JP5263545B2 - Vinyl chloride resin composition for powder molding, vinyl chloride resin molded body and laminate - Google Patents

Description

  The present invention provides a vinyl chloride resin composition for powder molding which does not contain a large amount of plasticizer and gives a molded article having good heat aging resistance and excellent fogging resistance even when foamed polyurethane molded articles are laminated, The present invention relates to a vinyl chloride resin molded article formed by powder slush molding of a vinyl chloride resin composition for powder molding, and a laminate provided with the vinyl chloride resin molded article and a polyurethane foam molded article.

The automobile instrument panel has a structure in which a foamed polyurethane layer is provided between a skin made of a vinyl chloride resin and a base material. The skin made of vinyl chloride resin discolors over time and its heat aging resistance decreases. One of the causes of this discoloration is the vinyl chloride of the tertiary amine used as a catalyst during the formation of the polyurethane foam layer. It is a chemical reaction that accompanies the transition to the epidermis made of resin. In order to prevent discoloration of the skin, a granular catcher that traps volatile organic compounds generated in the foamed polyurethane layer is covered with a sheet material of open cells, and the vicinity of the sealing part of the foamed polyurethane layer terminal by the skin material and the base material The urethane integrated foam molded product arranged in (1) was examined (for example, see Patent Document 1). However, there is a portion where the skin and the polyurethane foam layer are in contact with each other, discoloration of the skin material due to the chemical reaction cannot be prevented for a long time, and the heat aging resistance of the skin material is lowered.
On the other hand, a laminate in which a synthetic resin foam layer for joining the core material and the skin is provided, and a gas vent hole for discharging gas generated in the foam layer is provided in the core material has been studied (for example, Patent Document 2). The skin and the synthetic resin foam layer are also in contact with each other, discoloration of the skin material due to the chemical reaction cannot be prevented for a long period of time, and the heat aging resistance of the skin material is reduced.

And a molded article comprising a polyurethane molded article, a skin layer containing a vinyl chloride resin and covering at least one surface of the polyurethane molded article, and an amine catcher agent layer interposed between the polyurethane molded article and the skin layer. (For example, refer patent document 3). However, the amine catcher agent is easy to volatilize, and the transition of the tertiary amine to the skin made of vinyl chloride resin cannot be prevented for a long time, so the discoloration of the skin material due to the chemical reaction cannot be prevented for a long time, and the skin material The heat aging resistance is reduced.
By the way, a vinyl chloride resin composition for powder molding in which a specific trimellitate plasticizer is blended has been studied as a raw material for a skin material of an automobile interior material (for example, see Patent Document 4). When improving the heat aging resistance of the skin material obtained by powder molding of the vinyl chloride resin composition for powder molding, the blending amount of the plasticizer must be increased, and a sticky feeling derived from the plasticizer occurs. To do.

JP 2007-216506 A JP-A-8-90697 Japanese Patent Publication No.4-26303 Japanese Patent Laid-Open No. 2-138355

In recent years, there has been a demand for further heat aging resistance and fogging resistance of automobile instrument panel skins on which a polyurethane foam layer is laminated. There wasn't.
The problem to be solved by the present invention is to provide a vinyl chloride resin composition for powder molding which does not contain a large amount of plasticizer and gives a molded article having good heat aging resistance even when a foamed polyurethane layer is laminated. is there. Another problem to be solved by the present invention is that the above powder molding vinyl chloride resin composition is formed by powder slush molding. Even if a polyurethane foam layer is laminated, heat aging resistance is good and fogging resistance is good. Is a vinyl chloride resin molded article, and a laminate provided with the vinyl chloride resin molded article and the polyurethane foam molded article.

  The inventor of the present invention has intensively studied to solve the above problems, and as a result, (a) a vinyl chloride resin, (b) a plasticizer and (c) a specific glycidyl ether compound is mixed. The present inventors have found that a vinyl resin composition can solve the above problems and have completed the present invention.

（Ｒ¹〜Ｒ⁷は、いずれも独立して水素原子、水酸基又は炭素数１〜６のアルキル基である。ｍは１〜２０の整数である。ｎは１〜２０の整数である。） The present invention is selected from the group consisting of (a) 100 parts by mass of vinyl chloride resin, (b) 70 to 130 parts by mass of plasticizer, and (c) glycidyl ether compounds represented by the following formulas (1) to (3). It is a vinyl chloride resin composition for powder molding formed by blending 0.05 to 12 parts by mass of at least one compound.

(R ^{1 to} R ⁷ are each independently a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 6 carbon atoms. M is an integer of 1 to 20. n is an integer of 1 to 20.)

The vinyl chloride resin composition for powder molding is preferably used for powder slush molding.
The present invention is a vinyl chloride resin molded article obtained by powder slush molding of a vinyl chloride resin composition for powder molding. The vinyl chloride resin molded body is preferably an automobile instrument panel skin.
Furthermore, the present invention is a laminate provided with a foamed polyurethane molded body and the vinyl chloride resin molded body. The preferred laminate is a laminate for an automobile instrument panel.

  Since the vinyl chloride resin composition for powder molding of the present invention does not contain a large amount of plasticizer, the vinyl chloride resin molding of the present invention formed by powder slush molding of the vinyl chloride resin composition for powder molding of the present invention. The body does not generate a sticky feeling derived from the plasticizer. Furthermore, the molded article of the present invention has high heat aging resistance even when the polyurethane foam layer is laminated. In addition, volatile components are hardly generated from the vinyl chloride resin molded article of the present invention, and the fogging resistance of the vinyl chloride resin molded article of the present invention is high.

  The vinyl chloride resin composition for powder molding of the present invention contains (a) a vinyl chloride resin. The (a) vinyl chloride resin includes a copolymer containing vinyl chloride units, preferably 50% by mass or more, more preferably 70% by mass or more, in addition to a vinyl chloride homopolymer. 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 monomers exemplified above are only a part of monomers copolymerizable with vinyl chloride, and “polyvinyl chloride” edited by the Kinki Chemical Association Vinyl Division, Nikkan Kogyo Shimbun (1988) 75-104. Various monomers exemplified on the page can be used. One or more of these monomers can be used. The (a) vinyl chloride resin may be prepared by adding (1) vinyl chloride or ((1) vinyl chloride or ((1) vinyl chloride resin) to resins such as ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, and chlorinated polyethylene. 2) Also includes a resin obtained by graft polymerization of the above-mentioned copolymerizable monomer with vinyl chloride.

  The (a) vinyl chloride resin can be produced by any conventionally known production method such as suspension polymerization method, emulsion polymerization method, solution polymerization method or bulk polymerization method. In particular, a vinyl chloride resin produced by a suspension polymerization method is preferable.

  The average polymerization degree of the (a) vinyl chloride resin is 1000 or more, preferably 1500 to 3000. When the average degree of polymerization of the vinyl chloride resin (a) is less than 1000, the powder flowability of the vinyl chloride resin composition for powder molding becomes low. The average degree of polymerization is measured according to JIS K 6720-2.

  The average particle diameter of the (a) vinyl chloride resin is not particularly limited. The average particle diameter is preferably 50 to 500 μm, more preferably 50 to 250 μm, and still more preferably 100 to 200 μm. (A) When the average particle diameter of a vinyl chloride resin is too small, the powder fluidity | liquidity of a vinyl chloride resin composition will become low. On the other hand, when the average particle diameter of (a) vinyl chloride resin is too large, the smoothness of the molded body formed by powder slush molding of the vinyl chloride resin composition is lost. The average particle diameter is measured in accordance with a sieving method using a JIS standard sieve specified in JIS Z 8801.

The vinyl chloride resin composition for powder molding of the present invention contains (b) a plasticizer conventionally used for processing vinyl chloride resins. The (b) plasticizer is not limited to a specific compound. A specific example of a suitable plasticizer (b) is a trimellitate plasticizer represented by the following formula (4).

In formula (4), R < ₁ > -R < ₃ > is an alkyl group, Comprising: You may mutually be same or different. The linear ratio of R _{1 to} R ₃ is 95 mol% or more. The linear ratio is the ratio of the linear alkyl group to the total alkyl groups of R _{1 to} R ₃ . Specific examples of the linear alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, and n-nonyl group. N-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-hexadecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group and n-stearyl group. Specific examples of the branched alkyl group include i-propyl group, i-butyl group, i-pentyl group, i-hexyl group, i-heptyl group, i-octyl group, i-nonyl group, i-decyl group, i -Undecyl group, i-dodecyl group, i-tridecyl group, i-hexadecyl group, i-pentadecyl group, i-hexadecyl group, i-heptadecyl group, i-octadecyl group, t-butyl group, t-pentyl group, t -Hexyl group, t-heptyl group, t-octyl group, t-nonyl group, t-decyl group, t-undecyl group, t-dodecyl group, t-tridecyl group, t-hexadecyl group, t-pentadecyl group, t -Hexadecyl group, t-heptadecyl group, t-octadecyl group, 2-ethylhexyl group. The ratio of the alkyl group having 7 or less carbon atoms to the total alkyl groups of R _{1 to} R ₃ is 0 to 10 mol%. Ratio of an alkyl group R ₁ to R carbon atoms to the total alkyl groups of ₃ 8 and 9 are 0 to 85 mol%, preferably 0 to 75 mol%. The ratio of the alkyl group having 10 carbon atoms to all the alkyl groups of R _{1 to} R ₃ is 15 to 100 mol%, preferably 25 to 100 mol%. The ratio of the alkyl group having 11 or more carbon atoms to the total alkyl groups of R _{1 to} R ₃ is 0 to 10 mol%.
The trimellitate plasticizer may be a single compound or a mixture. Usually, what is marketed is a mixture, and it is preferable to select a commercially available mixture that satisfies the above-mentioned regulations.

Specific examples of plasticizers other than the trimellitate plasticizer include epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil; dimethyl phthalate, diethyl phthalate, dibutyl phthalate, di- (2-ethylhexyl) phthalate, di-n Phthalic acid derivatives such as octyl phthalate, diisobutyl phthalate, diheptyl phthalate, diphenyl phthalate, diisodecyl phthalate, ditridecyl phthalate, diundecyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, dinonyl phthalate, dicyclohexyl phthalate; dimethyl isophthalate, di Isophthalic acid derivatives such as-(2-ethylhexyl) isophthalate and diisooctylisophthalate; di- (2-ethylhexyl) tetrahydrophthalate, di-n Tetrahydrophthalic acid derivatives such as octyltetrahydrophthalate and diisodecyltetrahydrophthalate, di-n-butyl adipate, di (2-ethylhexyl) adipate, adipic acid derivatives such as diisodecyl adipate and diisononyl adipate; di- (2-ethylhexyl) azelate, di Azelaic acid derivatives such as isooctyl azelate and di-n-hexyl azelate; sebacic acid such as di-n-butyl sebacate, di- (2-ethylhexyl) sebacate, diisodecyl sebacate, di- (2-butyloctyl) sebacate Derivatives; maleic acid derivatives such as di-n-butyl maleate, dimethyl maleate, diethyl maleate, di- (2-ethylhexyl) maleate; di-n-butyl fumarate, di- (2-ethyl) Xylyl) fumarate derivatives such as fumarate; tri- (2-ethylhexyl) trimellitate, tri-n-octyl trimellitate, triisodecyl trimellitate, triisooctyl trimellitate, tri-n-hexyl trimellitate, Trimellitic acid derivatives such as triisononyl trimellitate; pyromellitic acid derivatives such as tetra- (2-ethylhexyl) pyromellitate, tetra-n-octylpyromellitate; triethyl citrate, tri-n-butyl citrate, acetyl Citric acid derivatives such as triethyl citrate and acetyl tri- (2-ethylhexyl) citrate; monomethyl itaconate, monobutyl itaconate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, di- (2-ethylhexyl) Itaconic acid derivatives such as itaconate; oleic acid derivatives such as butyl oleate, glyceryl monooleate, and diethylene glycol monooleate; Stearic acid derivatives such as n-butyl stearate and diethylene glycol distearate; other fatty acid derivatives such as diethylene glycol monolaurate, diethylene glycol dipelargonate and pentaerythritol fatty acid ester; triethyl phosphate, tributyl phosphate, tri- (2-ethylhexyl); ) Phosphate, tributoxyethyl phosphate, triphenyl phosphate, cresyl diphe Phosphate derivatives such as ruphosphate, tricresyl phosphate, trixylenyl phosphate, tris (chloroethyl) phosphate; diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, triethylene glycol di- (2-ethylbutyrate) Rate), triethylene glycol di- (2-ethylhexoate), glycol derivatives such as dibutylmethylene bisthioglycolate; glycerol derivatives such as glycerol monoacetate, glycerol triacetate, glycerol tributyrate; diisodecyl epoxyhexahydrophthalate , Epoxy triglycerides, epoxidized octyl oleate, epoxidized decyl oleate, etc .; adipic acid So-called primary plasticizers such as polyester plasticizers such as polyester, sebacic acid polyester and phthalic polyester; and fatty acid esters of glycols such as chlorinated paraffin and triethylene glycol dicaprylate, butyl epoxy stearate, phenyl oleate Secondary plasticizers such as methyl dihydroabietate; One or more plasticizers can be used. When a secondary plasticizer is used, a primary plasticizer with an equal mass or more is preferably used in combination.
(B) The compounding quantity of a plasticizer is 70-130 mass parts with respect to 100 mass parts of (a) vinyl chloride resin.

（Ｒ¹〜Ｒ⁷は、いずれも独立して水素原子、水酸基又は炭素数１〜６のアルキル基である。ｍは１〜２０の整数である。ｎは１〜２０の整数である。） The vinyl chloride resin composition for powder molding of the present invention contains (c) at least one compound selected from the group consisting of glycidyl ether compounds represented by the following formulas (5) to (7).

(R ^{1 to} R ⁷ are each independently a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 6 carbon atoms. M is an integer of 1 to 20. n is an integer of 1 to 20.)

Preferred R ^{1 to} R ⁷ are all independently a hydrogen atom, a hydroxyl group or a methyl group, and more preferred R ^{1 to} R ⁷ are a methyl group.
Preferred m is 1 to 5, more preferred m is 1 to 3, and particularly preferred m is 1.
Preferred n is 2 to 15, more preferred n is 3 to 10, particularly preferred n is 5 to 9, and most preferred n is 7.

  (C) The compounding quantity of the at least 1 sort (s) of compound chosen from the group which consists of a glycidyl ether compound represented by said formula (5)-(7) is 0.05 with respect to 100 mass parts of (a) vinyl chloride resin. It is -12 mass parts, The said preferable compounding quantity is 0.1-10 mass parts, The more preferable said compounding quantity is 0.15-5 mass parts, The said especially preferable said compounding quantity is 0.2-2 mass parts. Part.

  The vinyl chloride resin composition for powder molding of the present invention may contain a saturated fatty acid having a hydroxyl group and / or a metal soap. Specific examples of the saturated fatty acid having a hydroxyl group include hydroxystearic acid, hydroxymyristic acid, and hydroxylauric acid. Specific examples of the metal soap include lithium stearate, magnesium stearate, aluminum stearate, calcium stearate, strontium stearate, barium stearate, zinc stearate, calcium laurate, barium laurate, zinc laurate, 2-ethylhexanoic acid Barium, zinc 2-ethylhexanoate, barium ricinoleate, zinc ricinoleate and the like. The metal soap is preferably a fatty acid metal salt, more preferably a fatty acid polyvalent metal salt, and even more preferably a fatty acid zinc salt. A saturated fatty acid and / or metal soap having one or more hydroxyl groups is blended. The compounding quantity of the saturated fatty acid and / or metal soap which has a hydroxyl group is not limited to a specific range. The said preferable compounding quantity is 0.1-3 mass parts with respect to 100 mass parts of (a) vinyl chloride resin.

The vinyl chloride resin composition for powder molding of the present invention may contain hydrotalcite. Hydrotalcite is a non _- stoichiometric compound represented by the general formula [Mg _1-x Al _x (OH) ₂ ] ^{x +} [(CO ₃ ) _{x / 2} · mH ₂ O] ^x- and is a positively charged base layer It is an inorganic substance having a layered crystal structure consisting of [Mg _1-x Al _x (OH) ₂ ] ^{x +} and a negatively charged intermediate layer [(CO ₃ ) _{x / 2} · mH ₂ O] ^x- . Here, x is a number in a range greater than 0 and less than or equal to 0.33. Natural hydrotalcite is Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O. Synthesized hydrotalcite Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ .3.5H ₂ O is commercially available. A method for synthesizing synthetic hydrotalcite is described in Japanese Patent Publication No. 61-174270.
The blending amount of hydrotalcite is not limited to a specific range. The said preferable compounding quantity is 0.5-10 mass parts with respect to 100 mass parts of (a) vinyl chloride resin.

The vinyl chloride resin composition for powder molding of the present invention can contain zeolite as a stabilizer. Zeolite has the general formula M _{x / n} · [(AlO ₂ ) _x · (SiO ₂ ) _y ] · zH ₂ O
Where M is a metal ion of valence n, x + y is the number of tetrahedrons per singleton lattice, and z is the number of moles of water. Includes monovalent or divalent metals such as Na, Li, Ca, Mg, Zn, and mixed types thereof.
The blending amount of zeolite is not limited to a specific range. The said preferable compounding quantity is 0.1-5 mass parts with respect to 100 mass parts of (a) vinyl chloride resin.

  The vinyl chloride resin composition for powder molding of the present invention may contain a dusting agent (powder fluidity improver). Specific examples of dusting agents include inorganic fine particles such as calcium carbonate, talc, and aluminum oxide; vinyl chloride resin fine particles, polyacrylonitrile resin fine particles, poly (meth) acrylate resin fine particles, polystyrene resin fine particles, polyethylene resin fine particles. Organic fine particles such as polypropylene resin fine particles, polyester resin fine particles, and polyamide resin fine particles. In particular, inorganic fine particles having an average particle diameter of 10 to 100 nm and vinyl chloride resin fine particles having an average particle diameter of 0.1 to 10 μm are preferable. The degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin fine particles as the dusting agent is 500 to 2000, preferably 800 to 1500. The addition amount of the vinyl chloride resin fine particles as the dusting agent is not limited to a specific range. The amount added is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, with respect to 100 parts by mass of the above (a) vinyl chloride resin.

  The vinyl chloride resin composition for powder molding of the present invention comprises a colorant, an impact modifier, a perchloric acid compound (sodium perchlorate, potassium perchlorate, etc.), an antioxidant, an antifungal agent, and a flame retardant. , Antistatic agents, fillers, ultraviolet absorbers, light stabilizers, foaming agents, β-diketones and the like.

  Specific examples of the colorant are quinacridone pigments, perylene pigments, polyazo condensation pigments, isoindolinone pigments, copper phthalocyanine pigments, titanium white, and carbon black. 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.

  Specific examples of the impact modifier include acrylonitrile-butadiene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, chlorinated polyethylene, and vinyl chloride graft copolymer to ethylene-vinyl acetate copolymer. Ethylene-vinyl acetate copolymer, chlorosulfonated polyethylene, and the like. One or more impact modifiers 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 vinyl chloride resin (a), and the impact resistance of the vinyl chloride resin composition is improved.

Specific examples of the antioxidant are a phenol-based antioxidant, a sulfur-based antioxidant, and a phosphorus-based antioxidant.
Specific examples of the antifungal agent include aliphatic ester antifungal agents, hydrocarbon antifungal agents, organic nitrogen antifungal agents, organic nitrogen sulfur antifungal agents, and the like.

Specific examples of the flame retardant include halogen flame retardants such as chlorinated paraffin; phosphorus flame retardants such as phosphate esters; inorganic hydroxides such as magnesium hydroxide and aluminum hydroxide;
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.

Specific examples of the filler are silica, talc, mica, calcium carbonate, clay and the like.
Specific examples of the light stabilizer include benzotriazole-based, benzophenone-based, nickel chelate-based ultraviolet absorbers, hindered amine-based light stabilizers, and the like.

  Specific examples of the blowing agent include azo compounds such as azocarbonamide 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;

The β-diketones are used for more effectively suppressing fluctuations in the initial color tone of a vinyl chloride resin molded product obtained by powder molding of the vinyl chloride resin composition for powder molding of the present invention. Specific examples of β-diketones include dibenzoylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, and the like. These β-diketones may be used alone or in combination of two or more.
The compounding quantity of (beta) -diketone is not limited to a specific range. The said preferable compounding quantity is 0.1-3 mass parts with respect to 100 mass parts of (a) vinyl chloride resin.

  (A) vinyl chloride resin, (b) plasticizer, (c) at least one compound selected from the group consisting of glycidyl ether compounds represented by the above formulas (5) to (7), and optionally added The mixing method of other additives to be used is not limited. A preferred mixing method is dry blending.

  The vinyl chloride resin molded article of the present invention is obtained by powder slush molding the vinyl chloride resin composition for powder molding of the present invention. The molded body of the present invention is suitably used as an automobile interior material, for example, a skin of an instrument panel, a door trim or the like.

The vinyl chloride resin molded product and the foamed polyurethane molded product of the present invention are laminated to obtain the laminate of the present invention. The lamination method is a method in which a vinyl chloride resin molded body and a foamed polyurethane molded body are separately prepared, and then bonded together by heat fusion, thermal bonding, or using a known adhesive; on the vinyl chloride resin molded body In addition, polymerization is performed by reacting isocyanates and polyols, which are raw materials of the foamed polyurethane molded body, and a method of laminating by foaming polyurethane by a known method.
The laminate of the present invention is suitably used as an automobile interior material such as an instrument panel and a door trim.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples. Various physical properties were measured as follows.

(1) Breaking elongation at low temperature after heat aging Sprinkle the vinyl chloride resin composition for powder molding on a mold with a texture heated to 250 ° C. and let it stand for 10 seconds to melt, and shake the surplus composition Dropped. When 60 seconds have passed since the composition was sprinkled onto the mold, the mold was cooled with cooling water, and when the mold temperature was cooled to 40 ° C., a molded sheet of 145 mm × 175 mm × 1 mm was removed from the mold. Typed. The molded sheet was laid in a 210 mm × 300 mm × 10 mm mold, 40 parts by mass of 4,4′-diphenylmethane-diisocyanate (MDI) and polyether polyol (EXENOL 820 manufactured by Asahi Glass Urethane Co., Ltd., trifunctional And a hydroxyl value of 34 mg KOH / g, containing 1.0% by mass of triethylenediamine and 1.6% by mass of water) and pouring a mixture with 80 parts by mass onto the molded sheet, sealing the mold, and after 10 minutes, 1 mm thickness A sample made of a vinyl chloride resin molded sheet and a foamed polyurethane molded product 9 mm thick was lined from the mold. The sample was placed in an oven and heated at 130 ° C. for 100 hours, and then the polyurethane foam layer was peeled off from the sample. The resulting vinyl chloride resin molded sheet was punched with a No. 1 dumbbell, and the elongation at break of the sheet was measured according to JIS. Measurement was performed at -35 ° C based on -K-6301. When the elongation at break is 100% or more, the heat aging resistance is good.
(2) Glossiness retention ratio A substantially circular test sheet having a diameter of 80 mm was punched out from the vinyl chloride resin molded sheet not backing the foamed polyurethane molded body. The obtained test sheet was put in a glass bottle, covered with a transparent glass plate, allowed to stand in a silicon oil bath at 100 ° C. for 3 hours, then the glass plate was removed and left to stand for 1 hour. Then, the 60 degree reflectance was measured for the glass plate using the glossiness tester (Tokyo Denshoku GP-60). In addition, the 60 degree reflectance of the glass plate before a test was measured previously, and the glossiness retention rate (%) of the glass plate was calculated | required by the following formula.
Glossiness retention (%) = [(Glossiness of glass plate after test) / (Glossiness of glass plate before test)] × 100

Example 1
Ingredients shown in Table 1 except for plasticizer (Trimerix NSK manufactured by Kao Corporation) and paste vinyl chloride resin are mixed in a Henschel mixer, and when the temperature of the mixture rises to 80 ° C, the plasticizer And then dry-up (refers to a state where the plasticizer is absorbed by the vinyl chloride resin particles and the mixture is further improved), and then dusting is performed when the composition is cooled to 70 ° C. or lower. A paste vinyl chloride resin as an agent was added to prepare a vinyl chloride resin composition for powder molding. Thereafter, the heat aging resistance and the glass haze were measured according to the methods described above. The results are shown in Table 1.

Examples 2-8, Comparative Examples 1 and 2
The same operation as in Example 1 was performed except that the ingredients were changed as shown in Table 1. The results are shown in Table 1.

1) ZEST2000ZZ (average degree of polymerization 2000, average particle size 125 μm) manufactured by Shin Daiichi Vinyl Co., Ltd.
2) Trimerix NSK manufactured by Kao Corporation
3) ADEKA O-130P
4) Alkamizer 5 manufactured by Kyowa Chemical Industry Co., Ltd.
5) Mizuscalar DS made by Mizusawa Chemical Co., Ltd.
6) Karenz DK-1 manufactured by Showa Denko K.K.
7) IRGANOX1010 manufactured by Ciba Specialty Chemicals
8) ADEKA ADEKA STAB LA-67
9) TINUVIN P manufactured by Ciba Specialty Chemicals
10) Paste vinyl chloride resin (ZEST PQLT manufactured by Shin Daiichi Vinyl Co., Ltd., degree of polymerization 800, average particle size 1 μm
11) 0.6 parts by mass of DA P 1050 White manufactured by Dainichi Seika Co., Ltd. and 3.8 parts by mass of DA PX 1720 (A) Black manufactured by Dainichi Seika Co., Ltd.

（ただし、Ｒ¹＝ＣＨ₃、ｍ＝１、ｎ＝約７、主成分のｎ＝７） Diglycidyl ether (1): Polypropylene glycol diglycidyl ether represented by the following formula (8) (Epolite 400P manufactured by Kyoeisha Chemical Co., Ltd.)

(However, R ¹ = CH ₃ , m = 1, n = about 7, and n = 7 of the main component)

（ただし、Ｒ²＝Ｒ³＝ＣＨ₃） Diglycidyl ether (2): Hydrogenated bisphenol A diglycidyl ether represented by the following formula (9) (Epolite 4000 manufactured by Kyoeisha Chemical Co., Ltd.)

(However, R ² = R ³ = CH ₃ )

（ただし、Ｒ⁴＝Ｒ⁵＝Ｒ⁶＝Ｒ⁷＝ＣＨ₃） Diglycidyl ether (3); bisphenol A propylene oxide 2 mol adduct diglycidyl ether represented by the following formula (10) (Epolite 3002 manufactured by Kyoeisha Chemical Co., Ltd.)

(However, R ⁴ = R ⁵ = R ⁶ = R ⁷ = CH ₃ )

The heat aging resistance of the vinyl chloride resin molded body when the vinyl chloride resin molded body formed by powder slush molding of the vinyl chloride resin composition for powder molding of Examples 1 to 8 and the foamed polyurethane molded body is laminated is high. It was. Furthermore, the gloss retention of the glass plate of these vinyl chloride resin moldings was high, and the fogging resistance of these vinyl chloride resin moldings was excellent.
On the other hand, when the vinyl chloride resin molded article formed by powder slush molding of the vinyl chloride resin composition for powder molding of Comparative Example 1 containing no diglycidyl ether compound and the polyurethane foam molded article are laminated, the vinyl chloride resin molded article The heat aging resistance of the body was low. Too much diglycidyl ether compound is added. The glass sheet of the vinyl chloride resin molded article obtained by powder slush molding of the vinyl chloride resin composition for powder molding of Comparative Example 2 has a low gloss retention and its fogging resistance. Was low.

  The vinyl chloride resin composition for powder molding of the present invention is suitably molded on the skin of automobile interior materials such as instrument panels and door trims.

Claims (6)

(A) 100 parts by mass of vinyl chloride resin, (b) 70 to 130 parts by mass of plasticizer and (c) at least one selected from the group consisting of glycidyl ether compounds represented by the following formulas (1) to (3) A vinyl chloride resin composition for powder molding comprising 0.05 to 12 parts by mass of a compound.

(R ^{1 to} R ⁷ are each independently a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 6 carbon atoms. M is an integer of 1 to 20. n is an integer of 1 to 20.)   The vinyl chloride resin composition for powder molding according to claim 1, which is used for powder slush molding.   A vinyl chloride resin molded article obtained by powder slush molding of the vinyl chloride resin composition for powder molding described in claim 1 or 2.   The vinyl chloride resin molded article according to claim 3, which is an automotive instrument panel skin.   A laminate provided with the foamed polyurethane molded article and the vinyl chloride resin molded article according to claim 3 or 4.   The laminate according to claim 5, which is a laminate for an automobile instrument panel.