JP6589881B2 - Vinyl chloride resin composition for powder molding and manufacturing method thereof, vinyl chloride resin molded body and manufacturing method thereof, and laminate - Google Patents

Description

  The present invention provides a vinyl chloride resin composition for powder molding having high adhesion after sintering to a foamed polyurethane molded article and excellent meltability during sintering, and the vinyl chloride resin composition for powder molding described above. Vinyl chloride resin molded body formed by powder molding, laminate having the vinyl chloride resin molded body and foamed polyurethane molded body, method for producing vinyl chloride resin composition for powder molding, and vinyl chloride resin molded body It relates to the manufacturing method.

  The automobile instrument panel has a structure in which a foamed polyurethane layer is provided between a skin made of resin and a base material. A skin made of a resin is required to have a property that a surface state does not change due to heat aging when it is molded by a powder molding method. Further, the resin composition used in the powder molding method needs to maintain powder fluidity regardless of the number of moldings. Then, the thermoplastic elastomer composition containing hydrogenated styrene butadiene rubber, polypropylene resin, an internal mold release agent, and polyethylene wax was examined (for example, refer patent document 1).

  By the way, a vinyl chloride resin composition containing a vinyl chloride resin, a plasticizer, and polyethylene wax has been studied in order to obtain a molded article that is rich in wood texture and suitable for building materials and furniture materials (for example, see Patent Document 2). .

JP 2000-109609 A JP-A-11-92608

In recent years, there has been a demand for a vinyl chloride resin composition for powder molding that has high adhesiveness after sintering to a polyurethane foam molded body and excellent meltability during sintering. However, such a vinyl chloride resin composition for powder molding has not been obtained.
Therefore, the problem to be solved by the present invention is to provide a vinyl chloride resin composition for powder molding having high adhesion after sintering to a foamed polyurethane molded article and excellent meltability during sintering. . In addition, another problem to be solved by the present invention is that a vinyl chloride resin molded body obtained by powder molding the above-mentioned vinyl chloride resin composition for powder molding, and the above vinyl chloride resin molded body and foamed polyurethane molded body. It is providing the laminated body which has these. Furthermore, another problem to be solved by the present invention is to provide a method for producing the vinyl chloride resin composition for powder molding and a method for producing the vinyl chloride resin molded body.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have (a) vinyl chloride resin particles, (b) a plasticizer, (c) a specific amount of polyolefin wax modified with a polar group, and ( d) It has been found that a vinyl chloride resin composition for powder molding containing vinyl chloride resin fine particles has high adhesiveness after sintering to a foamed polyurethane molded body and excellent meltability during sintering. It came to complete.

The present invention includes (a) vinyl chloride resin particles, (b) a plasticizer, (c) a polyolefin wax modified with polar groups, and (d) vinyl chloride resin fine particles, and is modified with the above (c) polar groups. The polyolefin wax content is 0.1 parts by mass or more and 6.5 parts by mass or less with respect to 100 parts by mass of the total content of the (a) vinyl chloride resin particles and the (d) vinyl chloride resin fine particles. And a vinyl chloride resin composition for powder molding.
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.

  In the vinyl chloride resin composition for powder molding of the present invention, a preferred average particle size of the polyolefin wax modified with the polar group (c) is 20 μm or less.

  In the vinyl chloride resin composition for powder molding of the present invention, a preferable average particle size of the (a) vinyl chloride resin particles is 50 μm or more and 500 μm or less.

  In the vinyl chloride resin composition for powder molding of the present invention, a preferable average particle size of the (d) vinyl chloride resin fine particles is 0.1 μm or more and 10 μm or less.

  A preferred application of the vinyl chloride resin composition for powder molding of the present invention is powder slush molding.

  Moreover, this invention is a vinyl chloride resin molded object formed by carrying out the powder slush molding of the said any vinyl chloride resin composition for powder forming.

  The vinyl chloride resin molded article of the present invention is preferably for an automotive instrument panel skin.

  Moreover, this invention is a laminated body which has a foaming polyurethane molding and one of the said vinyl chloride resin moldings.

  The laminate of the present invention is preferably for an automobile instrument panel.

  Furthermore, the present invention includes any one of the above, comprising mixing (a) vinyl chloride resin particles, (b) a plasticizer, (c) a polyolefin wax modified with a polar group, and (d) vinyl chloride resin fine particles. This is a method for producing a vinyl chloride resin composition for powder molding.

  Further, the present invention is a vinyl chloride characterized by powder slush molding any one of the above-mentioned vinyl chloride resin compositions for powder molding or a vinyl chloride resin composition for powder molding produced according to the above production method It is a manufacturing method of a resin molding.

  The vinyl chloride resin composition for powder molding of the present invention has high adhesiveness after sintering to a foamed polyurethane molded product and excellent meltability during sintering.

(Vinyl chloride resin composition for powder molding)
The vinyl chloride resin composition for powder molding of the present invention comprises (a) vinyl chloride resin particles, (b) a plasticizer, (c) a polyolefin wax modified with a polar group, and (d) vinyl chloride resin fine particles. And optionally further containing additives.

<Vinyl chloride resin>
Here, as the vinyl chloride resin that can constitute (a) vinyl chloride resin particles and (d) vinyl chloride resin fine particles, in addition to a vinyl chloride homopolymer, vinyl chloride units are preferably 50% by mass or more, more preferably Is a copolymer containing 70% by mass or more. 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 illustrated 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 (a) vinyl chloride resin particles and (d) the 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.

  The vinyl chloride resin can be produced by any conventionally known production method such as suspension polymerization method, emulsion polymerization method, solution polymerization method, bulk polymerization method and the like.

  In the powder molding vinyl chloride resin composition, (a) vinyl chloride resin particles function as a matrix resin. Moreover, (d) vinyl chloride resin fine particles function as a dusting agent (powder fluidity improver) described later.

<(A) Vinyl chloride resin particles>
Here, the average particle diameter of the (a) vinyl chloride resin particles is preferably 50 μm or more and 500 μm or less, more preferably 50 μm or more and 250 μm or less, and further preferably 100 μm or more and 200 μm or less. (A) When the average particle diameter of the vinyl chloride resin particles is in the above range, the powder flowability of the vinyl chloride resin composition for powder molding is good, and the vinyl chloride resin composition for powder molding is Adhesiveness after sintering to the foamed polyurethane molded body and meltability during sintering are improved.
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 average degree of polymerization of the vinyl chloride resin constituting the (a) vinyl chloride resin particles is preferably 800 or more and 5000 or less, and more preferably 800 or more and 3000 or less. (A) When the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles is in the above range, the vinyl chloride resin molded article obtained by powder molding the vinyl chloride resin composition has good heat aging resistance. Can be granted.
The “average degree of polymerization” is measured according to JIS K6720-2.

<(D) Vinyl chloride resin fine particles>
The vinyl chloride resin composition for powder molding of the present invention contains (d) vinyl chloride resin fine particles together with the above (a) vinyl chloride resin particles. The (d) vinyl chloride resin fine particles function as a dusting agent that improves the powder fluidity of the vinyl chloride resin composition for powder molding.

Moreover, the preferable average particle diameter of said (d) vinyl chloride resin microparticles | fine-particles is 0.1 to 10 micrometer. (D) It is because the powder fluidity | liquidity of the vinyl chloride resin composition for powder molding will improve that the average particle diameter of vinyl chloride resin microparticles | fine-particles 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.

  The average degree of polymerization of the vinyl chloride resin constituting the (d) vinyl chloride resin fine particles is preferably 500 or more and 5000 or less, more preferably 600 or more and 3000 or less, and still more preferably 700 or more and 2500 or less. (D) When the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin fine particles is within the above range, the powder flowability of the vinyl chloride resin composition for powder molding is good, and the above powder molding The adhesiveness after sintering of the vinyl chloride resin composition for use to the foamed polyurethane molded article and the meltability during sintering are improved.

  The preferable content of the (d) vinyl chloride resin fine particles is 5% by mass or more and 35% by mass with respect to the total content (100% by mass) of the (a) vinyl chloride resin particles and the (d) vinyl chloride resin fine particles. % Or less, more preferably 5% by mass or more and 30% by mass or less, and further preferably 5% by mass or more and 25% by mass or less. When the content of the (d) vinyl chloride resin fine particles is within the above range, the powder flowability of the vinyl chloride resin composition for powder molding is good, and the vinyl chloride resin composition for powder molding is Adhesiveness after sintering to the foamed polyurethane molded body and meltability during sintering are improved.

<Plasticizer>
The plasticizer (b) contained in the vinyl chloride resin composition for powder molding 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.

  Specific examples of the monohydric alcohol are not particularly limited, and include 1-hexanol, 1-heptanol, 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, and the like. Is mentioned.

Among them, the preferable trimellitic acid ester plasticizer 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.

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 alkyl groups having different carbon numbers [provided that the number of carbon atoms is 6 to 12]), trimellitic acid trialkyl esters (alkyl groups having different carbon numbers [however, carbon number Is an ester having 2 or more types in the molecule), and mixtures thereof.
Specific examples of more preferable trimellitic acid ester plasticizers are trimellitic acid tri-n-octyl, trimellitic acid tri- (2-ethylhexyl), trimellitic acid tri-n-nonyl, trimellitic acid tri-n-decyl , Trimellitic acid tri-n-alkyl esters (esters having two or more types of alkyl groups having different carbon numbers [wherein the number of carbon atoms is 8 to 10]), and mixtures thereof.

  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 for powder molding of the present invention include the following primary plasticizer and secondary plasticizer. Can be mentioned.

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 number of carbons, Pyromellitic acid ester plasticizer, such as ester 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, 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, 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 epoxy hexahydrophthalate diisodecyl, epoxy triglyceride, epoxidized octyl oleate, epoxidized decyl oleate;
Polyester plasticizers such as adipic acid polyester, sebacic acid polyester, phthalic acid polyester;
Etc.

  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 dihydroabietate.

Among the plasticizers other than the trimellitic acid ester plasticizer, pyromellitic acid ester plasticizer is preferable, and pyromellitic acid tetra- (2-ethylhexyl) is more preferable.
In addition, in the vinyl chloride resin composition for powder molding of this invention, 1 type (s) or 2 or more types of other plasticizers 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.

  The total content of the (b) plasticizer is preferably 5 parts by mass or more and 200 parts by mass with respect to 100 parts by mass of the total content of the (a) vinyl chloride resin particles and the (d) vinyl chloride resin fine particles. It is not more than part by mass, more preferably not less than 30 parts by mass and not more than 180 parts by mass, and still more preferably not less than 50 parts by mass and not more than 150 parts by mass. When the content of the plasticizer (b) is in the above range, good flexibility at low temperatures can be imparted to a vinyl chloride resin molded article obtained by powder molding a vinyl chloride resin composition.

<(C) Polyolefin wax modified with polar groups>
The vinyl chloride resin composition for powder molding according to the present invention comprises (c) a polyolefin wax modified with a polar group, and a total content of (a) vinyl chloride resin particles and (d) vinyl chloride resin fine particles. It is necessary to contain 0.1 part by mass or more and 6.5 parts by mass or less with respect to part by mass. The content of the polyolefin wax modified with the polar group (c) is 0.15 with respect to 100 parts by mass of the total content of the (a) vinyl chloride resin particles and the (d) vinyl chloride resin fine particles. It is preferably at least part by mass, more preferably at least 0.5 part by mass, and preferably at most 6.0 part by mass. When the content is within the above range, the adhesiveness after sintering of the vinyl chloride resin composition for powder molding to the foamed polyurethane molded article and the meltability during sintering are improved.

  Here, (c) the average particle diameter of the polyolefin wax modified with a polar group is preferably 20 μm or less, more preferably 15 μm or less, and even more preferably 10 μm or less. When the average particle size is in the above range, the adhesiveness after sintering of the vinyl chloride resin composition for powder molding to the foamed polyurethane molded product and the meltability during sintering are improved. From the viewpoint of handleability, the average particle size of the polyolefin wax modified with (c) polar group is preferably 0.1 μm or more.

  The melting point of the polyolefin wax modified with (c) polar group is preferably 100 ° C. or higher, preferably 100 ° C. or higher and 200 ° C. or lower, more preferably 105 ° C. or higher and 180 ° C. or lower, and more preferably 110 ° C. or higher and 160 ° C. or lower. preferable. When the melting point is within the above range, the adhesiveness after sintering the foamed polyurethane molded article of the vinyl chloride resin composition for powder molding and the meltability during sintering are improved.

  Further, (c) the molecular weight of the polyolefin wax modified with a polar group is preferably 1000 or more and 10,000 or less (number average molecular weight). The said molecular weight can be calculated | required as a standard polystyrene conversion value using a gel permeation chromatography (GPC).

  Here, (c) the polyolefin wax modified with a polar group is, for example, a polyolefin wax such as polyethylene wax, polypropylene wax, polybutylene wax, and the like such as carboxy group, sulfonic acid group, phosphoric acid group, and silicate group. An acid group; a hydroxyl group; an epoxy group; an amino group; an amide group; a (meth) acryloxy group; a carbonyl group; In addition, what is modified with an acid group may be referred to as “acid modification”.

  Among these, preferred (c) polyolefin wax modified with a polar group is acid-modified polyethylene wax.

<Additives>
[Perchloric acid-treated hydrotalcite]
The vinyl chloride resin composition for powder molding of the present invention may contain perchloric acid-treated hydrotalcite. The perchloric acid-treated hydrotalcite is prepared by adding hydrotalcite to a dilute aqueous solution of perchloric acid, stirring the solution, and then filtering, dehydrating or drying as necessary. It can be easily produced by substituting 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). Although the molar ratio of the hydrotalcite and the perchloric acid can be arbitrarily set, it is generally 0.1 to 2 mol of perchloric acid with respect to 1 mol 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, 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. Chloride formed by powder molding a vinyl chloride resin composition for powder molding because the substitution rate of carbonate anions in untreated (unsubstituted) hydrotalcite to perchlorate anions is within the above range. Good flexibility at low temperature can be imparted to the vinyl resin molded article.

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 consisting 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. Natural hydrotalcite is Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O. Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ .3.5H ₂ O is commercially available as the synthesized hydrotalcite. A method for synthesizing synthetic hydrotalcite is described in, for example, Japanese Patent Publication No. 61-174270.

  The preferable content of perchloric acid-treated hydrotalcite with respect to 100 parts by mass of the total content of the above (a) vinyl chloride resin particles and (d) vinyl chloride resin fine particles is 0.5 parts by mass or more and 7 parts by mass or less. Yes, more preferable content is 1 part by mass or more and 6 parts by mass or less, and further preferable content is 1.5 part 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 low temperature can be imparted to the vinyl chloride resin composition for powder molding.

[Zeolite]
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 (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, Zn, and mixed types thereof.

  A preferable content of the zeolite with respect to 100 parts by mass of the total content of the (a) vinyl chloride resin particles and the (d) vinyl chloride resin fine particles is 0.1 parts by mass or more and 5 parts by mass or less.

[Fatty acid metal salt]
The vinyl chloride resin composition for powder molding of the present invention may contain a fatty acid metal salt. A preferable fatty acid metal salt is a monovalent fatty acid metal salt, a more preferable fatty acid metal salt is a monovalent fatty acid metal salt having 12 to 24 carbon atoms, and a more preferable 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.

  The preferred content of the fatty acid metal salt with respect to 100 parts by mass of the total content of the (a) vinyl chloride resin particles and the (d) vinyl chloride resin fine particles is 0.05 parts by mass or more and 5 parts by mass or less. A preferable content is 0.1 part by mass or more and 1 part by mass or less, and a more preferable content is 0.1 part by mass or more and 0.5 part by mass or less. When the content of the fatty acid metal salt is within the above range, good flexibility at low temperatures can be imparted to the vinyl chloride resin composition for powder molding, and the color difference after the heat test can be reduced.

[Other dusting agents]
The vinyl chloride resin composition for powder molding of the present invention may contain a dusting agent (hereinafter, also referred to as “other dusting agent”) other than the above (d) vinyl chloride resin fine particles. 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. Among these, 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 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 total content of the (a) vinyl chloride resin particles and the (d) vinyl chloride resin fine particles. It is.

[Other additives]
The vinyl chloride resin composition for powder molding of the present invention comprises a colorant, an impact modifier, a perchloric acid compound other than perchloric acid-treated hydrotalcite (sodium perchlorate, potassium perchlorate, etc.), oxidation Other additives such as an inhibitor, an antifungal agent, a flame retardant, an antistatic agent, a filler, a light stabilizer, a foaming agent, a β-diketone, and a lubricant may be contained.

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-based pigment is obtained by a condensation reaction of 4,5,6,7-tetrachloroisoindolinone and an aromatic primary diamine, and exhibits a hue from 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 resistance improver include acrylonitrile-butadiene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, ethylene-vinyl acetate copolymer, and the like. In the vinyl chloride resin composition for powder molding 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 for powder molding. In the vinyl chloride resin composition for powder molding of the present invention, the chain and the polar group graft-polymerized to the elastic particles are compatible with the vinyl chloride resin particles (a), and the impact resistance of the vinyl chloride resin composition for powder molding is Improves.

  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.

  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 Nonionic antistatic agents such as ethers and 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 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;

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 singly or in combination of two or more.
In addition, content of (beta) -diketone is not limited to a specific range. The preferable content of β-diketones is 0.1 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total content of the (a) vinyl chloride resin particles and the (d) vinyl chloride resin fine particles. is there.

  Specific examples of the lubricant include 12-hydroxystearic acid oligomer.

(Method for producing vinyl chloride resin composition for powder molding)
The vinyl chloride resin composition for powder molding of the present invention can be produced by mixing the components described above. That is, the method for producing a vinyl chloride resin composition for powder molding of the present invention comprises at least (a) vinyl chloride resin particles, (b) a plasticizer, (c) a polyolefin wax modified with a polar group, and ( d) The content of the polyolefin wax modified with (c) the polar group in the vinyl chloride resin fine particles is 100 parts by mass with respect to the total content of (a) the vinyl chloride resin particles and (d) the vinyl chloride resin fine particles. It includes mixing so that it may become 0.1 to 6.5 mass parts. And in the manufacturing method of the vinyl chloride resin composition for powder molding of this invention, in addition to the said component, an additive may be mixed arbitrarily.
Here, (a) vinyl chloride resin particles, (b) plasticizer, (c) polyolefin wax modified with polar groups, (d) vinyl chloride resin fine particles, and additions added as necessary The mixing method of the agent 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 (d) 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.

(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 for powder molding 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.

(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 for powder molding. That is, at least one of the above-described vinyl chloride resin compositions for powder molding or a vinyl chloride resin composition for powder molding manufactured according to the above-described manufacturing method is used as the method of manufacturing the vinyl chloride resin molded body of the present invention. Is characterized by powder slush molding.

  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.

  In producing the vinyl chloride resin molded article of the present invention, for example, after the vinyl chloride resin composition for powder molding of the present invention is sprinkled on a mold in the above temperature range and left for 5 to 30 seconds. The excess vinyl chloride resin composition is shaken off and left for 30 seconds to 3 minutes. Thereafter, 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.

(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, 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 And so on. 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. .

  And the laminated body of this invention is used suitably as a vehicle interior material, for example, an instrument panel, a door trim, etc.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples. In addition, the measuring method of various physical properties is as follows.

<Average particle diameter of (a) vinyl chloride resin particles and (d) vinyl chloride resin fine particles>
In Examples and Comparative Examples, the average particle size (volume average particle size) of (a) vinyl chloride resin particles and (d) vinyl chloride resin fine particles used in the vinyl chloride resin composition for powder molding is vinyl chloride resin. Disperse the particles and vinyl chloride resin fine particles in the water tank, measure and analyze the light diffraction / scattering intensity distribution using the following equipment, and measure the particle size and volume-based particle size distribution. Based on the above calculation.
・ Apparatus: Laser diffraction particle size distribution analyzer (manufactured by Shimadzu Corporation, model number “SALD-2300”)
Measurement method: Laser diffraction and scattering Measurement range: 0.017 μm to 2500 μm
Light source: Semiconductor laser (wavelength 680 nm, output 3 mW)

<Melting temperature of vinyl chloride resin composition for powder molding>
The melting temperature of the vinyl chloride resin composition for powder molding obtained in Examples and Comparative Examples was measured using a heated mold. Specifically, the mold was placed on a hot plate heated stepwise at equal intervals in a range from 170 ° C. to 270 ° C. to obtain a mold heated stepwise. Then, the vinyl chloride resin composition for powder molding was melted by sprinkling on the mold heated stepwise and leaving it for a predetermined time. Next, the excess vinyl chloride resin composition for powder molding is shaken off, and the mold is cooled with water, whereby the vinyl chloride resin molding sheet in which the vinyl chloride resin for powder molding is formed into a belt shape is molded. Demolded from. The surface of the demolded vinyl chloride resin molded sheet was visually observed, and the temperature of the melted portion was taken as the melting temperature. In addition, the said melted location was judged as a location which has a smooth surface, without leaving particle shape in the shape | molded vinyl chloride resin molded sheet. A lower melting temperature indicates that the vinyl chloride resin composition for powder molding has better meltability during sintering. The results are shown in Tables 1 and 2.

<Polyurethane adhesiveness after heat resistance test of vinyl chloride resin composition for powder molding>
A vinyl chloride resin molded sheet backed with a foamed polyurethane molded body as a laminate was placed in an oven and heated at 130 ° C. for 100 hours, and then the vinyl chloride resin molded sheet was peeled off from the foamed polyurethane molded body. Of the surface of the vinyl chloride resin molded sheet after peeling, the surface on which the foamed polyurethane molded product was lined was visually confirmed, and the polyurethane adhesion after the heat resistance test of the powdered vinyl chloride resin composition was evaluated. When the surface part of the foamed polyurethane molded product remains on the entire surface of the vinyl chloride resin molded sheet visually confirmed as “foam breakage”, the surface part of the foamed polyurethane molded product remains on any part of the entire surface of the vinyl chloride resin molded sheet. The case where there was no “interfacial peeling” was indicated, and the case where the vinyl chloride resin molded sheet was not molded due to extremely low meltability and the polyurethane adhesiveness could not be measured after the heat resistance test was represented by “−”. . It shows that the adhesiveness after sintering to the foaming polyurethane molded object of the vinyl chloride resin composition for powder molding is so high that foam destruction is confirmed. The results are shown in Tables 1 and 2.

(Examples 1-5 and Comparative Examples 1-5)
Among the ingredients shown in Tables 1 and 2, the components except the plasticizer (trimellitic acid ester plasticizer and epoxidized soybean oil) and the dusting agent vinyl chloride resin fine particles are mixed in a Henschel mixer. did. Then, when the temperature of the mixture rose to 80 ° C., a plasticizer was added and dried up (referred to as a state in which the plasticizer was absorbed into the vinyl chloride resin particles and the mixture was further improved). Thereafter, when the dried-up mixture was cooled to 70 ° C. or less, vinyl chloride resin fine particles as a dusting agent were added to produce a vinyl chloride resin composition for powder molding.
And the melting temperature of the obtained vinyl chloride resin composition for powder molding was measured by the said method.
Next, the obtained vinyl chloride resin composition for powder molding is sprinkled on a metal mold with a texture heated to 250 ° C., and is allowed to stand for a period of time adjusted so that the thickness of the vinyl chloride resin molded sheet is 1 mm. The excess vinyl chloride resin composition for powder molding 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. In Comparative Examples 3 and 4, since the meltability of the obtained vinyl chloride resin composition for powder molding was low, a vinyl chloride resin molded sheet could not be molded.
Two sheets of the obtained vinyl chloride resin molded sheet were placed so as not to overlap in a 210 mm × 300 mm × 10 mm mold, and placed with the embossed surface down.
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, 1.2 parts by mass of triethanolamine, 0.5 parts by mass of triethylamine, and 0.5 parts by mass of a foam stabilizer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name" F-122 ") A polyol mixture consisting of parts and polymethylene polyphenylene polyisocyanate (polymeric MDI) are mixed at a ratio of an index of 98 and mixed. Liquid 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 305 mm × 395 mm × 20 mm. Five minutes after sealing, the laminate, in which the foamed polyurethane molded body having a thickness of 9 mm and a density of 0.18 g / cm ³ is lined with a skin made of a vinyl chloride resin molded sheet having a thickness of 1 mm, is taken out from the mold, The polyurethane adhesion was measured after the heat resistance test by the method shown. The results are shown in Tables 1 and 2.

1) ZEST 2000Z manufactured by Shin Daiichi PVC Co., Ltd. ((a) vinyl chloride resin particles, average degree of polymerization 2000, average particle diameter 130 μm)
2) manufactured 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) manufactured by Big Chemie Japan Co., Ltd., CERAFLOUR 925 (acid-modified polyethylene wax, melting point 115 ° C., average particle size 6 μm)
10) HW NL500 manufactured by Mitsui Chemicals, Inc. (polyethylene wax, melting point 103 ° C., average particle diameter 250 μm)
11) CERAFLOUR 991 (polyethylene wax, melting point 115 ° C., average particle size 5 μm) manufactured by Big Chemie Japan Co., Ltd.
12) ZEST PQLTX ((d) vinyl chloride resin fine particles, average degree of polymerization 800, average particle size 2 μm), manufactured by Shin Daiichi Vinyl Co., Ltd.
13) DAPX-1720 Black (A), manufactured by Dainichi Seika Kogyo Co., Ltd.

  The vinyl chloride resin compositions for powder molding of Examples 1 to 5 had high adhesiveness after sintering to a foamed polyurethane molded body and excellent meltability during sintering. The vinyl chloride resin composition for powder molding of Comparative Example 1 having no polyolefin wax modified with a polar group had low meltability during sintering. Moreover, the polyurethane adhesiveness after the heat test of the vinyl chloride resin composition for powder molding of Comparative Example 2 in which the content of the polyolefin wax modified with a polar group is too large was low. The vinyl chloride resin composition for powder molding of Comparative Example 3 containing an unmodified polyolefin wax instead of the polyolefin wax modified with a polar group has extremely low meltability during sintering, and a vinyl chloride resin molded sheet Since it was not possible to form a laminate having a heat resistance test, polyurethane adhesion was not measured. Similarly, the melting temperature of the vinyl chloride resin composition for powder molding of Comparative Example 4 containing a large amount of unmodified polyolefin wax instead of polyolefin wax modified with polar groups is higher than 270 ° C. Adhesion was not measured. Furthermore, instead of the polyolefin wax modified with a polar group, polyurethane adhesiveness after a heat resistance test of the vinyl chloride resin composition for powder molding of Comparative Example 5 containing an unmodified polyolefin wax different from Comparative Examples 3 to 4 Was low.

  The vinyl chloride resin composition for powder molding 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 (11)

(A) vinyl chloride resin particles, (b) plasticizer, (c) polyolefin wax modified with polar groups, and (d) vinyl chloride resin fine particles,
The content of the polyolefin wax modified with the (c) polar group is 0.1 parts by mass with respect to 100 parts by mass of the total content of the (a) vinyl chloride resin particles and the (d) vinyl chloride resin fine particles. A vinyl chloride resin composition for powder molding, having a content of 6.5 parts by mass or less.   The vinyl chloride resin composition for powder molding according to claim 1, wherein the polyolefin wax modified with the polar group (c) has an average particle size of 20 µm or less.   The vinyl chloride resin composition for powder molding according to claim 1 or 2, wherein the average particle diameter of the (a) vinyl chloride resin particles is 50 µm or more and 500 µm or less.   The vinyl chloride resin composition for powder molding according to any one of claims 1 to 3, wherein the average particle diameter of the (d) vinyl chloride resin fine particles is 0.1 µm or more and 10 µm or less.   The vinyl chloride resin composition for powder molding according to any one of claims 1 to 4, which is used for powder slush molding.   A vinyl chloride resin molded article obtained by powder slush molding the vinyl chloride resin composition for powder molding according to any one of claims 1 to 5.   The vinyl chloride resin molded article according to claim 6, which is used for an automobile instrument panel skin.   The laminated body which has a foaming polyurethane molded object and the vinyl chloride resin molded object of Claim 6.   The laminate according to claim 8, which is used for an automotive instrument panel.   6. The method according to claim 1, comprising mixing (a) vinyl chloride resin particles, (b) a plasticizer, (c) a polyolefin wax modified with a polar group, and (d) vinyl chloride resin fine particles. The manufacturing method of the vinyl chloride resin composition for powder forming as described in a term.   Powder slush molding of the vinyl chloride resin composition for powder molding according to any one of claims 1 to 5 or the vinyl chloride resin composition for powder molding manufactured according to the manufacturing method according to claim 10. A method for producing a vinyl chloride resin molded article.