JPWO2016143343A1 - Vinyl chloride resin composition for powder molding, vinyl chloride resin molded body and laminate - Google Patents

Abstract

The present invention provides a vinyl chloride resin composition for powder molding that gives a molded article having excellent flexibility at low temperature, a vinyl chloride resin molded article having excellent flexibility at low temperature, and the vinyl chloride resin molded article and foamed polyurethane. Provided is a laminate having a molded body. The vinyl chloride resin composition for powder molding of the present invention comprises (a) vinyl chloride resin particles, (b) vinyl chloride resin fine particles, (c) an epoxy resin, and (d) a plasticizer.

Description

  The present invention provides a vinyl chloride resin composition for powder molding that gives a molded article excellent in flexibility at low temperature, a vinyl chloride resin molded body obtained by powder molding the vinyl chloride resin composition for powder molding, and the above The present invention relates to a laminate having a vinyl chloride resin molded body and a polyurethane foam molded body.

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. Here, when the skin is made of a vinyl chloride resin, the skin may discolor over time, and the heat aging resistance of the skin may decrease. One cause of the discoloration or the like is a chemical reaction associated with the transfer of the tertiary amine used as a catalyst during the formation of the foamed polyurethane layer to the skin made of vinyl chloride resin. Therefore, in order to prevent discoloration of the skin, it has been studied to introduce a granular catcher material that captures volatile organic compounds generated in the foamed polyurethane layer into the foamed polyurethane layer. Specifically, a urethane integrated foam-molded product in which the catcher material covered with the open-cell sheet material is disposed in the vicinity of the sealing portion of the foamed polyurethane layer terminal by the skin material and the base material was examined ( For example, see Patent Document 1). However, in the urethane integrated foam molded article described in Patent Document 1, since the skin and the foamed polyurethane layer are in contact with each other, discoloration of the skin material due to the chemical reaction cannot be prevented for a long period of time. The heat aging resistance is reduced.
Also, in a laminate provided with a synthetic resin foam layer that joins the core material (base material) and the skin, a laminate in which a vent hole for discharging gas generated in the foam layer is provided in the core material. The body was examined (for example, refer patent document 2). However, even in the laminate described in Patent Document 2, since the skin and the synthetic resin 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 resistance of the skin material can be prevented. Aging is reduced.

Furthermore, it comprises a polyurethane molded body, a skin layer containing a vinyl chloride resin and covering at least one surface of the polyurethane molded body, and an amine catcher agent layer interposed between the polyurethane molded body and the skin layer. Molded bodies have been studied (see, for example, Patent Document 3). However, the amine catcher agent is volatile. Therefore, even in the molded article described in Patent Document 3, it is impossible to prevent the tertiary amine from moving to the skin made of the vinyl chloride resin for a long period of time. As a result, 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 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 skin materials used for automobile interior materials (see, for example, Patent Document 4). In order to improve the heat aging resistance of the skin material obtained by powder molding the powder molding vinyl chloride resin composition, the amount of the plasticizer must be increased. There was a problem that a sticky feeling originated.
Further, a vinyl chloride resin for powder molding containing 100 parts by mass of vinyl chloride resin particles composed of a vinyl chloride resin having an average polymerization degree of 1500 or more and 110 to 150 parts by mass of a specific trimellitate plasticizer. Resin compositions have been studied (see, for example, Patent Document 5).

JP 2007-216506 A JP-A-8-90697 Japanese Patent Publication No.4-26303 Japanese Patent Laid-Open No. 2-138355 International Publication No. 2009/107463

In recent years, in automotive instrument panel skins with polyurethane foam layers laminated, the skin is cracked as designed at low temperatures and the airbag is inflated. There has been a demand for an automobile instrument panel having a skin with excellent flexibility. However, an automobile instrument panel having such a skin has not been realized.
Therefore, the problem to be solved by the present invention is to provide a vinyl chloride resin composition for powder molding that gives a molded article having excellent flexibility at low temperatures. Another problem to be solved by the present invention is that a vinyl chloride resin molded article excellent in flexibility at low temperature, which is obtained by powder molding the vinyl chloride resin composition for powder molding, and the vinyl chloride resin molded article It is provision of the laminated body which has a body and a foaming polyurethane molding.

  The inventor of the present invention has intensively studied to solve the above problems, and as a result, (a) vinyl chloride resin particles, (b) vinyl chloride resin fine particles, (c) epoxy resin, and (d) a powder containing a plasticizer. The present inventors have found that a vinyl chloride resin composition for body molding gives a molded body having particularly excellent flexibility at low temperature, and has completed the present invention.

  The present invention is a vinyl chloride resin composition for powder molding comprising (a) vinyl chloride resin particles, (b) vinyl chloride resin fine particles, (c) an epoxy resin, and (d) a plasticizer.

  Here, in the vinyl chloride resin composition for powder molding of the present invention, a preferable content of the (c) epoxy resin is a total of 100 of the (a) vinyl chloride resin particles and the (b) vinyl chloride resin fine particles. It is 0.2 mass part or more and 20 mass parts or less with respect to a mass part.

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. And in the vinyl chloride resin composition for powder molding of the present invention, the preferred average particle diameter of the (b) vinyl chloride resin fine particles is 0.1 μm or more and 10 μm or less.
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. The “particle diameter” and “average particle diameter” of (a) vinyl chloride resin particles and (b) vinyl chloride resin fine particles can be measured by a laser diffraction method in accordance with JIS Z8825.

  The vinyl chloride resin composition for powder molding of the present invention is preferably used for powder slush molding.

  Moreover, this invention is a vinyl chloride resin molded object formed by powder-molding any of the vinyl chloride resin compositions for powder molding described above.

  Here, the vinyl chloride resin molded article of the present invention is preferably formed by powder slush molding of the above-described vinyl chloride resin composition for powder molding.

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

  And this invention is a laminated body which has a foaming polyurethane molding and one of the vinyl chloride resin moldings mentioned above.

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

  The vinyl chloride resin composition for powder molding of the present invention gives a molded article having excellent flexibility at low temperatures.

(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) vinyl chloride resin fine particles, (c) an epoxy resin, and (d) a plasticizer. It further contains an additive.

<(A) Vinyl chloride resin particles>
(A) Vinyl chloride resin particles are resin particles made of vinyl chloride resin. (A) The vinyl chloride resin particles usually function as a matrix resin in a vinyl chloride resin composition for powder molding.
And (a) As a vinyl chloride resin which comprises vinyl chloride resin particle | grains, the copolymer which contains a vinyl chloride unit preferably 50 mass% or more more preferably 70 mass% or more other than the homopolymer of vinyl chloride (Vinyl chloride copolymer).
Specific examples of monomers (comonomers) copolymerizable with vinyl chloride in vinyl chloride copolymers include olefins such as ethylene and propylene; allyl chloride, vinylidene chloride, vinyl fluoride, trifluoride chloride Halogenated olefins such as ethylene; carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as isobutyl vinyl ether and cetyl vinyl ether; allyls such as allyl-3-chloro-2-oxypropyl ether and allyl glycidyl ether Ethers; unsaturated carboxylic acids such as acrylic acid, maleic acid, itaconic acid, 2-hydroxyethyl acrylate, methyl methacrylate, monomethyl maleate, diethyl maleate, maleic anhydride, their esters or their acid anhydrides Acrylonitrile, Unsaturated nitriles such as tacrylonitrile; acrylamides such as acrylamide, N-methylolacrylamide, acrylamide-2-methylpropanesulfonic acid, (meth) acrylamidepropyltrimethylammonium chloride; allylamine benzoate, diallyldimethylammonium chloride, etc. Allylamine and its derivatives; The monomers exemplified above are only a part of the comonomer, and examples of the comonomer include “Polyvinyl Chloride” edited by Kinki Chemical Association Vinyl Division, Nikkan Kogyo Shimbun (1988), No. 75- Various monomers exemplified on page 104 can be used. One or more of these monomers can be used. The vinyl chloride resin constituting the vinyl chloride resin particles (a) is a resin such as ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, chlorinated polyethylene, It also includes (1) vinyl chloride or (2) a resin obtained by graft polymerization of vinyl chloride and the comonomer.
Here, in this specification, “(meth) acryl” means acryl and / or methacryl.

  Here, the vinyl chloride resin constituting the vinyl chloride resin particles (a) is produced by any conventionally known production method such as suspension polymerization method, emulsion polymerization method, solution polymerization method or bulk polymerization method. Can be done. In particular, (a) the vinyl chloride resin constituting the vinyl chloride resin particles is preferably a vinyl chloride resin produced by suspension polymerization.

  The average particle diameter of the vinyl chloride resin particles (a) is preferably 50 μm or more, more preferably 100 μm or more, preferably 500 μm or less, more preferably 250 μm or less, and further preferably 200 μm. It is as follows. (A) When the average particle size of the vinyl chloride resin 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 The smoothness of the vinyl chloride resin molded product formed by powder molding is improved.

  The average degree of polymerization of the vinyl chloride resin constituting the (a) vinyl chloride resin particles is preferably 800 or more, preferably 5000 or less, more preferably 3000 or less, still more preferably 2200 or less, Especially preferably, it is 2000 or less. When the average degree of polymerization of the above (a) vinyl chloride resin particles is within the above range, good heat resistance can be imparted to a vinyl chloride resin molded article obtained by powder molding a vinyl chloride resin composition for powder molding. . The “average degree of polymerization” is measured according to JIS K 6720-2.

<(B) Vinyl chloride resin fine particles>
(B) Vinyl chloride resin fine particles are resin fine particles made of vinyl chloride resin. (B) The vinyl chloride resin fine particles function as a dusting agent (powder fluidity improver) for improving the powder fluidity of the powdered vinyl chloride resin composition in the powdered vinyl chloride resin composition. To do.
Here, as the vinyl chloride resin constituting the vinyl chloride resin fine particles (b), the same vinyl chloride resin as the vinyl chloride resin particles (a) described above can be used.
And as (b) vinyl chloride resin which comprises vinyl chloride resin microparticles | fine-particles, the vinyl chloride resin manufactured by the emulsion polymerization method is especially preferable.

  The average particle diameter of the (b) vinyl chloride resin fine particles is preferably 0.1 μm or more, and preferably 10 μm or less. When the average particle diameter of the (b) vinyl chloride resin fine particles is within the above range, the powder flowability of the powder moldable vinyl chloride resin composition is improved.

  The average degree of polymerization of the vinyl chloride resin constituting the (b) vinyl chloride resin fine particles is preferably 500 or more, more preferably 600 or more, still more preferably 700 or more, preferably 5000 or less. More preferably, it is 3000 or less, More preferably, it is 2500 or less, More preferably, it is 2000 or less, Especially preferably, it is 1500 or less, Most preferably, it is 1000 or less. (B) When the average degree of polymerization of 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 vinyl chloride resin composition for powder molding is The adhesiveness after sintering to the foamed polyurethane molded article and the meltability during sintering are improved.

  The preferable content of the (b) vinyl chloride resin fine particles is preferably 5% by mass or more, and 35% by mass with respect to the total of the (a) vinyl chloride resin particles and the (b) vinyl chloride resin fine particles. % Or less, more preferably 30% by mass or less, and further preferably 25% by mass or less. When the content of the (b) 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 The adhesiveness after sintering to the foamed polyurethane molded article and the meltability during sintering are improved.

<(C) Epoxy resin>
The vinyl chloride resin composition for powder molding of the present invention contains (c) an epoxy resin.
Here, in the present invention, (c) epoxy resin does not include (d) epoxidized vegetable oil such as epoxidized soybean oil used as a plasticizer. That is, (c) an epoxy resin excludes epoxidized vegetable oil.
Moreover, (c) epoxy resin is not specifically limited except the said conditions, Any of an aromatic epoxy resin, an alicyclic epoxy resin, and an aliphatic epoxy resin can be used. Preferable (c) epoxy resin is an aromatic epoxy resin. Specific examples of aromatic epoxy resins include bisphenol A liquid epoxy resin, bisphenol A solid epoxy resin, bisphenol F and epichlorohydrin, which are obtained by reacting bisphenol A and epichlorohydrin in the presence of alkali. Bisphenol F type epoxy resins obtained by reaction under these conditions, brominated resins of these resins, urethane modified resins of these resins, phenol novolac type epoxy compounds, cresol novolak type epoxy compounds, cresol type epoxy compounds, polyphenol type epoxy compounds And glycidyl ether type epoxy compounds such as hydrogenated bisphenol A type epoxy compounds. Among the above-mentioned, more preferable (c) epoxy resins are bisphenol A type liquid epoxy resin, bisphenol A type solid epoxy resin, and bisphenol F type epoxy resin. These (c) epoxy resins may be used alone or in combination of two or more.
In addition, the epoxy resin being “liquid” means that the epoxy resin is in a liquid state under a normal temperature and a normal pressure of a temperature of 25 ° C. and a pressure of 1 atm.

  Bisphenol A type liquid epoxy resins are commercially available, and specific examples thereof include, for example, trade names “jER828, jER828, jER828EL, jER828XA, jER834” (manufactured by Mitsubishi Chemical Corporation), trade names “EPICLON840, EPICLON840-”. S, EPICLON 850, EPICLON 850-S, EPICLON 850-CRP, EPICLON 850-LC ”(above, manufactured by DIC Corporation,“ EPICLON ”is a registered trademark), and the like. Further, bisphenol A type solid epoxy resins are commercially available, and specific examples thereof include, for example, trade names “EPICLON 860, EPICLON 1050, EPICLON 1055, EPICLON 3050, EPICLON 4050, EPICLON 7050, EPICLON AM-020-P, EPICLON AM-040-P, EPICLON HM-091, EPICLON HM-101 "(manufactured by DIC Corporation). Furthermore, bisphenol F type epoxy resins are commercially available, and specific examples thereof include, for example, trade names “EPICLON 830, EPICLON 830-S, EPICLON 830-LVP, EPICLON 835, EPICLON 835-LV” (manufactured by DIC Corporation). is there.

  Here, the epoxy equivalent of the (c) epoxy resin is preferably 100 g / eq or more, more preferably 150 g / eq or more, preferably 5000 g / eq or less, more preferably 1000 g / eq or less. More preferably, it is 600 g / eq or less. The “epoxy equivalent” is measured according to JIS K 7236.

  Further, the content of (c) epoxy resin with respect to 100 parts by mass in total of (a) vinyl chloride resin particles and (b) vinyl chloride resin fine particles is preferably 0.2 parts by mass or more, and more preferably. Is 0.5 parts by mass or more, more preferably 0.7 parts by mass or more, preferably 20 parts by mass or less, more preferably 18 parts by mass or less, and further preferably 17 parts by mass or less. . (C) When the content of the epoxy resin is within the above range, good flexibility at low temperature is imparted to a vinyl chloride resin molded body obtained by powder molding a vinyl chloride resin composition for powder molding. Can do.

<(D) Plasticizer>
The vinyl chloride resin composition for powder molding of the present invention contains (d) a plasticizer. Here, preferable (d) plasticizers include trimellitic acid ester plasticizers. And the vinyl chloride resin composition for powder molding of this invention can contain plasticizers (henceforth "other plasticizers") other than trimellitic acid ester plasticizer.

<< Trimellitic acid ester plasticizer >>
Examples of trimellitic acid ester plasticizers include ester compounds of trimellitic acid and monohydric alcohols. Here, specific examples of the monohydric alcohol that can form an ester compound with trimellitic acid include 1-hexanol, 1-heptanol, 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, and 1-undecanol. 1-dodecanol and the like.

  And as a trimellitic acid ester plasticizer, the triester compound which esterified substantially all the carboxylic acid of trimellitic acid with the monohydric alcohol mentioned above is preferable. In preparing the triester compound, one kind of monohydric alcohol may be used alone, or a plurality of kinds may be used in combination. That is, the alcohol residue part in the triester compound may be derived from a single monohydric alcohol or may be derived from different monohydric alcohols.

Specific examples of preferred trimellitic acid ester plasticizers include 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), trimellitic acid tri-n-alkyl ester Le (alkyl group carbon atoms are different [The number of carbon atoms is 8-10.] Ester having two or more in a molecule), and mixtures thereof.
Among these, 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 Ester (an ester having two or more kinds of alkyl groups having different carbon numbers [wherein the carbon number is 8 to 10] in the molecule) and a mixture thereof are more preferable.

  The trimellitic acid ester plasticizer may be a single compound or a mixture.

<< Other plasticizers >>
Specific examples of other plasticizers include the following primary plasticizers and secondary plasticizers.

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, An ester having two or more carbon atoms in the molecule), a pyromellitic acid ester plasticizer;
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;
Polyester plasticizers such as adipic acid polyester, sebacic acid polyester, phthalic acid polyester;
Etc. The primary plasticizer mentioned above may use 1 type (s) or 2 or more types.

  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. You may use 1 type (s) or 2 or more types as a secondary plasticizer. Especially, as a secondary plasticizer, an epoxidized vegetable oil is preferable and an epoxidized soybean oil is more preferable. In addition, when using a secondary plasticizer, it is preferable to use trimellitic acid ester and / or a primary plasticizer of equal mass or more together.

  The content of the plasticizer (d) with respect to a total of 100 parts by mass of (a) vinyl chloride resin particles and (b) vinyl chloride resin fine particles is preferably 5 parts by mass or more, more preferably 30 parts by mass or more, and 50 More preferably, not less than 200 parts by mass, more preferably not more than 180 parts by mass, and still more preferably not more than 150 parts by mass. When the content of the plasticizer is within the above range, a vinyl chloride resin molded product obtained by powder molding a vinyl chloride resin composition for powder molding can be given good low temperature flexibility, and The (d) plasticizer is well absorbed in the (a) vinyl chloride resin particles, and the powder moldability of the vinyl chloride resin composition for powder molding is improved.

<Additives>
As an additive that the vinyl chloride resin composition for powder molding may further contain in addition to (a) vinyl chloride resin particles, (b) vinyl chloride resin fine particles, (c) an epoxy resin, and (d) a plasticizer, Without being particularly limited, for example, perchloric acid-treated hydrotalcite, zeolite, fatty acid metal salt, (b) a dusting agent other than vinyl chloride resin fine particles, and other additives can be further included.

<< Perchloric acid-treated hydrotalcite >>
The vinyl chloride resin composition for powder molding 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 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 to the perchloric acid can be arbitrarily set, it is generally 0.1 mol or more and 2 mol or less 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 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. 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 a synthetic hydrotalcite is described in, for example, Japanese Patent Publication No. 61-174270.

  The content of perchloric acid-treated hydrotalcite with respect to a total of 100 parts by mass of (a) vinyl chloride resin particles and (b) vinyl chloride resin fine particles is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more. Preferably, 1.5 parts by mass or more is more preferable, 7 parts by mass or less is preferable, 6 parts by mass or less is more preferable, and 5.5 parts by mass or less is still more preferable. When the content of the perchloric acid-treated hydrotalcite is within the above range, good flexibility at low temperatures is imparted to a vinyl chloride resin molded product obtained by powder molding a vinyl chloride resin composition for powder molding. it can.

<< Zeolite >>
The vinyl chloride resin composition for powder molding of the present invention can contain zeolite as a stabilizer. Zeolite is represented by the general formula: M _{x / n} · [(AlO ₂ ) _x · (SiO ₂ ) _y ] · zH ₂ O (in the above general formula, M is a metal ion of valence n, x + y is four sides per unit cell) Body number, z is the number of moles of water), and the type of M in the general formula is a monovalent or divalent metal such as Na, Li, Ca, Mg, Zn, and the like. These mixed types are mentioned.

  The content of zeolite is not limited to a specific range. The content of zeolite is preferably 0.1 parts by mass or more and preferably 5 parts by mass or less with respect to 100 parts by mass in total of (a) vinyl chloride resin particles and (b) vinyl chloride resin fine particles. When the zeolite content is within the above range, good flexibility at low temperature can be imparted to a vinyl chloride resin molded article obtained by powder molding a vinyl chloride resin composition for powder molding.

<< Fatty acid metal salt >>
The vinyl chloride resin composition for powder molding of the present invention may contain a fatty acid metal salt. Preferred fatty acid metal salts are monovalent fatty acid metal salts, more preferred fatty acid metal salts are monovalent fatty acid metal salts having 12 to 24 carbon atoms, and more preferred fatty acid metal salts having 15 to 21 carbon atoms. It is a monovalent fatty acid metal salt. Specific examples of the fatty acid metal salt include lithium stearate, magnesium stearate, aluminum stearate, calcium stearate, strontium stearate, barium stearate, zinc stearate, calcium laurate, barium laurate, zinc laurate, 2-ethylhexane 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 content of fatty acid metal salt with respect to 100 parts by mass in total of (a) vinyl chloride resin particles and (b) vinyl chloride resin fine particles is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more. It is preferably no greater than 1 part by mass, more preferably no greater than 1 part by mass and even more preferably no greater than 0.5 parts by mass. When the content of the fatty acid metal salt is within the above range, the vinyl chloride resin molded product obtained by powder molding the vinyl chloride resin composition for powder molding can be imparted with good flexibility at a low temperature and further heat resistant. Discoloration after the test can be reduced.

<< Other dusting agents >>
The vinyl chloride resin composition for powder molding of the present invention may contain (b) a dusting agent other than the vinyl chloride resin fine particles (hereinafter sometimes referred to as “other dusting agents”). Specific examples of 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 Organic fine particles such as fine particles and polyamide 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 of the other dusting agent is preferably 20 parts by mass or less, more preferably 10 parts by mass with respect to a total of 100 parts by mass of (a) vinyl chloride resin particles and (b) vinyl chloride resin fine particles. It is as follows.

<< 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, and β-diketone may further 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 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, ethylene-vinyl acetate copolymer, chlorosulfonated polyethylene 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 (a) vinyl chloride resin particles, and the impact resistance of the vinyl chloride resin composition is improved. .

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-based flame retardants such as chlorinated paraffins; phosphorus-based 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.

β-diketone can be used to more effectively suppress fluctuations in the initial color tone of a vinyl chloride resin molded product obtained by powder molding the vinyl chloride resin composition for powder molding of the present invention. Specific examples of β-diketone are 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 content of β-diketone is preferably 0.1 parts by mass or more, and more preferably 5 parts by mass or less with respect to 100 parts by mass in total of (a) vinyl chloride resin particles and (b) vinyl chloride resin fine particles.

<Preparation of vinyl chloride resin composition for powder molding>
Here, the mixing method of (a) vinyl chloride resin particle, (b) vinyl chloride resin fine particle, (c) epoxy resin, (d) plasticizer, and the additive added as needed is not limited. In a preferred mixing method, the components excluding the dusting agent (including (b) vinyl chloride resin fine particles and other dusting agent added if necessary) are once mixed by dry blending, and then not added. This is a method of adding and mixing a dusting agent. The Henschel mixer is preferably used for dry blending. The temperature during dry blending is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, and preferably 100 ° C. or lower.

(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 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, a skin of an automobile instrument panel, a door trim or the like.

<Manufacture of vinyl chloride resin molding>
Here, the mold temperature at the time of powder slush molding is preferably 200 ° C. or higher, more preferably 220 ° C. or higher, preferably 300 ° C. or lower, more preferably 280 ° C. or lower.
In addition, the vinyl chloride resin molded body of the present invention is obtained by, for example, sprinkling a powder molding vinyl chloride resin composition on a mold in the above temperature range and leaving it for 5 seconds to 30 seconds, and then surplus vinyl chloride resin. The composition is shaken off, and is further allowed to stand for 30 seconds to 3 minutes at an arbitrary temperature. Thereafter, the mold is cooled to 10 ° C. or more and 60 ° C. or less, and the obtained vinyl chloride resin molded article is removed from the mold to be suitably obtained.

(Laminate)
The laminate of the present invention can be obtained by laminating the above-described vinyl chloride resin molded article and foamed polyurethane molded article. The lamination method is as follows: (1) A vinyl chloride resin molded body and a foamed polyurethane molded body are separately manufactured, and then bonded together by using thermal fusion, thermal bonding, or a known adhesive; (2) Chlorination Polymerization is performed by reacting isocyanates, which are raw materials of the foamed polyurethane molded body, and polyols on the vinyl resin molded body, and polyurethane is foamed by a known method, and the polyurethane foam is formed on the vinyl chloride resin molded body. And a method of directly forming a molded body. In the latter method (2), the process is simple, and even when a laminated body having various shapes is obtained, the vinyl chloride resin molded body and the foamed polyurethane molded body can be reliably bonded. Therefore, it is more preferable.

  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 polymerization degree of vinyl chloride resin>
The average degree of polymerization of (a) vinyl chloride resin particles and (b) vinyl chloride resin constituting the vinyl chloride resin fine particles is in accordance with JIS K6720-2. (A) Vinyl chloride resin particles and (b) vinyl chloride resin Each fine particle was calculated by dissolving in cyclohexanone and measuring the viscosity.

<Average particle diameter of vinyl chloride resin particles and vinyl chloride resin fine particles>
The average particle size of (a) vinyl chloride resin particles and (b) vinyl chloride resin fine particles is a volume average particle size, and each of the vinyl chloride resin particles and the vinyl chloride resin fine particles is dispersed in a water tank, and the following apparatus is used. Then, the diffraction / scattering intensity distribution of light was measured and analyzed, and the particle diameter distribution based on the particle diameter and volume was measured.
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)

<Low temperature tensile test (initial)>
A vinyl chloride resin molded sheet as the obtained vinyl chloride resin molded body was used as a sample, and the sample was punched with a No. 1 dumbbell described in JIS K 6251. Then, in accordance with JIS K 7113, tensile stress (MPa) and tensile elongation (%) were measured at a tensile rate of 200 mm / min and a low temperature of -35 ° C. A larger tensile elongation at a low temperature of −35 ° C. indicates that the vinyl chloride resin molded article is more excellent in flexibility at a low temperature. The results are shown in Table 1.

<Low temperature tensile test (after heating)>
The obtained laminate with a foamed polyurethane molded article was used as a sample, the sample was put in an oven, and the sample was heated in an environment at a temperature of 130 ° C. for 100 hours. Thereafter, the polyurethane foam layer was peeled from the sample, and the tensile stress (MPa) and the tensile elongation (%) were measured at a low temperature of −35 ° C. under the same conditions as in the low temperature tensile test (initial). It shows that the larger the tensile elongation at −35 ° C., the better the vinyl chloride resin molded body is in heat resistance (flexibility at low temperature after heating). The results are shown in Table 1.

(Examples 1-9 and Comparative Example 1)
<Preparation of vinyl chloride resin composition>
Among the blending components shown in Table 1, components other than epoxidized soybean oil as a plasticizer and vinyl chloride resin fine particles as a dusting agent were placed in a Henschel mixer and mixed. When the temperature of the mixture rises to 80 ° C., epoxidized soybean oil as a plasticizer is added to obtain a mixture, and the mixture is further heated to dry up (the plasticizer is made of vinyl chloride resin particles). And the mixture was further absorbed.). Thereafter, when the dried-up mixture was cooled to 90 ° C. or lower, vinyl chloride resin fine particles as a dusting agent were added to prepare a vinyl chloride resin composition for powder molding.

<Manufacture of vinyl chloride resin molding>
The obtained vinyl chloride resin composition for powder molding is sprinkled on a metal mold with a texture heated to a temperature of 250 ° C., and an arbitrary time of about 8 seconds to 20 seconds so that the thickness of the vinyl chloride resin molded sheet becomes 1 mm. After leaving it to melt, the excess vinyl chloride resin composition was shaken off. Thereafter, the embossed mold sprinkled with the vinyl chloride resin composition was allowed to stand in an oven set at a temperature of 200 ° C., and when 60 seconds had elapsed from the standing, the embossed mold was cooled with cooling water. When the mold temperature was cooled to 40 ° C., a vinyl chloride resin molded sheet of 150 mm × 200 mm × 1 mm was removed from the mold as a vinyl chloride resin molded body.
And the low-temperature tensile test (initial stage) was implemented about the obtained vinyl chloride resin molded sheet according to the above-mentioned method. The results are shown in Table 1.

<Manufacture of laminates>
Two sheets of the obtained vinyl chloride resin molded sheet were laid in a 200 mm × 300 mm × 10 mm mold so as not to overlap 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, 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 parts by mass A polyol mixture consisting of parts was prepared. Then, the prepared polyol mixture and polymethylene polyphenylene polyisocyanate (polymeric MDI) were mixed at a ratio of an index of 98 to prepare a mixed solution. 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. Five minutes after sealing the mold, a laminate of 9 mm thick and 0.18 g / cm ³ density foamed polyurethane molded product on the skin made of 1 mm thick vinyl chloride resin molded sheet is taken out from the mold. It was.
And the low-temperature tension test (after heating) was implemented about the obtained laminated body according to the above-mentioned method. The results are shown in Table 1.

1) ZEST 2000Z manufactured by Shin Daiichi Vinyl Co., Ltd. ((a) vinyl chloride resin particles, average degree of polymerization: 2000, average particle size: 130 μm)
2) manufactured by Kao Corporation, Trimex N-08
3) Adeka Sizer O-130S manufactured by ADEKA Corporation
4) EPICLON 850 manufactured by DIC Corporation (epoxy equivalent: 183 g / eq or more and 193 g / eq or less)
5) EPICLON 830 manufactured by DIC Corporation (epoxy equivalent: 165 g / eq or more and 177 g / eq or less)
6) EPICLON 1050 manufactured by DIC Corporation (epoxy equivalent: 450 g / eq or more and 500 g / eq or less)
7) Alkamizer 5 manufactured by Kyowa Chemical Industry Co., Ltd.
8) MIZUKALIZER DS, manufactured by Mizusawa Chemical Co., Ltd.
9) Sakai Chemical Industry Co., Ltd., SAKAI SZ2000
10) ADEKA Corporation, ADK STAB 522A
11) ADEKA Corporation, ADK STAB LS-12
12) ZEST PQLTX (vinyl chloride resin fine particles obtained by emulsion polymerization, 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 molded products obtained by powder slush molding of the vinyl chloride resin compositions for powder molding of Examples 1 to 9 have sufficient tensile properties after heating while maintaining sufficient initial tensile properties at low temperatures. It was excellent.
In addition, (c) a vinyl chloride resin molded product obtained by powder slush molding of the vinyl chloride resin composition for powder molding of Comparative Example 1 containing no epoxy resin has a tensile stress after heating at a low temperature and a temperature after heating. The tensile elongation value of was low, and the vinyl chloride resin molded article after heating was inferior in flexibility at low temperatures.

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

Claims (10)

  A vinyl chloride resin composition for powder molding comprising (a) vinyl chloride resin particles, (b) vinyl chloride resin fine particles, (c) an epoxy resin, and (d) a plasticizer.   The content of the (c) epoxy resin is 0.2 parts by mass or more and 20 parts by mass or less with respect to a total of 100 parts by mass of the (a) vinyl chloride resin particles and the (b) vinyl chloride resin fine particles. The vinyl chloride resin composition for powder molding according to claim 1.   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 (b) 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 molding the vinyl chloride resin composition for powder molding according to any one of claims 1 to 5.   A vinyl chloride resin molded article obtained by powder slush molding the powder molding vinyl chloride resin composition according to any one of claims 1 to 5.   The vinyl chloride resin molded article according to claim 6 or 7, 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 any one of Claims 6-8.   The laminate according to claim 9, which is used for an automobile instrument panel.