane molded article is improved.
  • the plasticizer (b) contained in the vinyl chloride resin composition of the present invention is preferably a 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.
  • the trimellitic acid ester plasticizer that is preferable as the plasticizer (b) 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 the trimellitic acid ester plasticizer that can be used as the plasticizer (b) contained in the vinyl chloride resin composition of the present invention include the following primary plasticizers and secondary plasticizers.
  • 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 (b) plasticizer is preferably 30 parts by weight or more and 190 parts by weight or less, and more preferably 60 parts by weight or more and 170 parts by weight, with respect to 100 parts by weight of the (a) vinyl chloride resin. Part or less, more preferably 90 parts by mass or more and 160 parts by mass or less.
  • the content of the plasticizer (b) is in the above range, high adhesion to the foamed polyurethane molded product can be imparted to the vinyl chloride resin molded product obtained by powder molding the vinyl chloride resin composition.
  • the (c) polyol compound having a molecular weight of 900 or more and 4000 or less contained in the vinyl chloride resin composition of the present invention is not limited to a specific polyol compound if the molecular weight is 900 or more and 4000 or less.
  • examples of the polyol compound include polyester polyols such as alkylene glycol polyester polyols and polycaprolactone polyester polyols; and polyether polyols.
  • alkylene glycol polyester polyol examples include condensates of alkylene glycol and aliphatic dibasic acid.
  • the alkylene glycol-based polyester polyol is, for example, a polyester polyol that is a condensate of alkylene glycol and adipic acid as an aliphatic dibase, such as ethylene adipate ester polyol, butylene adipate ester polyol, hexylene adipate ester polyol, ethylene propylene.
  • Examples include adipate ester polyol, ethylene butylene adipate ester polyol, and ethylene neopentylene adipate ester polyol.
  • polycaprolactone-based polyester polyol examples include polyester polyols obtained by bonding polycaprolactone obtained by ring-opening polymerization of caprolactone to the polyol.
  • Specific examples of the polycaprolactone-based polyester polyol include compounds represented by the following formulas (1) and (2).
  • a, b, and c are each independently preferably an integer of 3 or more and 8 or less, more preferably an integer of 4 or more and 7 or less, and still more preferably 5 or more. It is an integer of 6 or less, particularly preferably 5.
  • l, m, and n are each independently the same or different integers. The ranges of l, m, and n are not particularly limited as long as the molecular weight of the polycaprolactone-based polyester polyol represented by the formulas (1) and (2) is in the range of 900 to 4000.
  • Each range of l, m, and n is preferably a range in which the molecular weight is 900 or more and 3000 or less, and more preferably a range in which the molecular weight is 900 or more and 2000 or less.
  • l, m, and n are each independently an integer of 1 to 80.
  • R is a structure derived from triol or diol, and is not limited to a specific structure.
  • R is an organic group composed of two or more atoms selected from the group consisting of C, O, H, and N.
  • group polyester polyol shown by Formula (1) and (2) is marketed.
  • Examples of commercially available products of the polycaprolactone-based polyester polyol (polyester triol) of the formula (1) include Plaxel (registered trademark) 312 and Plaxel 320 (both manufactured by Daicel Corporation), and the polycaprolactone type of the formula (2)
  • Plaxel 210 manufactured by Daicel Corporation
  • polyether polyol examples include poly (oxytetramethylene) glycol and poly (oxypropylene) glycol.
  • polyol compounds may be used alone or in combination of two or more.
  • a polyester polyol is preferable, and a polycaprolactone-based polyester polyol is more preferable.
  • the molecular weight of the (c) polyol compound is 900 or more and 4000 or less, preferably 900 or more and 3000 or less, and more preferably 900 or more and 2000 or less.
  • the molecular weight of the (c) polyol compound is in the above range, high adhesion to the foamed polyurethane molded product can be imparted to the vinyl chloride resin molded product obtained by powder molding the vinyl chloride resin composition.
  • the content of the polyol compound (c) having a molecular weight of 900 or more and 4000 or less is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 100 parts by mass of the vinyl chloride resin (a). Is 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass.
  • a vinyl chloride resin molded product obtained by powder molding a vinyl chloride resin composition is highly suitable for a foamed polyurethane molded product. Adhesiveness can be imparted.
  • the vinyl chloride 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.
  • 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- It is an inorganic substance having a layered crystal structure composed of a layer [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 content of perchloric acid-treated hydrotalcite is preferably 0.5 parts by mass or more and 7 parts by mass or less, and more preferably 1 part by mass or more and 6 parts by mass or less with respect to 100 parts by mass of the vinyl chloride resin (a).
  • the more preferable content is 1.5 parts by mass or more and 5.5 parts by mass or less.
  • the vinyl chloride 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 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of (a) vinyl chloride resin.
  • the vinyl chloride resin composition of the present invention may contain a fatty acid metal salt.
  • a preferred fatty acid metal salt is a monovalent fatty acid metal salt
  • a more preferred fatty acid metal salt is a monovalent fatty acid metal salt having 12 to 24 carbon atoms
  • a more preferred fatty acid metal salt is a monovalent fatty acid metal salt having 15 to 21 carbon atoms. It is a fatty acid metal salt.
  • 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. Barium acid, zinc 2-ethylhexanoate, barium ricinoleate, zinc ricinoleate and the like.
  • 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 preferred content of the fatty acid metal salt with respect to 100 parts by mass of the (a) vinyl chloride resin is 0.05 parts by mass or more and 5 parts by mass or less, more preferably 0.1 parts by mass or more and 1 part by mass or less. More preferably, they are 0.1 mass part or more and 0.5 mass part or less.
  • the content of the fatty acid metal salt is within the above range, the value of the color difference after the thermoforming of the vinyl chloride resin composition can be reduced.
  • the vinyl chloride resin composition of the present invention may contain a dusting agent other than the above (a2) 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 the other dusting agent 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 (a) vinyl chloride resin.
  • the vinyl chloride resin composition of the present invention comprises a colorant, impact modifier, perchloric acid compound other than perchloric acid-treated hydrotalcite (sodium perchlorate, potassium perchlorate, etc.), antioxidant, Other additives such as fungicides, flame retardants, antistatic agents, fillers, UV absorbers, light stabilizers, foaming agents, ⁇ -diketones, lubricants and the like may be contained.
  • the colorant are quinacridone pigments, perylene pigments, polyazo condensation pigments, isoindolinone pigments, copper phthalocyanine pigments, titanium white, and carbon black.
  • 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.
  • the impact resistance improver include acrylonitrile-butadiene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, chlorinated polyethylene, ethylene-vinyl acetate copolymer, chlorosulfonated polyethylene and the like.
  • the vinyl chloride resin composition of the present invention one or more impact resistance improvers can be used.
  • the impact resistance improver is dispersed as a heterogeneous phase of fine elastic particles in the vinyl chloride resin composition.
  • the chain and the polar group graft-polymerized on the elastic particles are compatible with the (a1) vinyl chloride resin particles, and the impact resistance of the vinyl chloride resin molded product obtained by powder molding the vinyl chloride resin composition is improved.
  • the antioxidant include a phenol-based antioxidant, a sulfur-based antioxidant, and a phosphorus-based antioxidant.
  • Specific examples of the fungicide 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 vinyl chloride resin molded article obtained by powder molding the vinyl chloride 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.
  • the preferred content of ⁇ -diketones is 0.1 to 5 parts by mass with respect to 100 parts by mass of (a) vinyl chloride resin.
  • a specific example of the lubricant is 12-hydroxystearic acid oligomer.
  • the vinyl chloride resin composition of the present invention can be produced by mixing the components described above. That is, the method for producing a vinyl chloride resin composition of the present invention comprises at least (a) a vinyl chloride resin, (b) a plasticizer, and (c) a polyol compound having a molecular weight of 900 or more and 4000 or less (polyester polyol and / or Or mixing a polyether polyol). And in the manufacturing method of the vinyl chloride resin composition of this invention, in addition to the said component, an additive may be mixed arbitrarily.
  • the mixing method of the (a) vinyl chloride resin, the (b) plasticizer, the (c) polyol compound having a molecular weight of 900 or more and 4000 or less, and an additive added as necessary is not limited.
  • a preferred mixing method is to dry dry blend the components except for the plasticizer and the dusting agent (including the above (a2) 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.
  • the vinyl chloride resin molded article of the present invention is obtained by powder molding, preferably powder slush molding, of the above-described vinyl chloride resin composition of the present invention.
  • the vinyl chloride resin molded article of the present invention is suitably used as an automobile interior material, for example, as a skin for instrument panels, door trims, and the like.
  • the vinyl chloride resin molded article of the present invention can be produced using the above-described vinyl chloride resin composition. That is, the method for producing a vinyl chloride resin molded article of the present invention is at least one of the above-described vinyl chloride resin compositions or a vinyl chloride resin composition produced according to the above-described production method. It is characterized by slush molding.
  • 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.
  • the vinyl chloride resin composition of the present invention is sprinkled on a mold in the above temperature range and left for 5 seconds to 30 seconds, and then excess vinyl chloride is used.
  • 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 vinyl chloride resin molded article of the present invention is removed from the mold. To do.
  • the laminate of the present invention can be obtained by laminating the vinyl chloride resin molded product of the present invention and the foamed polyurethane molded product.
  • the lamination method is a method in which a vinyl chloride 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 vinyl chloride resin molded body, Polymerization by reacting isocyanates, which are raw materials for foamed polyurethane moldings, polyols, etc., and foaming polyurethane by a known method to directly form a foamed polyurethane molding on a vinyl chloride resin molding Etc.
  • the latter is more preferable because the process is simple and the vinyl chloride resin molded body and the polyurethane foam 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 present invention will be described in detail by way of examples, but the present invention is not limited to these examples.
  • the measuring method of various physical properties and the evaluation method of adhesiveness are as follows.
  • the average particle diameter (volume average particle diameter) of (a1) vinyl chloride resin particles and (a2) vinyl chloride resin fine particles used in the vinyl chloride resin composition is as follows: 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)
  • the average degree of polymerization of (a1) vinyl chloride resin particles and (a2) vinyl chloride resin fine particles used in the vinyl chloride 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.
  • Cohesive failure occurs in an area of 60% or more and less than 90% of the peeled surface
  • C Cohesive failure occurs in an area of less than 60% of the peeled surface.
  • the “cohesive failure” is a phenomenon in which the foamed polyurethane molded product is destroyed when the vinyl chloride resin molded sheet is peeled off, and a part of the foamed polyurethane molded product remains on the vinyl chloride resin molded sheet side.
  • Examples 1 to 3 and Comparative Examples 1 to 2 Among the blending components shown in Table 1, components other than plasticizers (trimellitic acid ester plasticizer and epoxidized soybean oil) and vinyl chloride resin fine particles as a dusting agent 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 lower, vinyl chloride resin fine particles as a dusting agent were added to produce a vinyl chloride resin composition.
  • plasticizers trimellitic acid ester plasticizer and epoxidized soybean oil
  • vinyl chloride resin fine particles as a dusting agent were added to produce a vinyl chloride resin composition.
  • the obtained vinyl chloride resin composition is sprinkled on a mold with a texture heated to 250 ° C., and left for a time (specifically, 12 to 14 seconds) adjusted so that the thickness of the vinyl chloride resin molded sheet becomes 1 mm. Then, the excess vinyl chloride resin composition was shaken off. Then, it is left still in an oven set at 200 ° C., and when 60 seconds have passed after standing, the mold is cooled with cooling water, and when the mold temperature is cooled to 40 ° C., 145 mm ⁇ 175 mm ⁇ 1 mm The vinyl resin molded sheet was removed from the mold.
  • 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 vinyl chloride resin molding sheets spread
  • ZEST 1000Z Vinyl chloride resin particles obtained by suspension polymerization, average degree of polymerization 1000, average particle size 145 ⁇ m), manufactured by Shin Daiichi PVC Co., Ltd.
  • Made by Kao Corporation, Trimex N-08 Adeka Sizer O-130S manufactured by ADEKA Corporation
  • Alkamizer 5 manufactured by Kyowa Chemical Industry Co., Ltd.
  • MIZUKALIZER DS manufactured by Mizusawa Chemical Co., Ltd.
  • Karenz DK-1 manufactured by Showa Denko K.K.
  • SAKAI SZ2000 manufactured by Sakai Chemical Industry Co., Ltd.
  • the molecular weights of the polyester polyols (polyester diol and polyester triol) used in the above examples and comparative examples are the values disclosed by Daicel Corporation in the catalog.
  • the molecular weight of polyol type compounds, such as polyester polyol can be computed as a number average molecular weight based on the hydroxyl value measured based on JISK1557.
  • the vinyl chloride resin molded articles obtained from the vinyl chloride resin compositions of Examples 1 to 3 are excellent in adhesiveness to the foamed polyurethane molded articles.
  • a foamed polyurethane molded article of a vinyl chloride resin molded article obtained from the vinyl chloride resin composition of Comparative Example 1 containing no polyester polyol, and a vinyl chloride resin composition of Comparative Example 2 containing a polyester polyol having a molecular weight of less than 900 It can be seen that any of the vinyl chloride resin moldings obtained from the products has low adhesion to the polyurethane foam molding.
  • the vinyl chloride 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.

Abstract

The purpose of the present invention is to provide a vinyl chloride resin composition with which it is possible to obtain a powder molded article having high adhesiveness to foamed polyurethane molded articles. This vinyl chloride resin composition includes (a) vinyl chloride resin, (b) a plasticizer, and (c) a polyol compound having a molecular weight of 900-4,000, the polyol compound being a polyester polyol and/or polyether polyol.

Description

塩化ビニル樹脂組成物及びその製造方法、塩化ビニル樹脂成形体及びその製造方法、並びに、積層体Vinyl chloride resin composition and method for producing the same, vinyl chloride resin molded article and method for producing the same, and laminate
 本発明は、発泡ポリウレタン成形体への接着性が高い粉体成形体を与える塩化ビニル樹脂組成物、上記塩化ビニル樹脂組成物を粉体成形してなる塩化ビニル樹脂成形体、上記塩化ビニル樹脂成形体と発泡ポリウレタン成形体とを有する積層体、上記塩化ビニル樹脂組成物の製造方法、及び上記塩化ビニル樹脂成形体の製造方法に関する。 The present invention relates to a vinyl chloride resin composition that gives a powder molded article having high adhesion to a foamed polyurethane molded article, a vinyl chloride resin molded article obtained by powder molding the vinyl chloride resin composition, and the vinyl chloride resin molded article. The present invention relates to a laminate having a body and a polyurethane foam molded body, a method for producing the vinyl chloride resin composition, and a method for producing the vinyl chloride resin molded body.
 自動車インスツルメントパネルは、発泡ポリウレタン層が、樹脂からなる表皮と基材との間に設けられた構造を有している。ここで樹脂からなる表皮は、主として塩化ビニル樹脂組成物が粉体成形されて製造される。しかし、塩化ビニル樹脂組成物の粉体成形体よりなる表皮と発泡ポリウレタン層との接着性は低く、これら2つは剥離しやすかった。
 そこで、発泡ポリウレタン層への接着性が高い粉体成形体を与える塩化ビニル樹脂組成物を得るため、塩化ビニル樹脂、可塑剤、過塩素酸処理ハイドロタルサイト、及びホワイトカーボンを含有する粉体成形用塩化ビニル樹脂組成物が検討された(例えば、特許文献1参照)。
 更に、粒状塩化ビニル系樹脂、微粒塩化ビニル系樹脂、糖質類、可塑剤、安定剤、及び顔料等を含む粉体成形用塩化ビニル系樹脂組成物が検討された(例えば、特許文献2参照)。
The automobile instrument panel has a structure in which a polyurethane foam layer is provided between a skin made of resin and a base material. Here, the skin made of resin is produced mainly by powder molding a vinyl chloride resin composition. However, the adhesiveness between the skin made of the powder molded body of the vinyl chloride resin composition and the polyurethane foam layer was low, and these two were easy to peel off.
Therefore, in order to obtain a vinyl chloride resin composition that gives a powder molded body having high adhesion to the foamed polyurethane layer, powder molding containing vinyl chloride resin, plasticizer, perchloric acid-treated hydrotalcite, and white carbon A vinyl chloride resin composition for use has been studied (for example, see Patent Document 1).
Furthermore, a vinyl chloride resin composition for powder molding containing a granular vinyl chloride resin, a fine vinyl chloride resin, a saccharide, a plasticizer, a stabilizer, a pigment, and the like has been studied (for example, see Patent Document 2). ).
特開平7-149984号公報Japanese Patent Laid-Open No. 7-149984 特開平5-105794号公報Japanese Patent Laid-Open No. 5-105794
 近年、発泡ポリウレタン成形体への接着性が高い粉体成形体を与える、従来の塩化ビニル樹脂組成物とは異なる組成の塩化ビニル樹脂組成物が要求されていた。しかし、そのような塩化ビニル樹脂組成物は得られていなかった。
 そこで、本発明が解決しようとする課題は、発泡ポリウレタン成形体への接着性が高い粉体成形体を与える塩化ビニル樹脂組成物の提供である。また、本発明が解決しようとする別の課題は、上記塩化ビニル樹脂組成物を粉体成形してなる塩化ビニル樹脂成形体、及び、上記塩化ビニル樹脂成形体と発泡ポリウレタン成形体を有する積層体の提供である。更に、本発明が解決しようとする別の課題は、上記塩化ビニル樹脂組成物の製造方法、及び、上記塩化ビニル樹脂成形体の製造方法の提供である。
In recent years, there has been a demand for a vinyl chloride resin composition having a composition different from that of a conventional vinyl chloride resin composition, which gives a powder molded article having high adhesion to a foamed polyurethane molded article. However, such a vinyl chloride resin composition has not been obtained.
Therefore, the problem to be solved by the present invention is to provide a vinyl chloride resin composition that gives a powder molded body having high adhesion to a foamed polyurethane molded body. Another problem to be solved by the present invention is a vinyl chloride resin molded article obtained by powder molding the vinyl chloride resin composition, and a laminate having the vinyl chloride resin molded article and a foamed polyurethane molded article. Is an offer. Furthermore, another subject which this invention tends to solve is provision of the manufacturing method of the said vinyl chloride resin composition, and the manufacturing method of the said vinyl chloride resin molded object.
 本発明の発明者は、上記課題を解決するために鋭意検討した結果、(a)塩化ビニル樹脂、(b)可塑剤、及び(c)特定範囲の分子量のポリオール系化合物を含む塩化ビニル樹脂組成物が、発泡ポリウレタン成形体への接着性が高い粉体成形体を与えることを見出し、本発明を完成させるに至った。 The inventor of the present invention has intensively studied to solve the above problems, and as a result, a vinyl chloride resin composition comprising (a) a vinyl chloride resin, (b) a plasticizer, and (c) a polyol compound having a molecular weight within a specific range. The product has been found to give a powder molded product having high adhesion to the foamed polyurethane molded product, and the present invention has been completed.
 本発明は、(a)塩化ビニル樹脂、(b)可塑剤、及び(c)分子量が900以上4000以下のポリオール系化合物を含み、前記ポリオール系化合物が、ポリエステルポリオールおよびポリエーテルポリオールの少なくとも一方である、塩化ビニル樹脂組成物である。 The present invention includes (a) a vinyl chloride resin, (b) a plasticizer, and (c) a polyol compound having a molecular weight of 900 to 4000, and the polyol compound is at least one of a polyester polyol and a polyether polyol. It is a certain vinyl chloride resin composition.
 ここで、本発明の塩化ビニル樹脂組成物において、前記(b)可塑剤の好ましい配合量は、前記(a)塩化ビニル樹脂100質量部に対し30質量部以上190質量部以下である。 Here, in the vinyl chloride resin composition of the present invention, a preferable blending amount of the (b) plasticizer is 30 parts by mass or more and 190 parts by mass or less with respect to 100 parts by mass of the (a) vinyl chloride resin.
 そして、本発明の塩化ビニル樹脂組成物において、前記(c)分子量が900以上4000以下のポリオール系化合物の好ましい配合量は、上記(a)塩化ビニル樹脂100質量部に対し0.1質量部以上30質量部以下である。 And in the vinyl chloride resin composition of the present invention, the preferred compounding amount of the (c) polyol compound having a molecular weight of 900 or more and 4000 or less is 0.1 parts by mass or more with respect to 100 parts by mass of the (a) vinyl chloride resin. 30 parts by mass or less.
 更に、本発明の塩化ビニル樹脂組成物は、70質量%以上100質量%以下の(a1)塩化ビニル樹脂粒子、及び0質量%以上30質量%以下の(a2)塩化ビニル樹脂微粒子のみからなることが好ましい。なお、本発明において、「樹脂粒子」とは、粒子径が30μm以上の粒子を指し、「樹脂微粒子」とは、粒子径が30μm未満の粒子を指す。 Furthermore, the vinyl chloride resin composition of the present invention comprises only 70% by mass to 100% by mass of (a1) vinyl chloride resin particles and 0% by mass to 30% by mass of (a2) vinyl chloride resin fine particles. Is preferred. In the present invention, “resin particles” refers to particles having a particle size of 30 μm or more, and “resin particles” refers to particles having a particle size of less than 30 μm.
 加えて、本発明の塩化ビニル樹脂組成物において、上記(a1)塩化ビニル樹脂粒子の好ましい平均粒子径は50μm以上500μm以下であり、上記(a2)塩化ビニル樹脂微粒子の好ましい平均粒子径は0.1μm以上10μm以下である。 In addition, in the vinyl chloride resin composition of the present invention, a preferable average particle size of the (a1) vinyl chloride resin particles is 50 μm or more and 500 μm or less, and a preferable average particle size of the (a2) vinyl chloride resin fine particles is 0.00. 1 μm or more and 10 μm or less.
 そして、本発明の塩化ビニル樹脂組成物の好ましい用途は粉体成形であり、更に好ましい用途はパウダースラッシュ成形である。 The preferred use of the vinyl chloride resin composition of the present invention is powder molding, and the more preferred use is powder slush molding.
 また、本発明は、前記いずれかの塩化ビニル樹脂組成物を粉体成形してなる塩化ビニル樹脂成形体である。 Further, the present invention is a vinyl chloride resin molded body obtained by powder molding any one of the above vinyl chloride resin compositions.
 ここで、本発明の塩化ビニル樹脂成形体は、好ましくは前記いずれかの塩化ビニル樹脂組成物をパウダースラッシュ成形してなる。 Here, the vinyl chloride resin molded article of the present invention is preferably formed by powder slush molding of any of the above vinyl chloride resin compositions.
 そして、本発明の塩化ビニル樹脂成形体は、好ましくは自動車インスツルメントパネル表皮用である。 The vinyl chloride resin molded product of the present invention is preferably for an automotive instrument panel skin.
 また、本発明は、発泡ポリウレタン成形体と、前記いずれかの塩化ビニル樹脂成形体とを有する積層体である。 Further, the present invention is a laminate having a foamed polyurethane molded product and any one of the vinyl chloride resin molded products.
 ここで、本発明の積層体は、好ましくは自動車インスツルメントパネル用である。 Here, the laminate of the present invention is preferably for an automotive instrument panel.
 また、本発明は、(a)塩化ビニル樹脂、(b)可塑剤、及び(c)分子量が900以上4000以下のポリオール系化合物を混合することを含み、前記ポリオール系化合物が、ポリエステルポリオールおよびポリエーテルポリオールの少なくとも一方である、前記いずれかの塩化ビニル樹脂組成物の製造方法である。 The present invention also includes mixing (a) a vinyl chloride resin, (b) a plasticizer, and (c) a polyol compound having a molecular weight of 900 or more and 4000 or less. The method for producing any one of the vinyl chloride resin compositions, which is at least one of ether polyols.
 また、本発明は、前記いずれかの塩化ビニル樹脂組成物、または、前記製造方法に従って製造した塩化ビニル樹脂組成物を粉体成形することを特徴とする、塩化ビニル樹脂成形体の製造方法である。 In addition, the present invention is a method for producing a vinyl chloride resin molded article, which comprises powder molding any one of the vinyl chloride resin compositions or the vinyl chloride resin composition produced according to the production method. .
 本発明の塩化ビニル樹脂組成物は、発泡ポリウレタン成形体への接着性が高い粉体成形体を与える。 The vinyl chloride resin composition of the present invention gives a powder molded body having high adhesiveness to the foamed polyurethane molded body.
(塩化ビニル樹脂組成物)
 本発明の塩化ビニル樹脂組成物は(a)塩化ビニル樹脂と、(b)可塑剤と、(c)分子量が900以上4000以下のポリオール系化合物とを含み、任意に添加剤を更に含有する。
(Vinyl chloride resin composition)
The vinyl chloride resin composition of the present invention contains (a) a vinyl chloride resin, (b) a plasticizer, and (c) a polyol compound having a molecular weight of 900 or more and 4000 or less, and optionally further contains an additive.
<(a)塩化ビニル樹脂>
 ここで本発明において、(a)塩化ビニル樹脂としては、樹脂粒子である(a1)塩化ビニル樹脂粒子と、樹脂微粒子である(a2)塩化ビニル樹脂微粒子とが挙げられる。
 (a1)塩化ビニル樹脂粒子および(a2)塩化ビニル樹脂微粒子を構成する塩化ビニル樹脂は、塩化ビニルの単独重合体の他、塩化ビニル単位を好ましくは50質量%以上、より好ましくは70質量%以上含有する共重合体を含む。塩化ビニル共重合体の共単量体の具体例は、エチレン、プロピレンなどのオレフィン類;塩化アリル、塩化ビニリデン、フッ化ビニル、三フッ化塩化エチレンなどのハロゲン化オレフィン類;酢酸ビニル、プロピオン酸ビニルなどのカルボン酸ビニルエステル類;イソブチルビニルエーテル、セチルビニルエーテルなどのビニルエーテル類;アリル-3-クロロ-2-オキシプロピルエーテル、アリルグリシジルエーテルなどのアリルエーテル類;アクリル酸、マレイン酸、イタコン酸、アクリル酸-2-ヒドロキシエチル、メタクリル酸メチル、マレイン酸モノメチル、マレイン酸ジエチル、無水マレイン酸などの不飽和カルボン酸、そのエステルまたはその酸無水物類;アクリロニトリル、メタクリロニトリルなどの不飽和ニトリル類;アクリルアミド、N-メチロールアクリルアミド、アクリルアミド-2-メチルプロパンスルホン酸、(メタ)アクリルアミドプロピルトリメチルアンモニウムクロライドなどのアクリルアミド類;アリルアミン安息香酸塩、ジアリルジメチルアンモニウムクロライドなどのアリルアミンおよびその誘導体類;などである。以上に例示される単量体は、塩化ビニルと共重合可能な単量体(共単量体)の一部に過ぎず、共単量体としては、近畿化学協会ビニル部会編「ポリ塩化ビニル」日刊工業新聞社(1988年)第75~104頁に例示されている各種単量体が使用され得る。これらの単量体の1種又は2種以上が使用され得る。上記(a1)塩化ビニル樹脂粒子および(a2)塩化ビニル樹脂微粒子を構成する塩化ビニル樹脂には、エチレン-酢酸ビニル共重合体、エチレン-メタクリル酸メチル共重合体、エチレン-アクリル酸エチル共重合体、塩素化ポリエチレンなどの樹脂に、(1)塩化ビニルまたは(2)塩化ビニルと前記共単量体とがグラフト重合された樹脂も含まれる。
 ここで、本明細書において、「(メタ)アクリル」とは、アクリル及び/又はメタクリルを意味する。
<(A) Vinyl chloride resin>
In the present invention, examples of (a) vinyl chloride resin include (a1) vinyl chloride resin particles that are resin particles and (a2) vinyl chloride resin particles that are resin fine particles.
The vinyl chloride resin constituting the (a1) vinyl chloride resin particles and the (a2) vinyl chloride resin fine particles, in addition to the vinyl chloride homopolymer, preferably has a vinyl chloride unit of 50% by mass or more, more preferably 70% by mass or more. Contains the containing copolymer. 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. As the comonomer, “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 (a1) vinyl chloride resin particles and (a2) vinyl chloride resin fine particles include ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, and ethylene-ethyl acrylate copolymer. Also included are 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.
Here, in this specification, “(meth) acryl” means acryl and / or methacryl.
 上記(a1)塩化ビニル樹脂粒子および(a2)塩化ビニル樹脂微粒子を構成する塩化ビニル樹脂は、懸濁重合法、乳化重合法、溶液重合法、塊状重合法など、従来から知られているいずれの製造法によっても製造され得る。 The vinyl chloride resin constituting the above (a1) vinyl chloride resin particles and (a2) 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.
 なお、塩化ビニル樹脂組成物において、(a1)塩化ビニル樹脂粒子は、マトリックス樹脂として機能する。また、(a2)塩化ビニル樹脂微粒子は、マトリックス樹脂として機能しつつ、後述するダスティング剤(粉体流動性改良剤)として機能する。 In the vinyl chloride resin composition, (a1) vinyl chloride resin particles function as a matrix resin. Moreover, (a2) vinyl chloride resin fine particles function as a dusting agent (powder fluidity improver) described later while functioning as a matrix resin.
[(a1)塩化ビニル樹脂粒子]
 ここで、(a1)塩化ビニル樹脂粒子の平均粒子径は、好ましくは50μm以上500μm以下、より好ましくは50μm以上250μm以下、更に好ましくは100μm以上200μm以下である。(a1)塩化ビニル樹脂粒子の平均粒子径が上記範囲であると、塩化ビニル樹脂組成物の粉体流動性が良好であり、かつ、上記塩化ビニル樹脂組成物を粉体成形してなる塩化ビニル樹脂成形体の、発泡ポリウレタン成形体への接着性が向上する。
 なお、「平均粒子径」は、JIS Z8825に準拠し、例えばレーザー回折法により測定される体積平均粒子径を指す。
[(A1) Vinyl chloride resin particles]
Here, the average particle diameter of the (a1) vinyl chloride resin particles is preferably 50 μm to 500 μm, more preferably 50 μm to 250 μm, and still more preferably 100 μm to 200 μm. (A1) When the average particle diameter of the vinyl chloride resin particles is within the above range, the powder flowability of the vinyl chloride resin composition is good and the vinyl chloride resin composition is obtained by powder molding the vinyl chloride resin composition. Adhesiveness of the resin molded body to the foamed polyurethane molded body is improved.
The “average particle diameter” refers to the volume average particle diameter measured by, for example, a laser diffraction method in accordance with JIS Z8825.
 上記(a1)塩化ビニル樹脂粒子を構成する塩化ビニル樹脂の平均重合度は、好ましくは800以上5000以下であり、より好ましくは800以上3000以下である。上記(a1)塩化ビニル樹脂粒子を構成する塩化ビニル樹脂の平均重合度が上記範囲であると、塩化ビニル樹脂組成物を粉体成形してなる塩化ビニル樹脂成形体に、発泡ポリウレタン成形体への高い接着性を付与できる。
 なお、「平均重合度」は、JIS K 6720-2に準拠して測定される。
The average degree of polymerization of the vinyl chloride resin constituting the (a1) vinyl chloride resin particles is preferably 800 or more and 5000 or less, and more preferably 800 or more and 3000 or less. When the average degree of polymerization of the vinyl chloride resin constituting the (a1) vinyl chloride resin particles is in the above range, the vinyl chloride resin molded product obtained by powder molding the vinyl chloride resin composition is converted into a foamed polyurethane molded product. High adhesion can be imparted.
The “average polymerization degree” is measured according to JIS K 6720-2.
 また、(a1)塩化ビニル樹脂粒子を構成する塩化ビニル樹脂としては、懸濁重合法により製造された塩化ビニル樹脂を用いることが好ましい。 (A1) As the vinyl chloride resin constituting the vinyl chloride resin particles, it is preferable to use a vinyl chloride resin produced by a suspension polymerization method.
[(a2)塩化ビニル樹脂微粒子]
 本発明の塩化ビニル樹脂組成物は、上記(a)塩化ビニル樹脂として、(a2)塩化ビニル樹脂微粒子を使用することもできる。上記(a2)塩化ビニル樹脂微粒子は、マトリックス樹脂として機能しつつ、塩化ビニル樹脂組成物の粉体流動性を向上させるダスティング剤として機能する。
[(A2) Vinyl chloride resin fine particles]
In the vinyl chloride resin composition of the present invention, (a2) vinyl chloride resin fine particles can also be used as the (a) vinyl chloride resin. The (a2) vinyl chloride resin fine particles function as a dusting agent that improves the powder fluidity of the vinyl chloride resin composition while functioning as a matrix resin.
 ここで、上記(a2)塩化ビニル樹脂微粒子の好ましい平均粒子径は0.1μm以上10μm以下である。(a2)塩化ビニル樹脂微粒子の平均粒子径が上記範囲であると、塩化ビニル樹脂組成物の粉体流動性が向上するからである。
 なお、「平均粒子径」は、JIS Z8825に準拠し、例えば、レーザー回折法により測定される体積平均粒子径を指す。
Here, the preferable average particle diameter of the (a2) vinyl chloride resin fine particles is 0.1 μm or more and 10 μm or less. (A2) It is because the powder fluidity | liquidity of a vinyl chloride resin composition will improve that the average particle diameter of vinyl chloride resin fine particle is the said range.
The “average particle diameter” refers to a volume average particle diameter measured by, for example, a laser diffraction method in accordance with JIS Z8825.
 上記(a2)塩化ビニル樹脂微粒子を構成する塩化ビニル樹脂の好ましい平均重合度は、好ましくは500以上5000以下であり、より好ましくは600以上3000以下であり、更に好ましくは700以上2500以下である。上記(a2)塩化ビニル樹脂微粒子を構成する塩化ビニル樹脂の平均重合度が上記範囲であると、塩化ビニル樹脂組成物の粉体流動性が良好であり、かつ、上記塩化ビニル樹脂組成物を粉体成形してなる塩化ビニル樹脂成形体の、発泡ポリウレタン成形体への接着性が向上する。 The preferable average degree of polymerization of the vinyl chloride resin constituting the (a2) 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. (A2) If the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin fine particles is in the above range, the powder flowability of the vinyl chloride resin composition is good, and the vinyl chloride resin composition is powdered. The adhesion of the molded body of the vinyl chloride resin to the foamed polyurethane molded body is improved.
 また、(a2)塩化ビニル樹脂微粒子を構成する塩化ビニル樹脂としては、乳化重合法により製造された塩化ビニル樹脂を用いることが好ましい。 (A2) As the vinyl chloride resin constituting the vinyl chloride resin fine particles, it is preferable to use a vinyl chloride resin produced by an emulsion polymerization method.
[(a)塩化ビニル樹脂中における(a1)塩化ビニル樹脂粒子及び(a2)塩化ビニル樹脂微粒子の配合割合]
 ここで(a)塩化ビニル樹脂は、好適には、少なくとも(a1)塩化ビニル樹脂粒子を含み、任意に、(a2)塩化ビニル樹脂微粒子を含む。例えば、(a)塩化ビニル樹脂100質量%が、70質量%以上100質量%以下の(a1)塩化ビニル樹脂粒子、及び0質量%以上30質量%以下の(a2)塩化ビニル樹脂微粒子のみからなることが好ましい。このような組成の(a)塩化ビニル樹脂を使用すれば、塩化ビニル樹脂組成物を粉体成形してなる塩化ビニル樹脂成形体の、発泡ポリウレタン成形体への接着性が向上する。
 そして(a)塩化ビニル樹脂100質量%は、70質量%以上99質量%以下の(a1)塩化ビニル樹脂粒子、及び1質量%以上30質量%以下の(a2)塩化ビニル樹脂微粒子のみからなることがより好ましく、75質量%以上95質量%以下の(a1)塩化ビニル樹脂粒子、及び5質量%以上25質量%以下の(a2)塩化ビニル樹脂微粒子のみからなることが更に好ましく、80質量%以上92質量%以下の(a1)塩化ビニル樹脂粒子、及び8質量%以上20質量%以下の(a2)塩化ビニル樹脂微粒子のみからなることが特に好ましい。上記(a1)塩化ビニル樹脂粒子及び(a2)塩化ビニル樹脂微粒子の配合割合が上記範囲であると、塩化ビニル樹脂組成物の粉体流動性が良好であり、かつ、上記塩化ビニル樹脂組成物を粉体成形してなる塩化ビニル樹脂成形体の、発泡ポリウレタン成形体への接着性が向上する。
[(A) Mixing ratio of (a1) vinyl chloride resin particles and (a2) vinyl chloride resin fine particles in vinyl chloride resin]
Here, the (a) vinyl chloride resin preferably contains at least (a1) vinyl chloride resin particles, and optionally (a2) vinyl chloride resin fine particles. For example, (a) 100% by mass of the vinyl chloride resin consists only of (a1) vinyl chloride resin particles of 70% by mass to 100% by mass and (a2) vinyl chloride resin fine particles of 0% by mass to 30% by mass. It is preferable. If (a) vinyl chloride resin of such a composition is used, the adhesiveness to the foaming polyurethane molding of the vinyl chloride resin molding formed by carrying out powder molding of the vinyl chloride resin composition will improve.
And (a) 100% by mass of the vinyl chloride resin consists only of 70% to 99% by mass of (a1) vinyl chloride resin particles and 1% to 30% by mass of (a2) vinyl chloride resin fine particles. More preferably, it is composed of only 75% by mass to 95% by mass of (a1) vinyl chloride resin particles and 5% by mass to 25% by mass of (a2) vinyl chloride resin fine particles, and more preferably 80% by mass or more. It is particularly preferable that the composition consists of 92% by mass or less of (a1) vinyl chloride resin particles and 8% by mass or more and 20% by mass or less of (a2) vinyl chloride resin fine particles. When the blending ratio of the (a1) vinyl chloride resin particles and (a2) vinyl chloride resin fine particles is within the above range, the powder flowability of the vinyl chloride resin composition is good, and the vinyl chloride resin composition is The adhesiveness of the vinyl chloride resin molded article formed by powder molding to the foamed polyurethane molded article is improved.
<可塑剤>
 本発明の塩化ビニル樹脂組成物が含有する(b)可塑剤は、好ましくは、トリメリット酸エステル可塑剤である。トリメリット酸エステル可塑剤は、トリメリット酸と一価アルコールとのエステル化合物である。
<Plasticizer>
The plasticizer (b) contained in the vinyl chloride resin composition of the present invention is preferably a trimellitic acid ester plasticizer. The trimellitic acid ester plasticizer is an ester compound of trimellitic acid and a monohydric alcohol.
 上記一価アルコールの具体例としては、特に限定されることなく、1-ヘキサノール、1-ヘプタノール、1-オクタノール、2-エチルヘキサノール、1-ノナノール、1-デカノール、1-ウンデカノール、1-ドデカノール等が挙げられる。 Specific examples of the monohydric alcohol 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.
 中でも、(b)可塑剤として好ましいトリメリット酸エステル可塑剤は、上述した一価アルコールによりトリメリット酸のカルボキシ基を実質的に全てエステル化したトリエステル化物である。トリエステル化物におけるアルコール残基部分は、同一のアルコール由来であってもよく、それぞれ異なるアルコール由来のものであってもよい。
 上記トリメリット酸エステル可塑剤は、単一の化合物からなるものであってもよいし、異なる化合物の混合物であってもよい。
Among them, the trimellitic acid ester plasticizer that is preferable as the plasticizer (b) 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.
 好適なトリメリット酸エステル可塑剤の具体例は、トリメリット酸トリ-n-ヘキシル、トリメリット酸トリ-n-ヘプチル、トリメリット酸トリ-n-オクチル、トリメリット酸トリ-(2-エチルヘキシル)、トリメリット酸トリ-n-ノニル、トリメリット酸トリ-n-デシル、トリメリット酸トリイソデシル、トリメリット酸トリ-n-ウンデシル、トリメリット酸トリ-n-ドデシル、トリメリット酸トリ-n-アルキルエステル(炭素数が異なるアルキル基〔但し、炭素数は6~12である。〕を分子内に2種以上有するエステル)、トリメリット酸トリアルキルエステル(炭素数が異なるアルキル基〔但し、炭素数は8~10である。〕を分子内に2種以上有するエステル)、及びこれらの混合物等である。
 より好ましいトリメリット酸エステル可塑剤の具体例は、トリメリット酸トリ-n-オクチル、トリメリット酸トリ-(2-エチルヘキシル)、トリメリット酸トリ-n-ノニル、トリメリット酸トリ-n-デシル、トリメリット酸トリ-n-アルキルエステル(炭素数が異なるアルキル基〔但し、炭素数は8~10である。〕を分子内に2種以上有するエステル)、及びこれらの混合物等である。
Specific examples of suitable 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.
Specific examples of more preferable 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.
 本発明の塩化ビニル樹脂組成物が含有する(b)可塑剤として用い得るトリメリット酸エステル可塑剤以外の可塑剤としては、例えば、以下の一次可塑剤及び二次可塑剤などが挙げられる。 Examples of the plasticizer other than the trimellitic acid ester plasticizer that can be used as the plasticizer (b) contained in the vinyl chloride resin composition of the present invention include the following primary plasticizers and secondary plasticizers.
 いわゆる一次可塑剤としては、
 ピロメリット酸テトラ-n-ヘキシル、ピロメリット酸テトラ-n-ヘプチル、ピロメリット酸テトラ-n-オクチル、ピロメリット酸テトラ-(2-エチルヘキシル)、ピロメリット酸テトラ-n-ノニル、ピロメリット酸テトラ-n-デシル、ピロメリット酸テトライソデシル、ピロメリット酸テトラ-n-ウンデシル、ピロメリット酸テトラ-n-ドデシル、ピロメリット酸テトラ-n-アルキルエステル(炭素数が異なるアルキル基〔但し、炭素数は6~12である。〕を分子内に2種以上有するエステル)等のピロメリット酸エステル可塑剤;
 ジメチルフタレート、ジエチルフタレート、ジブチルフタレート、ジ-(2-エチルヘキシル)フタレート、ジ-n-オクチルフタレート、ジイソブチルフタレート、ジヘプチルフタレート、ジフェニルフタレート、ジイソデシルフタレート、ジトリデシルフタレート、ジウンデシルフタレート、ジベンジルフタレート、ブチルベンジルフタレート、ジノニルフタレート、ジシクロヘキシルフタレート等のフタル酸誘導体;
 ジメチルイソフタレート、ジ-(2-エチルヘキシル)イソフタレート、ジイソオクチルイソフタレート等のイソフタル酸誘導体;
 ジ-(2-エチルヘキシル)テトラヒドロフタレート、ジ-n-オクチルテトラヒドロフタレート、ジイソデシルテトラヒドロフタレート等のテトラヒドロフタル酸誘導体;
 ジ-n-ブチルアジペート、ジ(2-エチルヘキシル)アジペート、ジイソデシルアジペート、ジイソノニルアジペート等のアジピン酸誘導体;
 ジ-(2-エチルヘキシル)アゼレート、ジイソオクチルアゼレート、ジ-n-ヘキシルアゼレート等のアゼライン酸誘導体;
 ジ-n-ブチルセバケート、ジ-(2-エチルヘキシル)セバケート、ジイソデシルセバケート、ジ-(2-ブチルオクチル)セバケート等のセバシン酸誘導体;
 ジ-n-ブチルマレエート、ジメチルマレエート、ジエチルマレエート、ジ-(2-エチルヘキシル)マレエート等のマレイン酸誘導体;
 ジ-n-ブチルフマレート、ジ-(2-エチルヘキシル)フマレート等のフマル酸誘導体;
 トリエチルシトレート、トリ-n-ブチルシトレート、アセチルトリエチルシトレート、アセチルトリ-(2-エチルヘキシル)シトレート等のクエン酸誘導体;
 モノメチルイタコネート、モノブチルイタコネート、ジメチルイタコネート、ジエチルイタコネート、ジブチルイタコネート、ジ-(2-エチルヘキシル)イタコネート等のイタコン酸誘導体;
 ブチルオレエート、グリセリルモノオレエート、ジエチレングリコールモノオレエート等のオレイン酸誘導体;
 メチルアセチルリシノレート、ブチルアセチルリシノレート、グリセリルモノリシノレート、ジエチレングリコールモノリシノレート等のリシノール酸誘導体;
 n-ブチルステアレート、ジエチレングリコールジステアレート等のステアリン酸誘導体;
 ジエチレングリコールモノラウレート、ジエチレングリコールジペラルゴネート、ペンタエリスリトール脂肪酸エステル等のその他の脂肪酸誘導体;
 トリエチルホスフェート、トリブチルホスフェート、トリ-(2-エチルヘキシル)ホスフェート、トリブトキシエチルホスフェート、トリフェニルホスフェート、クレジルジフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、トリス(クロロエチル)ホスフェート等のリン酸誘導体;
 ジエチレングリコールジベンゾエート、ジプロピレングリコールジベンゾエート、トリエチレングリコールジベンゾエート、トリエチレングリコールジ-(2-エチルブチレート)、トリエチレングリコールジ-(2-エチルヘキソエート)、ジブチルメチレンビスチオグリコレート等のグリコール誘導体;
 グリセロールモノアセテート、グリセロールトリアセテート、グリセロールトリブチレート等のグリセリン誘導体;
 エポキシヘキサヒドロフタル酸ジイソデシル、エポキシトリグリセライド、エポキシ化オレイン酸オクチル、エポキシ化オレイン酸デシル等のエポキシ誘導体;
 アジピン酸系ポリエステル、セバシン酸系ポリエステル、フタル酸系ポリエステル等のポリエステル系可塑剤
等が挙げられる。
As so-called 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 phthalate, dibutyl phthalate, di- (2-ethylhexyl) phthalate, di-n-octyl phthalate, diisobutyl phthalate, diheptyl phthalate, diphenyl phthalate, diisodecyl phthalate, ditridecyl phthalate, diundecyl phthalate, dibenzyl phthalate, Phthalic acid derivatives such as butylbenzyl phthalate, dinonyl phthalate, dicyclohexyl phthalate;
Isophthalic acid derivatives such as dimethyl isophthalate, di- (2-ethylhexyl) isophthalate, diisooctyl isophthalate;
Tetrahydrophthalic acid derivatives such as di- (2-ethylhexyl) tetrahydrophthalate, di-n-octyltetrahydrophthalate, diisodecyltetrahydrophthalate;
Adipic acid derivatives such as di-n-butyl adipate, di (2-ethylhexyl) adipate, diisodecyl adipate, diisononyl adipate;
Azelaic acid derivatives such as di- (2-ethylhexyl) azelate, diisooctylazelate, di-n-hexylazelate;
Sebacic acid derivatives such as di-n-butyl sebacate, di- (2-ethylhexyl) sebacate, diisodecyl sebacate, di- (2-butyloctyl) sebacate;
Maleic acid derivatives such as di-n-butyl maleate, dimethyl maleate, diethyl maleate, di- (2-ethylhexyl) maleate;
Fumaric acid derivatives such as di-n-butyl fumarate and di- (2-ethylhexyl) fumarate;
Citric acid derivatives such as triethyl citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tri- (2-ethylhexyl) citrate;
Itaconic acid derivatives such as monomethyl itaconate, monobutyl itaconate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, di- (2-ethylhexyl) itaconate;
Oleic acid derivatives such as butyl oleate, glyceryl monooleate, diethylene glycol monooleate;
Ricinoleic acid derivatives such as methylacetylricinoleate, butylacetylricinoleate, glycerylmonoricinoleate, diethylene glycol monoricinoleate;
stearic acid derivatives such as n-butyl stearate and diethylene glycol distearate;
Other fatty acid derivatives such as diethylene glycol monolaurate, diethylene glycol dipelargonate, pentaerythritol fatty acid ester;
Phosphoric acid derivatives such as triethyl phosphate, tributyl phosphate, tri- (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (chloroethyl) phosphate;
Diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, triethylene glycol di- (2-ethylbutyrate), triethylene glycol di- (2-ethylhexoate), dibutylmethylene bisthioglycolate, etc. 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.
 また、いわゆる二次可塑剤としては、エポキシ化大豆油、エポキシ化亜麻仁油等のエポキシ化植物油;塩素化パラフィン、トリエチレングリコールジカプリレート等のグリコールの脂肪酸エステル、ブチルエポキシステアレート、フェニルオレエート、ジヒドロアビエチン酸メチル等が挙げられる。 In addition, so-called 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.
 そして、上記トリメリット酸エステル可塑剤以外の可塑剤の中でも、エポキシ化植物油が好ましい。
 なお、本発明の塩化ビニル樹脂組成物では、1種又は2種以上の、上記トリメリット酸エステル可塑剤以外の可塑剤を使用しうる。また、二次可塑剤を用いる場合、当該二次可塑剤と等質量以上の一次可塑剤を併用することが好ましい。
Among the plasticizers other than the trimellitic acid ester plasticizer, epoxidized vegetable oil is preferable.
In the vinyl chloride resin composition of the present invention, one or more plasticizers other than the trimellitic acid ester plasticizer can be used. Moreover, when using a secondary plasticizer, it is preferable to use together the said secondary plasticizer and the primary plasticizer of equal mass or more.
 そして、上記(b)可塑剤の合計含有量は、上記(a)塩化ビニル樹脂100質量部に対して、好ましくは30質量部以上190質量部以下であり、より好ましくは60質量部以上170質量部以下であり、更に好ましくは90質量部以上160質量部以下である。上記(b)可塑剤の含有量が上記範囲であると、塩化ビニル樹脂組成物を粉体成形してなる塩化ビニル樹脂成形体に、発泡ポリウレタン成形体への高い接着性を付与できる。 The total content of the (b) plasticizer is preferably 30 parts by weight or more and 190 parts by weight or less, and more preferably 60 parts by weight or more and 170 parts by weight, with respect to 100 parts by weight of the (a) vinyl chloride resin. Part or less, more preferably 90 parts by mass or more and 160 parts by mass or less. When the content of the plasticizer (b) is in the above range, high adhesion to the foamed polyurethane molded product can be imparted to the vinyl chloride resin molded product obtained by powder molding the vinyl chloride resin composition.
<(c)分子量が900以上4000以下のポリオール系化合物>
 本発明の塩化ビニル樹脂組成物が含有する(c)分子量が900以上4000以下のポリオール系化合物は、分子量が900以上4000以下であれば特定のポリオール系化合物に限定されない。そして本発明においてポリオール系化合物としては、例えば、アルキレングリコール系ポリエステルポリオール、ポリカプロラクトン系ポリエステルポリオール等のポリエステルポリオール;ポリエーテルポリオ―ルが挙げられる。
<(C) Polyol compound having a molecular weight of 900 to 4000>
The (c) polyol compound having a molecular weight of 900 or more and 4000 or less contained in the vinyl chloride resin composition of the present invention is not limited to a specific polyol compound if the molecular weight is 900 or more and 4000 or less. In the present invention, examples of the polyol compound include polyester polyols such as alkylene glycol polyester polyols and polycaprolactone polyester polyols; and polyether polyols.
[ポリエステルポリオール]
 アルキレングリコール系ポリエステルポリオールとしては、アルキレングリコールと脂肪族二塩基酸との縮合体が挙げられる。そしてアルキレングリコール系ポリエステルポリオールは、例えば、アルキレングリコールと脂肪族二塩基としてのアジピン酸との縮合体であるポリエステルポリオールであり、エチレンアジペートエステルポリオール、ブチレンアジペートエステルポリオール、ヘキシレンアジペートエステルポリオール、エチレンプロピレンアジペートエステルポリオール、エチレンブチレンアジペートエステルポリオール、及びエチレンネオペンチレンアジペートエステルポリオール等が挙げられる。
[Polyester polyol]
Examples of the alkylene glycol polyester polyol include condensates of alkylene glycol and aliphatic dibasic acid. The alkylene glycol-based polyester polyol is, for example, a polyester polyol that is a condensate of alkylene glycol and adipic acid as an aliphatic dibase, such as ethylene adipate ester polyol, butylene adipate ester polyol, hexylene adipate ester polyol, ethylene propylene. Examples include adipate ester polyol, ethylene butylene adipate ester polyol, and ethylene neopentylene adipate ester polyol.
 ポリカプロラクトン系ポリエステルポリオールとしては、カプロラクトンを開環重合して得られるポリカプロラクトンをポリオールに結合して得られるポリエステルポリオールが挙げられる。そしてポリカプロラクトン系ポリエステルポリオールの具体例として、以下の式(1)、式(2)で示される化合物が挙げられる。 Examples of the polycaprolactone-based polyester polyol include polyester polyols obtained by bonding polycaprolactone obtained by ring-opening polymerization of caprolactone to the polyol. Specific examples of the polycaprolactone-based polyester polyol include compounds represented by the following formulas (1) and (2).
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
 式(1)及び(2)中、a、b、cは、それぞれ独立して、好ましくは3以上8以下の整数であり、より好ましくは4以上7以下の整数であり、更に好ましくは5以上6以下の整数であり、特に好ましくは5である。l、m、nはそれぞれ独立して同一の又は異なる整数である。そして、l、m、nの各々の範囲は、式(1)、式(2)で示されるポリカプロラクトン系ポリエステルポリオールの分子量が900以上4000以下となる範囲であれば特に限定されない。なおl、m、nの各々の範囲は、好ましくは、当該分子量が900以上3000以下となる範囲であり、より好ましくは当該分子量が900以上2000以下となる範囲である。例えばl、m、nは、それぞれ独立して1以上80以下の整数である。Rはトリオール又はジオール由来の構造であり、特定の構造に限定されない。例えばRは、C、O、H、及びNからなる群から選択される2種以上の原子で構成される有機基である。
 なお、式(1)及び(2)で示されるポリカプロラクトン系ポリエステルポリオールは市販されている。式(1)のポリカプロラクトン系ポリエステルポリオール(ポリエステルトリオール)の市販品としては、プラクセル(登録商標)312、プラクセル320(何れも(株)ダイセル製)が挙げられ、式(2)のポリカプロラクトン系ポリエステルポリオール(ポリエステルジオール)の市販品としては、プラクセル210((株)ダイセル製)が挙げられる。
In the formulas (1) and (2), a, b, and c are each independently preferably an integer of 3 or more and 8 or less, more preferably an integer of 4 or more and 7 or less, and still more preferably 5 or more. It is an integer of 6 or less, particularly preferably 5. l, m, and n are each independently the same or different integers. The ranges of l, m, and n are not particularly limited as long as the molecular weight of the polycaprolactone-based polyester polyol represented by the formulas (1) and (2) is in the range of 900 to 4000. Each range of l, m, and n is preferably a range in which the molecular weight is 900 or more and 3000 or less, and more preferably a range in which the molecular weight is 900 or more and 2000 or less. For example, l, m, and n are each independently an integer of 1 to 80. R is a structure derived from triol or diol, and is not limited to a specific structure. For example, R is an organic group composed of two or more atoms selected from the group consisting of C, O, H, and N.
In addition, the polycaprolactone type | system | group polyester polyol shown by Formula (1) and (2) is marketed. Examples of commercially available products of the polycaprolactone-based polyester polyol (polyester triol) of the formula (1) include Plaxel (registered trademark) 312 and Plaxel 320 (both manufactured by Daicel Corporation), and the polycaprolactone type of the formula (2) As a commercially available product of polyester polyol (polyester diol), Plaxel 210 (manufactured by Daicel Corporation) can be mentioned.
[ポリエーテルポリオール]
 ポリエーテルポリオールとしては、ポリ(オキシテトラメチレン)グリコール、ポリ(オキシプロピレン)グリコール等が挙げられる。
[Polyether polyol]
Examples of the polyether polyol include poly (oxytetramethylene) glycol and poly (oxypropylene) glycol.
 これらのポリオール系化合物は、1種単独で使用してもよく2種以上を併用してもよい。そして、これらの中でも、ポリオール系化合物としては、ポリエステルポリオールが好ましく、ポリカプロラクトン系ポリエステルポリオールがより好ましい。 These polyol compounds may be used alone or in combination of two or more. Among these, as the polyol-based compound, a polyester polyol is preferable, and a polycaprolactone-based polyester polyol is more preferable.
 ここで、上記(c)ポリオール系化合物の分子量は900以上4000以下であり、好ましくは900以上3000以下であり、より好ましくは900以上2000以下である。上記(c)ポリオール系化合物の分子量が上記範囲であると、塩化ビニル樹脂組成物を粉体成形してなる塩化ビニル樹脂成形体に、発泡ポリウレタン成形体への高い接着性を付与できる。 Here, the molecular weight of the (c) polyol compound is 900 or more and 4000 or less, preferably 900 or more and 3000 or less, and more preferably 900 or more and 2000 or less. When the molecular weight of the (c) polyol compound is in the above range, high adhesion to the foamed polyurethane molded product can be imparted to the vinyl chloride resin molded product obtained by powder molding the vinyl chloride resin composition.
 また上記(c)分子量が900以上4000以下のポリオール系化合物の含有量は、上記(a)塩化ビニル樹脂100質量部に対して好ましくは0.1質量部以上30質量部以下であり、より好ましくは0.1質量部以上20質量部以下であり、更に好ましくは0.2質量部以上10質量部以下である。上記(c)分子量が900以上4000以下のポリオール系化合物の含有量が上記範囲であると、塩化ビニル樹脂組成物を粉体成形してなる塩化ビニル樹脂成形体に、発泡ポリウレタン成形体への高い接着性を付与できる。 The content of the polyol compound (c) having a molecular weight of 900 or more and 4000 or less is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 100 parts by mass of the vinyl chloride resin (a). Is 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass. When the content of the polyol compound (c) having a molecular weight of 900 or more and 4000 or less is within the above range, a vinyl chloride resin molded product obtained by powder molding a vinyl chloride resin composition is highly suitable for a foamed polyurethane molded product. Adhesiveness can be imparted.
<添加剤>
[過塩素酸処理ハイドロタルサイト]
 本発明の塩化ビニル樹脂組成物は、過塩素酸処理ハイドロタルサイトを含有していてもよい。過塩素酸処理ハイドロタルサイトは、例えば、ハイドロタルサイトを過塩素酸の希薄水溶液中に加えて撹拌し、その後必要に応じて、ろ過、脱水または乾燥することによって、ハイドロタルサイト中の炭酸アニオン(CO 2-)の少なくとも一部を過塩素酸アニオン(ClO )で置換して(炭酸アニオン1モルにつき過塩素酸アニオン2モルが置換する)、容易に製造することができる。上記ハイドロタルサイトと上記過塩素酸とのモル比は任意に設定できるが、一般には、ハイドロタルサイト1モルに対し、過塩素酸0.1~2モルとする。
<Additives>
[Perchloric acid-treated hydrotalcite]
The vinyl chloride 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.
 未処理(未置換)のハイドロタルサイト中の炭酸アニオンの過塩素酸アニオンへの置換率は、好ましくは50モル%以上、より好ましくは70モル%以上、更に好ましくは85モル%以上である。また、未処理(未置換)のハイドロタルサイト中の炭酸アニオンの過塩素酸アニオンへの置換率は、好ましくは95モル%以下である。未処理(未置換)のハイドロタルサイト中の炭酸アニオンの過塩素酸アニオンへの置換率が上記の範囲内にあることにより、塩化ビニル樹脂組成物を粉体成形してなる塩化ビニル樹脂成形体に、良好な低温での柔軟性を付与できる。 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. A vinyl chloride resin molded article obtained by powder molding a vinyl chloride resin composition when the substitution rate of the carbonate anion in the untreated (unsubstituted) hydrotalcite is within the above range. In addition, good flexibility at low temperatures can be imparted.
 ハイドロタルサイトは、一般式:[Mg1-xAl(OH)]x+[(CO)x/2・mHO]x-で表される不定比化合物で、プラスに荷電した基本層[Mg1-xAl(OH)]x+と、マイナスに荷電した中間層[(CO)x/2・mHO]x-とからなる層状の結晶構造を有する無機物質である。ここで、上記一般式中、xは0より大きく0.33以下の範囲の数である。天然のハイドロタルサイトは、MgAl(OH)16CO・4HOである。合成されたハイドロタルサイトとしては、Mg4.5Al(OH)13CO・3.5HOが市販されている。合成ハイドロタルサイトの合成方法は、例えば特公昭61-174270号公報に記載されている。 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- It is an inorganic substance having a layered crystal structure composed of a layer [Mg 1-x Al x (OH) 2 ] x + and a negatively charged intermediate layer [(CO 3 ) x / 2 · mH 2 O] x− . Here, in the above general formula, 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.
 過塩素酸処理ハイドロタルサイトの、上記(a)塩化ビニル樹脂100質量部に対する好ましい含有量は0.5質量部以上7質量部以下であり、より好ましい含有量は1質量部以上6質量部以下であり、更に好ましい含有量は1.5質量部以上5.5質量部以下である。過塩素酸処理ハイドロタルサイトの含有量が上記範囲であると、塩化ビニル樹脂組成物を粉体成形してなる塩化ビニル樹脂成形体に、良好な低温での柔軟性を付与できる。 The content of perchloric acid-treated hydrotalcite is preferably 0.5 parts by mass or more and 7 parts by mass or less, and more preferably 1 part by mass or more and 6 parts by mass or less with respect to 100 parts by mass of the vinyl chloride resin (a). The more preferable content is 1.5 parts by mass or more and 5.5 parts by mass or less. When the content of the perchloric acid-treated hydrotalcite is within the above range, good flexibility at a low temperature can be imparted to a vinyl chloride resin molded article obtained by powder molding a vinyl chloride resin composition.
[ゼオライト]
 本発明の塩化ビニル樹脂組成物は、ゼオライトを安定剤として含有し得る。ゼオライトは、一般式:Mx/n・[(AlO・(SiO]・zHO(一般式中、Mは原子価nの金属イオン、x+yは単位格子当たりの四面体数、zは水のモル数である)で表される化合物である。当該一般式中のMの種類としてはNa、Li、Ca、Mg、Znなどの一価又は二価の金属及びこれらの混合型が挙げられる。
[Zeolite]
The vinyl chloride 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). Examples of M in the general formula include monovalent or divalent metals such as Na, Li, Ca, Mg, and Zn, and mixed types thereof.
 ゼオライトの含有量は特定の範囲に限定されない。ゼオライトの好ましい含有量は、(a)塩化ビニル樹脂100質量部に対して0.1質量部以上5質量部以下である。 Zeolite content is not limited to a specific range. A preferable content of zeolite is 0.1 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of (a) vinyl chloride resin.
[脂肪酸金属塩]
 本発明の塩化ビニル樹脂組成物は、脂肪酸金属塩を含有していてもよい。好ましい脂肪酸金属塩は、一価脂肪酸金属塩であり、より好ましい脂肪酸金属塩は、炭素数12~24の一価脂肪酸金属塩であり、更に好ましい脂肪酸金属塩は、炭素数15~21の一価脂肪酸金属塩である。脂肪酸金属塩の具体例は、ステアリン酸リチウム、ステアリン酸マグネシウム、ステアリン酸アルミニウム、ステアリン酸カルシウム、ステアリン酸ストロンチウム、ステアリン酸バリウム、ステアリン酸亜鉛、ラウリン酸カルシウム、ラウリン酸バリウム、ラウリン酸亜鉛、2-エチルヘキサン酸バリウム、2-エチルヘキサン酸亜鉛、リシノール酸バリウム、リシノール酸亜鉛等である。脂肪酸金属塩を構成する金属としては、多価陽イオンを生成しうる金属が好ましく、2価陽イオンを生成しうる金属がより好ましく、周期表第3周期~第6周期の、2価陽イオンを生成しうる金属が更に好ましく、周期表第4周期の、2価陽イオンを生成しうる金属が特に好ましい。最も好ましい脂肪酸金属塩はステアリン酸亜鉛である。
[Fatty acid metal salt]
The vinyl chloride resin composition of the present invention may contain a fatty acid metal salt. A preferred fatty acid metal salt is a monovalent fatty acid metal salt, a more preferred fatty acid metal salt is a monovalent fatty acid metal salt having 12 to 24 carbon atoms, and a more preferred fatty acid metal salt is a monovalent fatty acid metal salt having 15 to 21 carbon atoms. It is a 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. Barium acid, zinc 2-ethylhexanoate, barium ricinoleate, zinc ricinoleate and the like. 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.
 上記脂肪酸金属塩の、上記(a)塩化ビニル樹脂100質量部に対する好ましい含有量は0.05質量部以上5質量部以下であり、より好ましくは0.1質量部以上1質量部以下であり、更に好ましくは0.1質量部以上0.5質量部以下である。脂肪酸金属塩の含有量が上記範囲であると、塩化ビニル樹脂組成物の加熱成形後の色差の値を小さくできる。 The preferred content of the fatty acid metal salt with respect to 100 parts by mass of the (a) vinyl chloride resin is 0.05 parts by mass or more and 5 parts by mass or less, more preferably 0.1 parts by mass or more and 1 part by mass or less. More preferably, they are 0.1 mass part or more and 0.5 mass part or less. When the content of the fatty acid metal salt is within the above range, the value of the color difference after the thermoforming of the vinyl chloride resin composition can be reduced.
[その他のダスティング剤]
 本発明の塩化ビニル樹脂組成物は、上記(a2)塩化ビニル樹脂微粒子以外のダスティング剤(以下、「その他のダスティング剤」ということがある。)を含有し得る。その他のダスティング剤としては、炭酸カルシウム、タルク、酸化アルミニウム等の無機微粒子;ポリアクリロニトリル樹脂微粒子、ポリ(メタ)アクリレート樹脂微粒子、ポリスチレン樹脂微粒子、ポリエチレン樹脂微粒子、ポリプロピレン樹脂微粒子、ポリエステル樹脂微粒子、ポリアミド樹脂微粒子等の有機微粒子が挙げられる。中でも、平均粒子径が10nm以上100nm以下の無機微粒子が好ましい。
[Other dusting agents]
The vinyl chloride resin composition of the present invention may contain a dusting agent other than the above (a2) 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. Among these, inorganic fine particles having an average particle size of 10 nm to 100 nm are preferable.
 その他のダスティング剤の含有量は特定の範囲に限定されない。その他のダスティング剤の含有量は、(a)塩化ビニル樹脂100質量部に対して、好ましくは20質量部以下であり、更に好ましくは10質量部以下である。 The content of other dusting agents is not limited to a specific range. The content of the other dusting agent 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 (a) vinyl chloride resin.
[その他の添加剤]
 本発明の塩化ビニル樹脂組成物は、着色剤、耐衝撃性改良剤、過塩素酸処理ハイドロタルサイト以外の過塩素酸化合物(過塩素酸ナトリウム、過塩素酸カリウム等)、酸化防止剤、防カビ剤、難燃剤、帯電防止剤、充填剤、紫外線吸収剤、光安定剤、発泡剤、β-ジケトン類、滑剤等の、その他の添加剤を含有し得る。
[Other additives]
The vinyl chloride resin composition of the present invention comprises a colorant, impact modifier, perchloric acid compound other than perchloric acid-treated hydrotalcite (sodium perchlorate, potassium perchlorate, etc.), antioxidant, Other additives such as fungicides, flame retardants, antistatic agents, fillers, UV absorbers, light stabilizers, foaming agents, β-diketones, lubricants and the like may be contained.
 着色剤の具体例は、キナクリドン系顔料、ペリレン系顔料、ポリアゾ縮合顔料、イソインドリノン系顔料、銅フタロシアニン系顔料、チタンホワイト、カーボンブラックである。本発明の塩化ビニル樹脂組成物では、1種又は2種以上の顔料が使用される。キナクリドン系顔料は、p-フェニレンジアントラニル酸類が濃硫酸で処理されて得られ、黄みの赤から赤みの紫の色相を示す。キナクリドン系顔料の具体例は、キナクリドンレッド、キナクリドンマゼンタ、キナクリドンバイオレットである。
 ペリレン系顔料は、ペリレン-3,4,9,10-テトラカルボン酸無水物と芳香族第一級アミンの縮合反応により得られ、赤から赤紫、茶色の色相を示す。ペリレン系顔料の具体例は、ペリレンレッド、ペリレンオレンジ、ペリレンマルーン、ペリレンバーミリオン、ペリレンボルドーである。
 ポリアゾ縮合顔料は、アゾ色素が溶剤中で縮合されて高分子量化されて得られ、黄、赤系顔料の色相を示す。ポリアゾ縮合顔料の具体例は、ポリアゾレッド、ポリアゾイエロー、クロモフタルオレンジ、クロモフタルレッド、クロモフタルスカーレットである。
 イソインドリノン系顔料は、4,5,6,7-テトラクロロイソインドリノンと芳香族第一級ジアミンの縮合反応により得られ、緑みの黄色から、赤、褐色の色相を示す。イソインドリノン系顔料の具体例は、イソインドリノンイエローである。
 銅フタロシアニン系顔料は、フタロシアニン類に銅を配位した顔料で、黄みの緑から鮮やかな青の色相を示す。銅フタロシアニン系顔料の具体例は、フタロシアニングリーン、フタロシアニンブルーである。
 チタンホワイトは、二酸化チタンからなる白色顔料で、隠蔽力が大きく、アナタース型とルチル型がある。
 カーボンブラックは、炭素を主成分とし、酸素、水素、窒素を含む黒色顔料である。カーボンブラックの具体例は、サーマルブラック、アセチレンブラック、チャンネルブラック、ファーネスブラック、ランプブラック、ボーンブラックである。
Specific examples of the colorant are quinacridone pigments, perylene pigments, polyazo condensation pigments, isoindolinone pigments, copper phthalocyanine pigments, titanium white, and carbon black. In the vinyl chloride 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.
 耐衝撃性改良剤の具体例は、アクリロニトリル-ブタジエン-スチレン共重合体、メタクリル酸メチル-ブタジエン-スチレン共重合体、塩素化ポリエチレン、エチレン-酢酸ビニル共重合体、クロロスルホン化ポリエチレン等である。本発明の塩化ビニル樹脂組成物では、1種又は2種以上の耐衝撃性改良剤を使用できる。なお、耐衝撃性改良剤は、塩化ビニル樹脂組成物中で微細な弾性粒子の不均一相となって分散する。当該弾性粒子にグラフト重合した鎖及び極性基が(a1)塩化ビニル樹脂粒子と相溶し、塩化ビニル樹脂組成物を粉体成形してなる塩化ビニル樹脂成形体の耐衝撃性が向上する。 Specific examples of the impact resistance improver include acrylonitrile-butadiene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, chlorinated polyethylene, ethylene-vinyl acetate copolymer, chlorosulfonated polyethylene and the like. In the vinyl chloride resin composition of the present invention, one or more impact resistance improvers can be used. The impact resistance improver is dispersed as a heterogeneous phase of fine elastic particles in the vinyl chloride resin composition. The chain and the polar group graft-polymerized on the elastic particles are compatible with the (a1) vinyl chloride resin particles, and the impact resistance of the vinyl chloride resin molded product obtained by powder molding the vinyl chloride resin composition is improved.
 酸化防止剤の具体例は、フェノール系酸化防止剤、硫黄系酸化防止剤、リン系酸化防止剤等である。
 防カビ剤の具体例は、脂肪族エステル系防カビ剤、炭化水素系防カビ剤、有機窒素系防カビ剤、有機窒素硫黄系防カビ剤等である。
Specific examples of the antioxidant include a phenol-based antioxidant, a sulfur-based antioxidant, and a phosphorus-based antioxidant.
Specific examples of the fungicide include aliphatic ester fungicides, hydrocarbon fungicides, organic nitrogen fungicides, organic nitrogen sulfur fungicides and the like.
 難燃剤の具体例は、塩素化パラフィン等のハロゲン系難燃剤;リン酸エステル等のリン系難燃剤;水酸化マグネシウム、水酸化アルミニウム等の無機水酸化物;等である。 Specific examples of 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;
 帯電防止剤の具体例は、脂肪酸塩類、高級アルコール硫酸エステル類、スルホン酸塩類等のアニオン系帯電防止剤;脂肪族アミン塩類、第四級アンモニウム塩類のカチオン系帯電防止剤;ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアルキルフェノールエーテル類等のノニオン系帯電防止剤等である。 Specific examples of the antistatic agent 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.
 充填剤の具体例は、シリカ、タルク、マイカ、炭酸カルシウム、クレー等である。 Specific examples of the filler are silica, talc, mica, calcium carbonate, clay and the like.
 光安定剤の具体例は、ベンゾトリアゾール系、ベンゾフェノン系、ニッケルキレート系等の紫外線吸収剤、ヒンダートアミン系光安定剤等である。 Specific examples of light stabilizers include benzotriazole-based, benzophenone-based, nickel chelate-based ultraviolet absorbers, hindered amine-based light stabilizers, and the like.
 発泡剤の具体例は、アゾジカルボンアミド、アゾビスイソブチロニトリル等のアゾ化合物、N,N′-ジニトロソペンタメチレンテトラミン等のニトロソ化合物、p-トルエンスルホニルヒドラジド、p,p-オキシビス(ベンゼンスルホニルヒドラジド)等のスルホニルヒドラジド化合物等の有機発泡剤;フロンガス、炭酸ガス、水、ペンタン等の揮発性炭化水素化合物;これらを内包したマイクロカプセル等のガス系の発泡剤等である。 Specific examples of the blowing agent 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.
 β-ジケトン類は、本発明の塩化ビニル樹脂組成物を粉体成形して得られる塩化ビニル樹脂成形体の初期色調の変動をより効果的に抑えるために用いられる。β-ジケトン類の具体例は、ジベンゾイルメタン、ステアロイルベンゾイルメタン、パルミトイルベンゾイルメタン等である。これらのβ-ジケトン類は1種を単独で用いてもよいし、2種以上を組み合わせて用いてもよい。
 なお、β-ジケトン類の含有量は特定の範囲に限定されない。β-ジケトン類の好ましい含有量は、(a)塩化ビニル樹脂100質量部に対して0.1質量部以上5質量部以下である。
β-diketones are used to more effectively suppress fluctuations in the initial color tone of a vinyl chloride resin molded article obtained by powder molding the vinyl chloride resin composition of the present invention. Specific examples of β-diketones are dibenzoylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, and the like. One of these β-diketones may be used alone, or two or more thereof may be used in combination.
The content of β-diketones is not limited to a specific range. The preferred content of β-diketones is 0.1 to 5 parts by mass with respect to 100 parts by mass of (a) vinyl chloride resin.
 滑剤の具体例は、12-ヒドロキシステアリン酸オリゴマーなどである。 A specific example of the lubricant is 12-hydroxystearic acid oligomer.
(塩化ビニル樹脂組成物の製造方法)
 本発明の塩化ビニル樹脂組成物は、上述した成分を混合して製造することができる。即ち、本発明の塩化ビニル樹脂組成物の製造方法は、少なくとも、上記(a)塩化ビニル樹脂、(b)可塑剤、及び(c)分子量が900以上4000以下のポリオール系化合物(ポリエステルポリオールおよび/またはポリエーテルポリオール)を混合することを含む。そして、本発明の塩化ビニル樹脂組成物の製造方法では、上記成分に加え任意に添加剤が混合されてもよい。
 ここで、上記(a)塩化ビニル樹脂、上記(b)可塑剤、上記(c)分子量が900以上4000以下のポリオール系化合物、及び必要に応じて添加される添加剤の混合方法は限定されない。好ましい混合方法は、可塑剤及びダスティング剤(上記(a2)塩化ビニル樹脂微粒子と、必要に応じて添加されるその他のダスティング剤とを含む)を除く成分をドライブレンドにより混合し、その後、可塑剤、ダスティング剤を順次、混合する方法である。ドライブレンドには、ヘンシェルミキサーの使用が好ましい。また、ドライブレンド時の温度は、好ましくは50℃以上100℃以下、より好ましくは70℃以上80℃以下である。
(Method for producing vinyl chloride resin composition)
The vinyl chloride resin composition of the present invention can be produced by mixing the components described above. That is, the method for producing a vinyl chloride resin composition of the present invention comprises at least (a) a vinyl chloride resin, (b) a plasticizer, and (c) a polyol compound having a molecular weight of 900 or more and 4000 or less (polyester polyol and / or Or mixing a polyether polyol). And in the manufacturing method of the vinyl chloride resin composition of this invention, in addition to the said component, an additive may be mixed arbitrarily.
Here, the mixing method of the (a) vinyl chloride resin, the (b) plasticizer, the (c) polyol compound having a molecular weight of 900 or more and 4000 or less, and an additive added as necessary is not limited. A preferred mixing method is to dry dry blend the components except for the plasticizer and the dusting agent (including the above (a2) 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.
(塩化ビニル樹脂成形体)
 本発明の塩化ビニル樹脂成形体は、上述した本発明の塩化ビニル樹脂組成物を粉体成形、好ましくはパウダースラッシュ成形して得る。
 そして、本発明の塩化ビニル樹脂成形体は、自動車内装材、例えばインスツルメントパネル、ドアトリム等の表皮として好適に用いられる。
(Vinyl chloride resin molding)
The vinyl chloride resin molded article of the present invention is obtained by powder molding, preferably powder slush molding, of the above-described vinyl chloride resin composition of the present invention.
The vinyl chloride resin molded article of the present invention is suitably used as an automobile interior material, for example, as a skin for instrument panels, door trims, and the like.
(塩化ビニル樹脂成形体の製造方法)
 本発明の塩化ビニル樹脂成形体は、上述した塩化ビニル樹脂組成物を用いて製造することができる。即ち、本発明の塩化ビニル樹脂成形体の製造方法は、少なくとも、上述したいずれかの塩化ビニル樹脂組成物、または、上述した製造方法に従って製造した塩化ビニル樹脂組成物を粉体成形、好ましくはパウダースラッシュ成形することを特徴とする。
(Method for producing vinyl chloride resin molding)
The vinyl chloride resin molded article of the present invention can be produced using the above-described vinyl chloride resin composition. That is, the method for producing a vinyl chloride resin molded article of the present invention is at least one of the above-described vinyl chloride resin compositions or a vinyl chloride resin composition produced according to the above-described production method. It is characterized by slush molding.
 ここで、パウダースラッシュ成形時の金型温度は、好ましくは200℃以上300℃以下、より好ましくは220℃以上280℃以下である。 Here, 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.
 本発明の塩化ビニル樹脂成形体を製造する際には、上記温度範囲の金型に本発明の塩化ビニル樹脂組成物を振りかけて5秒以上30秒以下の間放置し、その後、余剰の塩化ビニル樹脂組成物を振り落とし、さらに30秒以上3分以下の間放置した後、金型を10℃以上60℃以下に冷却し、得られた本発明の塩化ビニル樹脂成形体を金型から脱型する。 In producing the vinyl chloride resin molded article of the present invention, the vinyl chloride resin composition of the present invention is sprinkled on a mold in the above temperature range and left for 5 seconds to 30 seconds, and then excess vinyl chloride is used. 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 vinyl chloride resin molded article of the present invention is removed from the mold. To do.
(積層体)
 本発明の積層体は、本発明の塩化ビニル樹脂成形体と発泡ポリウレタン成形体とを積層して得ることができる。積層方法は、塩化ビニル樹脂成形体と、発泡ポリウレタン成形体とを別途製造した後に、熱融着あるいは熱接着又は公知の接着剤などを用いることにより貼り合わせる方法;塩化ビニル樹脂成形体上で、発泡ポリウレタン成形体の原料となるイソシアネート類とポリオール類などとを反応させて重合を行うと共に、公知の方法によりポリウレタンの発泡を行い、塩化ビニル樹脂成形体上に発泡ポリウレタン成形体を直接形成する方法等が挙げられる。後者の方が、工程が簡素であり、かつ、種々の形状の積層体を得る場合においても、塩化ビニル樹脂成形体と発泡ポリウレタン成形体との接着を確実に行うことができるのでより好適である。
(Laminate)
The laminate of the present invention can be obtained by laminating the vinyl chloride resin molded product of the present invention and the foamed polyurethane molded product. The lamination method is a method in which a vinyl chloride 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 vinyl chloride resin molded body, Polymerization by reacting isocyanates, which are raw materials for foamed polyurethane moldings, polyols, etc., and foaming polyurethane by a known method to directly form a foamed polyurethane molding on a vinyl chloride resin molding Etc. The latter is more preferable because the process is simple and the vinyl chloride resin molded body and the polyurethane foam molded body can be securely bonded even when obtaining laminates of various shapes. .
 そして、本発明の積層体は、自動車内装材、例えばインスツルメントパネル、ドアトリム等として好適に用いられる。 And the laminated body of this invention is used suitably as a vehicle interior material, for example, an instrument panel, a door trim, etc.
 以下、実施例により本発明が詳細に説明されるが、本発明はこれらの実施例に限定されない。なお、各種物性の測定方法、接着性の評価方法は次の通りである。 Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to these examples. In addition, the measuring method of various physical properties and the evaluation method of adhesiveness are as follows.
<(a1)塩化ビニル樹脂粒子及び(a2)塩化ビニル樹脂微粒子の平均粒子径>
 実施例及び比較例において、塩化ビニル樹脂組成物に用いられる(a1)塩化ビニル樹脂粒子及び(a2)塩化ビニル樹脂微粒子の平均粒子径(体積平均粒子径)は、塩化ビニル樹脂粒子及び塩化ビニル樹脂微粒子を、それぞれ水槽内に分散させ、以下に示す装置を用いて、光の回折・散乱強度分布を測定・解析し、粒子径及び体積基準の粒子径分布を測定することにより、算出した。
 ・装置:レーザー回折式粒度分布測定機(島津製作所製、型番「SALD-2300」)
 ・測定方式:レーザー回折及び散乱
 ・測定範囲:0.017μm~2500μm
 ・光源:半導体レーザー(波長680nm、出力3mW)
<Average particle diameter of (a1) vinyl chloride resin particles and (a2) vinyl chloride resin fine particles>
In Examples and Comparative Examples, the average particle diameter (volume average particle diameter) of (a1) vinyl chloride resin particles and (a2) vinyl chloride resin fine particles used in the vinyl chloride resin composition is as follows: 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 μm to 2500 μm
Light source: Semiconductor laser (wavelength 680 nm, output 3 mW)
<(a1)塩化ビニル樹脂粒子及び(a2)塩化ビニル樹脂微粒子の平均重合度>
 実施例及び比較例において、塩化ビニル樹脂組成物に用いられる(a1)塩化ビニル樹脂粒子及び(a2)塩化ビニル樹脂微粒子の平均重合度は、JIS K6720-2に準拠し、塩化ビニル樹脂粒子及び塩化ビニル樹脂微粒子のそれぞれを、シクロヘキサノンに溶解させて粘度を測定することにより、算出した。
<Average polymerization degree of (a1) vinyl chloride resin particles and (a2) vinyl chloride resin particles>
In Examples and Comparative Examples, the average degree of polymerization of (a1) vinyl chloride resin particles and (a2) vinyl chloride resin fine particles used in the vinyl chloride 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.
<塩化ビニル樹脂成形体のポリウレタン接着性>
 実施例および比較例で得られた積層体において、塩化ビニル樹脂成形シートからなる表皮を発泡ポリウレタン成形体から剥離した。その後、剥離表面(塩化ビニル樹脂成形シート裏面及び発泡ポリウレタン成形体表面)の状態を目視で観察し、塩化ビニル樹脂成形体(シート)のポリウレタン接着性を以下の3段階の基準で判定した。
A:凝集破壊が剥離表面の90%以上の面積で起きている。
B:凝集破壊が剥離表面の60%以上90%未満の面積で起きている。
C:凝集破壊が剥離表面の60%未満の面積で起きている。
 なお「凝集破壊」とは、発泡ポリウレタン成形体が塩化ビニル樹脂成形シートの剥離時に材料破壊され、発泡ポリウレタン成形体の一部が塩化ビニル樹脂成形シート側に残存する現象である。
<Polyurethane adhesion of vinyl chloride resin molding>
In the laminates obtained in Examples and Comparative Examples, the skin made of a vinyl chloride resin molded sheet was peeled from the foamed polyurethane molded product. Thereafter, the state of the release surface (the back surface of the vinyl chloride resin molded sheet and the surface of the foamed polyurethane molded body) was visually observed, and the polyurethane adhesiveness of the vinyl chloride resin molded body (sheet) was determined based on the following three levels.
A: Cohesive failure occurs in an area of 90% or more of the peeled surface.
B: Cohesive failure occurs in an area of 60% or more and less than 90% of the peeled surface
C: Cohesive failure occurs in an area of less than 60% of the peeled surface.
The “cohesive failure” is a phenomenon in which the foamed polyurethane molded product is destroyed when the vinyl chloride resin molded sheet is peeled off, and a part of the foamed polyurethane molded product remains on the vinyl chloride resin molded sheet side.
(実施例1~3及び比較例1~2)
 表1に示す配合成分のうち可塑剤(トリメリット酸エステル可塑剤、及びエポキシ化大豆油)とダスティング剤である塩化ビニル樹脂微粒子を除く成分をヘンシェルミキサーに入れて混合した。そして、混合物の温度が80℃に上昇した時点で上記可塑剤を添加し、ドライアップ(可塑剤が塩化ビニル樹脂粒子に吸収されて、上記混合物がさらさらになった状態をいう。)させた。その後、ドライアップさせた混合物が70℃以下に冷却された時点でダスティング剤である塩化ビニル樹脂微粒子を添加し、塩化ビニル樹脂組成物を製造した。
 次に、得られた塩化ビニル樹脂組成物を250℃に加熱したシボ付き金型に振りかけ、塩化ビニル樹脂成形シートの厚みが1mmになるよう調整した時間(具体的には12~14秒間)放置して溶融させた後、余剰の塩化ビニル樹脂組成物を振り落とした。その後、200℃に設定したオーブンに静置し、静置後60秒経過した時点で金型を冷却水により冷却し、金型温度が40℃まで冷却された時点で145mm×175mm×1mmの塩化ビニル樹脂成形シートを金型から脱型した。
 得られた塩化ビニル樹脂成形シートを100mm×100mmに切り取り、切り取られた塩化ビニル樹脂成形シート2枚を、200mm×300mm×10mmの金型中に重ならないように敷き、シボ付き面を下にして置いた。
 別途、プロピレングリコールのプロピレンオキサイド・エチレンオキサイド(PO・EO)ブロック付加物(水酸基価28、末端EO単位の含有量=10%、内部EO単位の含有量4%)50質量部、グリセリンのPO・EOブロック付加物(水酸基価21、末端EO単位の含有量=14%)50質量部、水2.5質量部、トリエチレンジアミンのエチレングリコ-ル溶液(東ソー(株)製、商品名:「TEDA-L33」)0.2質量部、トリエタノールアミン1.2質量部、トリエチルアミン0.5質量部及び整泡剤(信越化学工業(株)製、商品名:「F-122」)0.5質量部からなるポリオール混合物と、ポリメチレンポリフェニレンポリイソシアネート(ポリメリックMDI))とを、インデックスが98になる比率で混合して混合液を調製した。そして、調製した混合液を、上述の通り金型中に敷かれた塩化ビニル樹脂成形シート2枚の上にそれぞれ注いだ。その後、348mm×255mm×10mmのアルミ板で金型に蓋をすることで金型を密閉した。密閉してから5分後、1mm厚の塩化ビニル樹脂成形シートからなる表皮に発泡ポリウレタン成形体が裏打ちされた積層体を金型から取り出した直後、上記に示す方法で塩化ビニル樹脂成形体のポリウレタン接着性を測定した。結果を表1に示す。
(Examples 1 to 3 and Comparative Examples 1 to 2)
Among the blending components shown in Table 1, components other than plasticizers (trimellitic acid ester plasticizer and epoxidized soybean oil) and vinyl chloride resin fine particles as a dusting agent 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 lower, vinyl chloride resin fine particles as a dusting agent were added to produce a vinyl chloride resin composition.
Next, the obtained vinyl chloride resin composition is sprinkled on a mold with a texture heated to 250 ° C., and left for a time (specifically, 12 to 14 seconds) adjusted so that the thickness of the vinyl chloride resin molded sheet becomes 1 mm. Then, the excess vinyl chloride resin composition was shaken off. Then, it is left still in an oven set at 200 ° C., and when 60 seconds have passed after standing, the mold is cooled with cooling water, and when the mold temperature is cooled to 40 ° C., 145 mm × 175 mm × 1 mm The vinyl resin molded sheet was removed from the mold.
Cut the obtained vinyl chloride 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.
Separately, propylene oxide / propylene oxide / ethylene oxide (PO / EO) block adduct (hydroxyl value 28, content of terminal EO unit = 10%, content of internal EO unit 4%), 50 parts by mass of glycerin PO. EO block adduct (hydroxyl value 21, terminal EO unit content = 14%) 50 parts by mass, water 2.5 parts by mass, ethylene glycol solution of triethylenediamine (manufactured by Tosoh Corporation, trade name: “TEDA” -L33 ") 0.2 parts by mass, triethanolamine 1.2 parts by mass, triethylamine 0.5 parts by mass and foam stabilizer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name:" F-122 ") 0.5 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. And the prepared liquid mixture was each poured on 2 sheets of vinyl chloride resin molding sheets spread | laid in the metal mold | die as above-mentioned. Thereafter, the mold was sealed by covering the mold with an aluminum plate of 348 mm × 255 mm × 10 mm. 5 minutes after sealing, immediately after taking out the laminated body in which the foamed polyurethane molded product is lined on the skin made of a 1 mm-thick vinyl chloride resin molded sheet from the mold, the polyurethane of the vinyl chloride resin molded product by the method described above is used. Adhesion was measured. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
1)新第一塩ビ(株)製、ZEST 1000Z(懸濁重合で得られた塩化ビニル樹脂粒子、平均重合度1000、平均粒子径145μm)
2)花王(株)製、トリメックスN-08
3)(株)ADEKA製、アデカサイザーO-130S
4)協和化学工業(株)製、アルカマイザー5
5)水澤化学工業(株)製、MIZUKALIZER DS
6)昭和電工(株)製、カレンズ DK-1
7)堺化学工業(株)製、SAKAI SZ2000
8)(株)ADEKA製、アデカスタブ LS-12
9)(株)ダイセル製、プラクセル 210
10)(株)ダイセル製、プラクセル 312
11)(株)ダイセル製、プラクセル 320
12)(株)ダイセル製、プラクセル 308
13)新第一塩ビ(株)製、ZEST PQLTX(乳化重合で得られた塩化ビニル樹脂微粒子、平均重合度800、平均粒子径2μm)
14)大日精化工業(株)製、DA PX-1720ブラック(A)
1) ZEST 1000Z (Vinyl chloride resin particles obtained by suspension polymerization, average degree of polymerization 1000, average particle size 145 μm), manufactured by Shin Daiichi PVC Co., Ltd.
2) Made by Kao Corporation, Trimex N-08
3) Adeka Sizer O-130S manufactured by ADEKA Corporation
4) Alkamizer 5 manufactured by Kyowa Chemical Industry Co., Ltd.
5) MIZUKALIZER DS, manufactured by Mizusawa Chemical Co., Ltd.
6) Karenz DK-1, manufactured by Showa Denko K.K.
7) SAKAI SZ2000, manufactured by Sakai Chemical Industry Co., Ltd.
8) Made by ADEKA, ADK STAB LS-12
9) Placel 210 manufactured by Daicel Corporation
10) Made by Daicel Corporation, Plaxel 312
11) Made by Daicel Corporation, Plaxel 320
12) Placel 308, manufactured by Daicel Corporation
13) New Daiichi PVC Co., Ltd., ZEST PQLTX (vinyl chloride resin fine particles obtained by emulsion polymerization, average degree of polymerization 800, average particle diameter 2 μm)
14) DA PX-1720 Black (A), manufactured by Dainichi Seika Kogyo Co., Ltd.
 なお、上記実施例および比較例で使用したポリエステルポリオール(ポリエステルジオールおよびポリエステルトリオール)の分子量は、(株)ダイセルがカタログで開示する値である。そしてポリエステルポリオール等のポリオール系化合物の分子量は、JIS K1557に準拠して測定される水酸基価に基づき、数平均分子量として算出することができる。 The molecular weights of the polyester polyols (polyester diol and polyester triol) used in the above examples and comparative examples are the values disclosed by Daicel Corporation in the catalog. And the molecular weight of polyol type compounds, such as polyester polyol, can be computed as a number average molecular weight based on the hydroxyl value measured based on JISK1557.
 表1より、実施例1~3の塩化ビニル樹脂組成物から得られた塩化ビニル樹脂成形体は、発泡ポリウレタン成形体への接着性に優れていることがわかる。一方、ポリエステルポリオールを含まない比較例1の塩化ビニル樹脂組成物から得られた塩化ビニル樹脂成形体の発泡ポリウレタン成形体、また分子量が900に満たないポリエステルポリオールを含む比較例2の塩化ビニル樹脂組成物から得られた塩化ビニル樹脂成形体は、いずれも発泡ポリウレタン成形体への接着性が低いことがわかる。 From Table 1, it can be seen that the vinyl chloride resin molded articles obtained from the vinyl chloride resin compositions of Examples 1 to 3 are excellent in adhesiveness to the foamed polyurethane molded articles. On the other hand, a foamed polyurethane molded article of a vinyl chloride resin molded article obtained from the vinyl chloride resin composition of Comparative Example 1 containing no polyester polyol, and a vinyl chloride resin composition of Comparative Example 2 containing a polyester polyol having a molecular weight of less than 900 It can be seen that any of the vinyl chloride resin moldings obtained from the products has low adhesion to the polyurethane foam molding.
 本発明の塩化ビニル樹脂組成物は、例えば、インスツルメントパネル、ドアトリム等の自動車内装材の表皮の成形材料として好適に用いられる。
 
The vinyl chloride 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.

Claims (15)

  1.  (a)塩化ビニル樹脂、(b)可塑剤、及び(c)分子量が900以上4000以下のポリオール系化合物を含み、前記ポリオール系化合物が、ポリエステルポリオールおよびポリエーテルポリオールの少なくとも一方である、塩化ビニル樹脂組成物。 (A) a vinyl chloride resin, (b) a plasticizer, and (c) a vinyl compound having a molecular weight of 900 to 4000, wherein the polyol compound is at least one of a polyester polyol and a polyether polyol. Resin composition.
  2.  前記(a)塩化ビニル樹脂100質量部に対し、前記(b)可塑剤を30質量部以上190質量部以下含む、請求項1に記載の塩化ビニル樹脂組成物。 The vinyl chloride resin composition according to claim 1, comprising 30 parts by weight or more and 190 parts by weight or less of the (b) plasticizer with respect to 100 parts by weight of the (a) vinyl chloride resin.
  3.  前記(a)塩化ビニル樹脂100質量部に対し、前記(c)分子量が900以上4000以下のポリオール系化合物を0.1質量部以上30質量部以下含む、請求項1又は2に記載の塩化ビニル樹脂組成物。 The vinyl chloride according to claim 1 or 2, comprising (c) 0.1 to 30 parts by mass of a polyol compound having a molecular weight of 900 to 4000 with respect to 100 parts by mass of the (a) vinyl chloride resin. Resin composition.
  4.  前記(a)塩化ビニル樹脂が、70質量%以上100質量%以下の(a1)塩化ビニル樹脂粒子、及び0質量%以上30質量%以下の(a2)塩化ビニル樹脂微粒子のみからなる、請求項1~3のいずれか1項に記載の塩化ビニル樹脂組成物。 The said (a) vinyl chloride resin consists only of 70 mass% or more and 100 mass% or less of (a1) vinyl chloride resin particle, and 0 mass% or more and 30 mass% or less of (a2) vinyl chloride resin fine particle. 4. The vinyl chloride resin composition according to any one of items 1 to 3.
  5.  前記(a1)塩化ビニル樹脂粒子の平均粒子径が50μm以上500μm以下である、請求項4に記載の塩化ビニル樹脂組成物。 The vinyl chloride resin composition according to claim 4, wherein the average particle diameter of the (a1) vinyl chloride resin particles is 50 µm or more and 500 µm or less.
  6.  前記(a2)塩化ビニル樹脂微粒子の平均粒子径が0.1μm以上10μm以下である、請求項4又は5に記載の塩化ビニル樹脂組成物。 The vinyl chloride resin composition according to claim 4 or 5, wherein the (a2) vinyl chloride resin fine particles have an average particle size of 0.1 µm or more and 10 µm or less.
  7.  粉体成形に用いられる、請求項1~6のいずれか1項に記載の塩化ビニル樹脂組成物。 The vinyl chloride resin composition according to any one of claims 1 to 6, which is used for powder molding.
  8.  パウダースラッシュ成形に用いられる、請求項1~7のいずれか1項の塩化ビニル樹脂組成物。 The vinyl chloride resin composition according to any one of claims 1 to 7, which is used for powder slush molding.
  9.  請求項1~8のいずれか1項に記載の塩化ビニル樹脂組成物を粉体成形してなる塩化ビニル樹脂成形体。 A vinyl chloride resin molded article obtained by powder molding the vinyl chloride resin composition according to any one of claims 1 to 8.
  10.  請求項1~8のいずれか1項に記載の塩化ビニル樹脂組成物をパウダースラッシュ成形してなる塩化ビニル樹脂成形体。 A vinyl chloride resin molded article obtained by powder slush molding the vinyl chloride resin composition according to any one of claims 1 to 8.
  11.  自動車インスツルメントパネル表皮用である、請求項9又は10に記載の塩化ビニル樹脂成形体。 The vinyl chloride resin molded article according to claim 9 or 10, which is used for an automobile instrument panel skin.
  12.  発泡ポリウレタン成形体と、請求項9~11のいずれか1項に記載の塩化ビニル樹脂成形体とを有する、積層体。 A laminate comprising a foamed polyurethane molded product and the vinyl chloride resin molded product according to any one of claims 9 to 11.
  13.  自動車インスツルメントパネル用である、請求項12に記載の積層体。 The laminate according to claim 12, which is for an automobile instrument panel.
  14.  (a)塩化ビニル樹脂、(b)可塑剤、及び(c)分子量が900以上4000以下のポリオール系化合物を混合することを含み、前記ポリオール系化合物が、ポリエステルポリオールおよびポリエーテルポリオールの少なくとも一方である、請求項1~8のいずれか1項に記載の塩化ビニル樹脂組成物の製造方法。 (A) a vinyl chloride resin, (b) a plasticizer, and (c) mixing a polyol compound having a molecular weight of 900 or more and 4000 or less, wherein the polyol compound is at least one of a polyester polyol and a polyether polyol. The method for producing a vinyl chloride resin composition according to any one of claims 1 to 8.
  15.  請求項1~8のいずれか1項に記載の塩化ビニル樹脂組成物、または、請求項14に記載の製造方法に従って製造した塩化ビニル樹脂組成物を粉体成形することを特徴とする、塩化ビニル樹脂成形体の製造方法。
     
    A vinyl chloride resin composition according to any one of claims 1 to 8, or a vinyl chloride resin composition produced according to the production method according to claim 14, wherein the vinyl chloride resin composition is powder-molded. Manufacturing method of resin molding.
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