JP6750435B2 - Vinyl chloride resin composition, vinyl chloride resin molding, and laminate - Google Patents

Description

The present invention relates to a vinyl chloride resin composition, a vinyl chloride resin molded product, and a laminate.

Vinyl chloride resins are generally used in various applications because of their excellent properties such as cold resistance, heat resistance, and oil resistance.
Specifically, for example, conventionally, in the formation of automobile interior parts such as automobile instrument panels, a skin made of a vinyl chloride resin molded body or a skin made of a vinyl chloride resin molded body is lined with a foamed material such as polyurethane foam. Automotive interior materials such as a laminated body formed by using are used. And, in the vinyl chloride resin molded body that constitutes the skin of automobile interior parts such as automobile instrument panels, for example, various performances such as good surface slipperiness with suppressed stickiness of the molded body surface are required. There is.

Therefore, in recent years, for example, attempts have been made to improve a vinyl chloride resin composition and a vinyl chloride resin molded body that can be suitably used for manufacturing automobile interior parts such as automobile instrument panels.

Specifically, for example, in Patent Document 1, a vinyl chloride resin molded product is formed using a vinyl chloride resin composition for powder molding in which a plasticizer and a hydroxyl group-modified silicone oil (silanol modified silicone oil) are mixed. .. Then, in the vinyl chloride resin molded article of Patent Document 1, the bleeding property of the plasticizer (ease of exudation to the surface) and the fuzzing property (ease of attachment of fiber residue when the surface is wiped with a cloth, surface stickiness) (Attachability) is reduced.
Further, for example, in Patent Document 2, a vinyl chloride resin composition obtained by mixing vinyl chloride resin particles, a plasticizer, vinyl chloride resin fine particles, and acrylic modified polyorganosiloxane particles in a specific amount. Is disclosed. Then, in the vinyl chloride resin sheet obtained by using the vinyl chloride resin composition described in Patent Document 2, it is difficult for fibers to adhere to the surface of the sheet rubbed with gauze, and surface non-adhesion (surface slipperiness) Is good.

JP2012-7026A JP, 2005-117314, A

However, as a result of repeated studies by the present inventor, a laminated body obtained by backing a foamed polyurethane molded body on a vinyl chloride resin molded body formed by using the conventional vinyl chloride resin composition described in Patent Document 1 was produced. As a result, it became clear that although the vinyl chloride resin molded article had good surface slipperiness, relatively large voids (voids) were formed in the foamed polyurethane molded article. Further, in the vinyl chloride resin molded body formed by using the conventional vinyl chloride resin composition described in Patent Document 2, the problem that voids are generated in the foamed polyurethane molded body is not noticeable, but the vinyl chloride resin There was room for improvement in further improving the surface slipperiness of the molded product.

Therefore, the present invention is capable of producing a vinyl chloride resin molded article having excellent surface slipperiness and capable of suppressing the occurrence of voids in the laminated polyurethane foam molded article, and the vinyl chloride resin molded article. An object is to provide a vinyl chloride resin composition.
It is another object of the present invention to provide a laminate having a foamed polyurethane molded body and a vinyl chloride resin molded body, which has excellent surface slipperiness and in which generation of voids is suppressed.

The present inventor has conducted earnest studies for the purpose of solving the above problems. Then, the present inventor has found that when an ether-modified silicone oil and silicone particles are used in combination, good surface slipperiness of the vinyl chloride resin molded product and voids in the foamed polyurethane molded product laminated on the vinyl chloride resin molded product. The present invention has been completed by finding that both suppression of occurrence can be achieved.

That is, the present invention is intended to advantageously solve the above problems, the vinyl chloride resin composition of the present invention, a vinyl chloride resin, a plasticizer, an ether-modified silicone oil, and silicone particles. It is characterized by including. Thus, if the vinyl chloride resin composition contains a vinyl chloride resin, a plasticizer, an ether-modified silicone oil and silicone particles, the vinyl chloride resin molded article obtained by molding the composition has excellent surface slipperiness, and It is possible to suppress the generation of voids in the polyurethane foam molded article when laminated with the polyurethane foam molded article.

Here, in the vinyl chloride resin composition of the present invention, the silicone particles are preferably acryl-modified silicone particles. By using the acrylic-modified silicone particles, the surface of the vinyl chloride resin molded body can be suppressed while suppressing the occurrence of voids in the polyurethane foam molded body laminated on the vinyl chloride resin molded body obtained by molding the vinyl chloride resin composition. This is because the slipperiness can be improved.

Further, in the vinyl chloride resin composition of the present invention, the content of the silicone particles is preferably 0.3 parts by mass or less based on 100 parts by mass of the vinyl chloride resin. This is because when the content of the silicone particles is at most the above upper limit, the tensile elongation of the vinyl chloride resin molded product at low temperature can be increased.

Further, in the vinyl chloride resin composition of the present invention, the content of the silicone particles is preferably 0.3 parts by mass or less based on 100 parts by mass of the plasticizer. This is because when the content of the silicone particles is at most the above upper limit, the tensile elongation of the vinyl chloride resin molded product at low temperature can be increased.

Further, in the vinyl chloride resin composition of the present invention, the content of the silicone particles is preferably 0.5 times or more and 10 times or less the content of the ether modified silicone oil in terms of mass. This is because when the content of the silicone particles relative to the content of the ether-modified silicone oil is at least the above lower limit, the surface slipperiness of the vinyl chloride resin molded product can be further improved. Further, when the content of the silicone particles relative to the content of the ether-modified silicone oil is not more than the above upper limit, it is possible to further suppress the occurrence of voids in the foamed polyurethane molded body laminated on the vinyl chloride resin molded body, and This is because the tensile elongation of the vinyl resin molding at a low temperature can be sufficiently secured.

Further, in the vinyl chloride resin composition of the present invention, the ether-modified silicone oil preferably has an HLB value of 1.5 or more. This is because the use of an ether-modified silicone oil having an HLB value of at least the above lower limit can further suppress the formation of voids in the polyurethane foam molded product laminated on the vinyl chloride resin molded product.
In the present invention, the “HLB value” refers to Hydrophile-Lipophile Balance, which is represented by the following formula (1) according to the Griffin method:
HLB value = 20 x
(Sum of Formula Weights of Chain Ethylene Oxide Structure/Molecular Weight) (1)
Is an index indicating the degree of hydrophilicity and lipophilicity represented by. Here, in the present invention, the “chain ethylene oxide structure” is a chain ethylene oxide structure described in detail later, and does not include, for example, a cyclic ethylene oxide structure such as an epoxy group.

Further, the vinyl chloride resin composition of the present invention is preferably used for powder molding. When the vinyl chloride resin composition is used for powder molding, for example, the vinyl chloride resin composition is more preferably used for forming a vinyl chloride resin molded body used for automobile interior parts such as automobile instrument panels. Because you can

The vinyl chloride resin composition of the present invention is preferably used for powder slush molding. If the vinyl chloride resin composition is used for powder slush molding, for example, the vinyl chloride resin composition is more preferably used for forming a vinyl chloride resin molded body used for automobile interior parts such as automobile instrument panels. Because you can

Further, the present invention has an object to advantageously solve the above problems, and the vinyl chloride resin molded product of the present invention is characterized by being formed by molding any one of the above-mentioned vinyl chloride resin compositions. And By forming a vinyl chloride resin molded product using the vinyl chloride resin composition, while realizing good surface slipperiness, it is possible to favorably generate voids in the foamed polyurethane molded product laminated on the vinyl chloride resin molded product. Can be suppressed.

Here, it is preferable that the vinyl chloride resin molded product of the present invention is for a skin of an automobile instrument panel. By using the vinyl chloride resin molded product of the present invention as a skin of an automobile instrument panel, it is possible to produce an automobile instrument panel in which stickiness on the surface is favorably suppressed and a polyurethane foam molded product is favorably lined. Because you get it.

Further, the present invention has an object to advantageously solve the above problems, and a laminate of the present invention has a foamed polyurethane molded body and any one of the above-mentioned vinyl chloride resin molded bodies. Characterize. If a foamed polyurethane molded product and the above-mentioned vinyl chloride resin molded product are used to form a laminate, for example, the foamed polyurethane molded product and vinyl chloride resin molded product suitable for automobile interior materials are favorably laminated and have a surface slipperiness. It is possible to obtain an excellent laminate.

According to the present invention, a vinyl chloride resin molded article having excellent surface slipperiness and capable of suppressing the occurrence of voids in a laminated polyurethane foam molded article, and the vinyl chloride resin molded article can be produced. A vinyl chloride resin composition can be provided.
Further, according to the present invention, it is possible to provide a laminate having a foamed polyurethane molded body and a vinyl chloride resin molded body, which has excellent surface slipperiness and in which generation of voids is suppressed.

Hereinafter, embodiments of the present invention will be described in detail.
The vinyl chloride resin composition of the present invention can be used, for example, in obtaining the vinyl chloride resin molded product of the present invention. Moreover, the vinyl chloride resin molded product obtained by molding the vinyl chloride resin composition of the present invention can be used, for example, for producing the laminate of the present invention having the vinyl chloride resin molded product. The vinyl chloride resin molded product of the present invention can be suitably used as an automobile interior material such as a skin of an automobile interior part such as an automobile instrument panel.

(Vinyl chloride resin composition)
The vinyl chloride resin composition of the present invention contains a vinyl chloride resin, a plasticizer, an ether-modified silicone oil, and silicone particles, and may optionally further contain additives and the like. Since the vinyl chloride resin composition of the present invention contains the above-mentioned predetermined components, a vinyl chloride resin molded product having excellent surface slipperiness can be obtained by using the vinyl chloride resin composition of the present invention. Further, when a polyurethane foam molded article is laminated on a vinyl chloride resin molded article obtained by molding the vinyl chloride resin composition of the present invention, generation of voids in the polyurethane foam molded article is suppressed, It is possible to favorably manufacture a laminate having a molded body and a urethane foam molded body.

<Vinyl chloride resin>
Here, the vinyl chloride resin contained in the vinyl chloride resin composition may contain, for example, one kind or two or more kinds of vinyl chloride resin particles, and optionally one kind or two or more kinds of vinyl chloride resin fine particles. Can be further included. Among them, the vinyl chloride resin preferably contains at least vinyl chloride resin particles, more preferably contains vinyl chloride resin particles and vinyl chloride resin fine particles, and one kind of vinyl chloride resin particles and two kinds of vinyl chloride resin It is more preferable to contain fine particles.
In the present specification, "resin particles" refer to particles having a particle diameter of 30 µm or more, and "resin fine particles" refer to particles having a particle diameter of less than 30 µm.
The vinyl chloride resin can be produced by any conventionally known production method such as suspension polymerization method, emulsion polymerization method, solution polymerization method and bulk polymerization method.

<< composition >>
As the vinyl chloride resin, in addition to homopolymers composed of vinyl chloride monomer units, vinyl chloride copolymers containing 50% by mass or more, and more preferably 70% by mass or more of vinyl chloride monomer units may be used. Can be mentioned. Specific examples of the monomer (comonomer) capable of forming a vinyl chloride-based copolymer and copolymerizable with a vinyl chloride monomer include olefins such as ethylene and propylene; allyl chloride, vinylidene chloride, Halogenated olefins such as vinyl fluoride and ethylene trifluoride chloride; carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as isobutyl vinyl ether and cetyl vinyl ether; allyl-3-chloro-2-oxypropyl Allyl ethers such as ether and allyl glycidyl ether; unsaturated carboxylic acids such as acrylic acid, maleic acid, itaconic acid, 2-hydroxyethyl acrylate, methyl methacrylate, monomethyl maleate, diethyl maleate and maleic anhydride, Esters or acid anhydrides thereof; unsaturated nitriles such as acrylonitrile and methacrylonitrile; acrylamides such as acrylamide, N-methylolacrylamide, acrylamido-2-methylpropanesulfonic acid, (meth)acrylamidopropyltrimethylammonium chloride; Allylamine benzoate, allylamine such as diallyldimethylammonium chloride and derivatives thereof; and the like. The above-exemplified monomers are only a part of the comonomer, and as the comonomer, “polyvinyl chloride” edited by the Kinki Chemical Society, Vinyl Section, Nikkan Kogyo Shimbun (1988) No. 75- Various monomers exemplified on page 104 can be used. These comonomers may be used alone or in combination of two or more. The vinyl chloride resin may be a resin such as ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, chlorinated polyethylene, and (1) vinyl chloride or ( 2) A resin obtained by graft-polymerizing vinyl chloride and the comonomer is also included.
Here, in this specification, "(meth)acryl" means acryl and/or methacryl.

<< vinyl chloride resin particles >>
In the vinyl chloride resin composition, the vinyl chloride resin particles usually function as a matrix resin (base material). The vinyl chloride resin particles are preferably produced by a suspension polymerization method.

[Average degree of polymerization]
Here, the average degree of polymerization of the vinyl chloride resin particles is preferably 500 or more, more preferably 1000 or more, further preferably 1500 or more, more preferably 5000 or less, more preferably 3000 or less, further preferably 2500 or less, and 2000 or less. More preferable. If the average degree of polymerization of the vinyl chloride resin particles is not less than the above lower limit, for example, a vinyl chloride resin molded body can be used for automobiles while sufficiently ensuring the physical strength of the vinyl chloride resin molded body obtained by molding the vinyl chloride resin composition. This is because the tensile elongation at low temperature, which is suitable when used as the skin of an instrument panel, can be improved. Further, if the average degree of polymerization of the vinyl chloride resin particles is not more than the above upper limit, the meltability of the vinyl chloride resin composition can be improved and the surface smoothness can be improved.
In addition, in this invention, "average degree of polymerization" can be measured based on JISK6720-2.

[Average particle size]
The average particle size of the vinyl chloride resin particles is usually 30 μm or more, preferably 50 μm or more, more preferably 100 μm or more, preferably 500 μm or less, and more preferably 200 μm or less. This is because if the average particle diameter of the vinyl chloride resin particles is at least the above lower limit, the powder fluidity of the vinyl chloride resin composition will be further improved. Further, when the average particle diameter of the vinyl chloride resin particles is not more than the above upper limit, the meltability of the vinyl chloride resin composition is further improved, and the surface smoothness of the vinyl chloride resin molded product formed using the composition is improved. This is because it can be further improved.
In the present invention, the “average particle diameter” can be measured as a volume average particle diameter by a laser diffraction method according to JIS Z8825.

[Content ratio]
The content ratio of the vinyl chloride resin particles in the vinyl chloride resin is preferably 70% by mass or more, more preferably 80% by mass or more, and 100% by mass with respect to 100% by mass of the total vinyl chloride resin. Can be set, and is preferably 95% by mass or less, more preferably 90% by mass or less. When the content ratio of the vinyl chloride resin particles in the vinyl chloride resin is at least the above lower limit, while sufficiently securing the physical strength of the vinyl chloride resin molded product obtained by molding the vinyl chloride resin composition, tensile at low temperature This is because the elongation can be improved. Further, if the content ratio of the vinyl chloride resin particles in the vinyl chloride resin is not more than the above upper limit, the powder fluidity of the vinyl chloride resin composition is further improved.

<<Vinyl chloride resin particles>>
In the vinyl chloride resin composition, the vinyl chloride resin fine particles usually function as a dusting agent (powder fluidity improver). The vinyl chloride resin fine particles are preferably produced by an emulsion polymerization method.

[Average degree of polymerization]
Here, the average degree of polymerization of the vinyl chloride resin fine particles is preferably 500 or more, more preferably 700 or more, preferably 5000 or less, more preferably 3000 or less, and further preferably 2500 or less. Then, for example, when two kinds of vinyl chloride resin fine particles having different average degrees of polymerization are used together as the dusting agent, the average value of the average degrees of polymerization of the combined dusting agents is preferably 1000 or more, and less than 1500. Is preferred. When the average degree of polymerization of the vinyl chloride resin fine particles as the dusting agent is at least the above lower limit, the powder flowability of the vinyl chloride resin composition will be better and the low temperature of the molded article obtained by using the composition will be improved. This is because the tensile elongation at is better. Further, when the average degree of polymerization of the vinyl chloride resin fine particles is not more than the above upper limit, the meltability of the vinyl chloride resin composition is further improved, and the surface smoothness of the vinyl chloride resin molded product obtained by molding the composition is more excellent. Because it will improve.

[Average particle size]
The average particle size of the vinyl chloride resin fine particles is usually less than 30 μm, preferably 10 μm or less, and more preferably 0.1 μm or more. This is because if the average particle size of the vinyl chloride resin fine particles is at least the above lower limit, the powder flowability of the vinyl chloride resin composition can be more favorably exhibited without making the size of the dusting agent excessively small. .. Further, when the average particle diameter of the vinyl chloride resin fine particles is not more than the above upper limit, the meltability of the vinyl chloride resin composition is further increased, and the smoothness of the formed vinyl chloride resin molded product can be further improved. is there.

[Content ratio]
The content ratio of the vinyl chloride resin fine particles in the vinyl chloride resin is preferably 5% by mass or more, more preferably 10% by mass or more, and 30% by mass or less with respect to 100% by mass of the vinyl chloride resin. Is preferable, 20% by mass or less is more preferable, and 0% by mass may be sufficient. This is because if the content ratio of the vinyl chloride resin fine particles in the vinyl chloride resin is at least the above lower limit, the powder fluidity of the vinyl chloride resin composition will be further improved. Further, when the content ratio of the vinyl chloride resin fine particles in the vinyl chloride resin is not more than the above upper limit, the physical strength and the tensile elongation at low temperature of the vinyl chloride resin molded product obtained by molding the vinyl chloride resin composition are further improved. This is because it can be increased.

<Plasticizer>
The vinyl chloride resin composition of the present invention needs to further contain a plasticizer. If the vinyl chloride resin composition does not contain a plasticizer, a vinyl chloride resin molded article cannot be satisfactorily obtained using the vinyl chloride resin composition.

<< content >>
Here, the content of the plasticizer is preferably 70 parts by mass or more, more preferably 80 parts by mass or more, and further preferably 90 parts by mass or more with respect to 100 parts by mass of the vinyl chloride resin. The amount is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, further preferably 100 parts by mass or less, and further preferably 95 parts by mass or less. When the content of the plasticizer is at least the above lower limit, it imparts excellent flexibility to the vinyl chloride resin composition, and for example, it can be easily processed into a vinyl chloride resin molded article, and the resulting vinyl chloride resin molded article is obtained. This is because good tensile elongation can be imparted at low temperatures. Further, if the content of the plasticizer is not more than the above upper limit, the stickiness of the surface of the obtained vinyl chloride resin molded product can be further suppressed, and the surface slipperiness can be further enhanced.

<<Type>>
Here, specific examples of the plasticizer include the following primary plasticizers and secondary plasticizers.
Examples of so-called primary plasticizers include trimethyl trimellitate, triethyl trimellitate, tri-n-propyl trimellitate, tri-n-butyl trimellitate, tri-n-pentyl trimellitate, and trim-n trimellitate. -Hexyl, tri-n-heptyl trimellitate, tri-n-octyl trimellitate, tri-n-nonyl trimellitate, tri-n-decyl trimellitate, tri-n-undecyl trimellitate, trimellitate Acid tri-n-dodecyl, trimellitic acid tri-n-tridecyl, trimellitic acid tri-n-tetradecyl, trimellitic acid tri-n-pentadecyl, trimellitic acid tri-n-hexadecyl, trimellitic acid trim-n- Heptadecyl, trimellitic acid tri-n-stearyl, trimellitic acid tri-n-alkyl ester (here, the number of carbon atoms of the alkyl group of trimellitic acid tri-n-alkyl ester is different from each other in one molecule) ) Etc., a linear trimellitic acid ester in which the alkyl group constituting the ester is linear [Note that these trimellitic acid esters are a mixture even if they are composed of a single compound. May be. ];
Tri-i-propyl trimellitate, tri-i-butyl trimellitate, tri-i-pentyl trimellitate, tri-i-hexyl trimellitate, tri-i-heptyl trimellitate, trimellitate tri- i-octyl, trimellitic acid tri-(2-ethylhexyl), trimellitic acid tri-i-nonyl, trimellitic acid tri-i-decyl, trimellitic acid tri-i-undecyl, trimellitic acid tri-i-dodecyl , Trimellitic acid tri-i-tridecyl, trimellitic acid tri-i-tetradecyl, trimellitic acid tri-i-pentadecyl, trimellitic acid tri-i-hexadecyl, trimellitic acid tri-i-heptadecyl, trimellitic acid trimellitic acid An alkyl group constituting the ester such as -i-octadecyl or trimellitic acid trialkyl ester (wherein the alkyl group of the trimellitic acid trialkyl ester may have different carbon numbers in one molecule). A branched trimellitic acid ester [wherein these trimellitic acid esters may be composed of a single compound or may be a mixture. ];
Tetramethyl pyromellitic acid, tetraethyl pyromellitic acid, tetra-n-propyl pyromellitic acid, tetra-n-butyl pyromellitic acid, tetra-n-pentyl pyromellitic acid, tetra-n-hexyl pyromellitic acid, pyromellitic acid Tetra-n-heptyl, tetra-n-octyl pyromellitic acid, tetra-n-nonyl pyromellitic acid, tetra-n-decyl pyromellitic acid, tetra-n-undecyl pyromellitic acid, tetra-n-dodecyl pyromellitic acid , Tetra-n-tridecyl pyromellitic acid, tetra-n-tetradecyl pyromellitic acid, tetra-n-pentadecyl pyromellitic acid, tetra-n-hexadecyl pyromellitic acid, tetra-n-heptadecyl pyromellitic acid, tetra pyromellitic acid tetra -N-stearyl, pyromellitic acid tetra-n-alkyl ester (wherein the carbon number of the alkyl group of the pyromellitic acid tetra-n-alkyl ester may be different from each other in one molecule), and the like. Linear pyromellitic acid ester in which the alkyl group constituting the ester is linear [Note that these pyromellitic acid esters may be composed of a single compound or may be a mixture. ];
Tetra-i-propyl pyromellitic acid, tetra-i-butyl pyromellitic acid, tetra-i-pentyl pyromellitic acid, tetra-i-hexyl pyromellitic acid, tetra-i-heptyl pyromellitic acid, tetra-pyromellitic acid tetra- i-octyl, tetra-(2-ethylhexyl) pyromellitic acid, tetra-i-nonyl pyromellitic acid, tetra-i-decyl pyromellitic acid, tetra-i-undecyl pyromellitic acid, tetra-i-dodecyl pyromellitic acid , Tetra-i-tridecyl pyromellitic acid, tetra-i-tetradecyl pyromellitic acid, tetra-i-pentadecyl pyromellitic acid, tetra-i-hexadecyl pyromellitic acid, tetra-i-heptadecyl pyromellitic acid, tetra pyromellitic acid tetra -I-octadecyl, pyromellitic acid tetraalkyl ester (wherein, carbon atoms of the alkyl groups of pyromellitic acid tetraalkyl ester may be different from each other in one molecule), etc., and an alkyl group constituting the ester. Is a branched pyromellitic acid ester [Note that these pyromellitic acid esters may be composed of a single compound or may be a mixture. ];
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 and 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, diisooctyl azelate and di-n-hexyl azelate;
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 and di-(2-ethylhexyl) itaconate;
Oleic acid derivatives such as butyl oleate, glyceryl monooleate, diethylene glycol monooleate;
Ricinoleic acid derivatives such as methyl acetyl ricinoleate, butyl acetyl ricinoleate, glyceryl monoricinoleate and diethylene glycol monoricinoleate;
Stearic acid derivatives such as n-butyl stearate and diethylene glycol distearate (excluding 12-hydroxystearic acid and its ester);
Other fatty acid derivatives such as diethylene glycol monolaurate, diethylene glycol dipelargonate and 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-ethyl butyrate), triethylene glycol di-(2-ethylhexoate), dibutyl methylene bisthioglycolate, etc. A glycol derivative of
Glycerin derivatives such as glycerol monoacetate, glycerol triacetate, glycerol tributyrate;
Epoxy derivatives such as diisodecyl hexahydrophthalate, epoxy triglyceride, epoxidized octyl oleate, and epoxidized decyl oleate;
Polyester plasticizers such as adipic acid type polyester, sebacic acid type polyester, phthalic acid type polyester;
And so on.

Further, as so-called secondary plasticizers, epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil; chlorinated paraffins, fatty acid esters of glycols such as triethylene glycol dicaprylate, butyl epoxy stearate, phenyl oleate. , Methyl dihydroabietate, and the like.

Note that these plasticizers may be used alone or in combination of two or more kinds such as a primary plasticizer and a secondary plasticizer. When a secondary plasticizer is used, it is preferable to use the secondary plasticizer in combination with a primary plasticizer having an equal mass or more.

From the viewpoint of improving the moldability of the vinyl chloride resin composition, it is preferable to use trimellitic acid ester and/or pyromellitic acid ester among the above-mentioned plasticizers, and trimellitic acid ester is used. Is more preferable, and it is more preferable to use a linear trimellitic acid ester, and it is more preferable to use a linear trimellitic acid ester having two or more alkyl groups having different carbon numbers in the molecule. The alkyl group preferably has 8 to 10 carbon atoms, and the alkyl group is more preferably an n-octyl group or an n-decyl group. Then, it is preferable to further use epoxidized soybean oil together with the trimellitic acid ester.

<Ether-modified silicone oil>
The vinyl chloride resin composition of the present invention is characterized by further containing an ether-modified silicone oil together with the silicone particles described in detail later. When the vinyl chloride resin composition further contains an ether-modified silicone oil, the vinyl chloride resin molded article obtained by molding the vinyl chloride resin composition containing a plasticizer can have good surface slipperiness and at the same time, the vinyl chloride resin molded article. It is possible to satisfactorily suppress the generation of voids in the foamed polyurethane molded article laminated with
It should be noted that the compatibility between the improvement of the surface slipperiness and the suppression of the generation of voids by including the ether-modified silicone oil together with the silicone particles is required when the content of the plasticizer is relatively large, specifically, 100 mass% of the vinyl chloride resin. It is more effectively realized when the content of the plasticizer with respect to the parts is 70 parts by mass or more.

<<Type>>
Here, the ether-modified silicone oil usually has an ether group introduced into at least one of a main chain composed of a siloxane bond (—Si—O—Si—), a side chain of the main chain, and an end of the main chain. It becomes. Here, when an ether group is introduced into the main chain, the ether group is block-bonded in the middle of the main chain. When an ether group is introduced at the above-mentioned end, it may be introduced at one end or both ends. Further, the ether-modified silicone oil may further have other substituents other than the ether group introduced at the main chain, the side chains of the main chain, and/or the ends of the main chain.
The ether-modified silicone oil preferably has an ether group introduced into at least a side chain.

[Ether group]
Examples of the ether group include a substituent having one or more chain alkylene oxide structures. Specifically, as the ether group, for example, the following general formula (2):
[Chemical 1]
_{- (C 2 H 4 O)} x - (2)
[In the formula (2), x is a natural number of 1 or more. ] A substituent having only a chain ethylene oxide structure represented by the following formula (in the formula (2), when x is a natural number of 2 or more, it is also referred to as "polyethylene oxide group"); General formula (3):
[Chemical 2]
_{- (C 3 H 6 O)} y - (3)
[In Formula (3), y is a natural number of 1 or more. ] A substituent having a chain propylene oxide structure represented by the following formula (in the formula (3), when y is a natural number of 2 or more, it is also referred to as "polypropylene oxide group"); the above chain ethylene oxide in addition to the structure, any organic structure other than chain alkylene oxide structure (. the following, "R", indicated as "R '") further having substituent _{(e.g., -R- (C 2 H 4 O} ) x - R′); a substituent having a chain alkylene oxide structure such as the chain ethylene oxide structure and the chain propylene oxide structure described above, and further having any of the above organic structures R and R′ (for example, —R—(C ₂ H ₄ O) _x (C ₃ H ₆ O) _y —R′); and the like. Here, for example, the _{-R- (C 2 H 4 O)} x -R ' and _{-R- (C 2 H 4 O)} x (C 3 H 6 O) y -R' any organic structure in R and Only one of R'may be present.

Among them, while increasing the surface slipperiness of the vinyl chloride resin molded body, from the viewpoint of further suppressing the generation of voids in the foamed polyurethane molded body adjacent to the vinyl chloride resin molded body, the reason is not clear, the ether group is , Preferably at least a chain ethylene oxide structure, more preferably a chain ethylene oxide structure and a chain propylene oxide structure, more preferably a plurality of chain ethylene oxide structure and a chain propylene oxide structure, Further, from the viewpoint of excellent heat aging resistance, it is more preferable not to have an unsaturated bond.

[Other substituents]
Other substituents that can be further introduced into the ether-modified silicone oil are not particularly limited and include, for example, an alkyl group (—C _a H _2a+1 ; where a is any natural number), an aralkyl group (eg, − _{CH 2 -CH (CH 3) -C} 6 H 5; _wherein, C 6 _{H 5} is a phenyl group) and the like.

<<HLB value>>
The HLB value of the ether-modified silicone oil is preferably 1.5 or more, preferably 10 or less, more preferably 8 or less, and further preferably 6.5 or less. This is because when the HLB value of the ether-modified silicone oil is at least the above lower limit, it is possible to further suppress the generation of voids during the lamination process of the polyurethane foam molding. Further, if the HLB value of the ether-modified silicone oil is not more than the above upper limit, the vinyl chloride resin molded product can exhibit better surface slipperiness. And, because good surface slipperiness of the vinyl chloride resin molded product obtained by molding the vinyl chloride resin composition and the suppression of the occurrence of voids in the foamed polyurethane molded product can be compatible at a higher level. is there.
Here, the HLB value is an index that can be represented by the above equation (1).

<<<viscosity>>>
Further, the viscosity of the ether-modified silicone oil at a temperature of 25° C. is preferably 65 cs or more, more preferably 100 cs or more, further preferably 300 cs or more, and more preferably 4000 cs or less, It is more preferably 3000 cs or less, further preferably 1000 cs or less. When the viscosity of the ether-modified silicone oil is at least the above lower limit, the defoaming effect is reduced, and the polyurethane foam molding is performed while maintaining the surface slipperiness of the vinyl chloride resin molded product obtained by molding the vinyl chloride resin composition to be better. This is because it is possible to further suppress the generation of voids in the body stacking process. Further, if the viscosity of the ether-modified silicone oil is not more than the above upper limit, the handling property of the ether-modified silicone oil is excellent.
In the present invention, the “viscosity” can be measured according to ASTM D 445-46T at a temperature of 25° C. according to the method described in the examples.

<< content >>
The content of the ether-modified silicone oil is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and 1 part by mass or less with respect to 100 parts by mass of the vinyl chloride resin. The amount is preferably 0.5 parts by mass or less, more preferably 0.4 parts by mass or less, and further preferably 0.4 parts by mass or less. When an ether-modified silicone oil having a content not less than the above lower limit is used in combination with silicone particles, the stickiness of the surface of the vinyl chloride resin molded article can be sufficiently reduced, the surface slipperiness can be further improved, and the adjacent foamed polyurethane molded article can be formed. This is because voids in the body can be sufficiently suppressed. In addition, if the content of the ether-modified silicone oil is not more than the above upper limit, for example, even when a vinyl chloride resin molded body is continuously molded, the molding die is caused by an excessive amount of the ether-modified silicone oil. This is because it is possible to suppress contamination of the surface such as.

The content of the ether-modified silicone oil is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and 1 part by mass or less with respect to 100 parts by mass of the plasticizer. It is preferably 0.5 part by mass or less, more preferably 0.4 part by mass or less. Generally, plasticizers are apt to cause stickiness on the surface of molded articles, but if an ether-modified silicone oil with a content above the above lower limit is used in combination with silicone particles, the stickiness on the surface of vinyl chloride resin molded articles will be sufficient. This is because the amount can be reduced, the surface slipperiness can be further improved, and the voids in the laminated polyurethane foam molded article can be sufficiently suppressed. In addition, if the content of the ether-modified silicone oil is not more than the above upper limit, for example, even when a vinyl chloride resin molded body is continuously molded, the molding die is caused by an excessive amount of the ether-modified silicone oil. This is because it is possible to suppress contamination of the surface such as.

In the present invention, the ether-modified silicone oil generally has fluidity at room temperature. And in this invention, "normal temperature" points out 23 degreeC.

<Silicone particles>
The vinyl chloride resin composition of the present invention is characterized by further containing silicone particles in addition to the above-mentioned vinyl chloride resin, plasticizer and ether-modified silicone oil. When the vinyl chloride resin composition further contains silicone particles together with the above ether-modified silicone oil, it is possible to suppress the occurrence of voids in the foamed polyurethane molded article to be laminated with the vinyl chloride resin molded article, while using a plasticizer. It is possible to improve the surface slipperiness of the vinyl chloride resin molded product obtained by molding the vinyl chloride resin composition containing the same.
It should be noted that the improvement of the surface slipperiness and the suppression of the generation of voids can be achieved at the same time by including the silicone particles together with the ether-modified silicone oil, when the content of the plasticizer is relatively large, specifically, 100 parts by mass of the vinyl chloride resin. When the content of the plasticizer is 70 parts by mass or more, it is more effectively realized.

<< structure >>
Here, the silicone particles contained in the vinyl chloride resin composition of the present invention are usually particles in which a polymer having a polysiloxane main skeleton composed of a siloxane bond (—Si—O—Si—) has a particle shape. Here, the polysiloxane main skeleton includes, for example, a random structure randomly polymerized; a ladder structure polymerized to form a two-dimensional repeating structure; a cage structure polymerized to form a three-dimensional repeating three-dimensional structure; It can have a structure.
In addition, in the polysiloxane main skeleton, the silicone particles preferably have a methyl group (—CH ₃ ) and/or an ethyl group in addition to the oxygen atom (O) in the silicon atom (Si) forming the main skeleton. (-C 2 _{H 5)} is coupled, and more preferably, an oxygen atom and a methyl group is attached. Further, the silicone particles are preferably polyorganosiloxane (organic modified silicone particles) having a structure in which a silicon atom (Si) is bonded to any one or more organic groups R″, and R″ is − OCOCH = CH ₂ or -OCOC _(CH 3) = represented by CH _2, more preferably (meth) acrylic-modified silicone particles, acrylic-modified silicone which the R '' is represented by -OCOCH = CH ₂ More preferably, they are particles. This is because the use of the (meth)acryl-modified silicone particles, especially the acrylic-modified silicone particles, can further improve the surface slipperiness of the vinyl chloride resin molded product.
Note that, for example, the acrylic-modified silicone particles are a silicone-acrylic graft copolymer introduced by graft-polymerizing a —OCOCH═CH ₂ group to a polysiloxane main skeleton.

<< shape >>
In addition, the shape of the silicone particles is not particularly limited, and may be any shape such as spherical shape; spherical shape with a projection in which a spherical body has a protruding portion; indeterminate shape; Above all, the shape of the silicone particles is preferably spherical from the viewpoint of giving the vinyl chloride resin molded article excellent surface slipperiness.

<< content >>
The content of silicone particles is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and less than 1 part by mass with respect to 100 parts by mass of the vinyl chloride resin. Is preferred, more preferably 0.5 parts by mass or less, still more preferably 0.3 parts by mass or less. When the silicone particles having a content of the above lower limit or more are used in combination with the ether-modified silicone oil, the occurrence of voids in the laminated polyurethane foam molded article is sufficiently suppressed, and the stickiness of the surface of the vinyl chloride resin molded article is good. This is because the surface slipperiness can be further improved. Further, if the content of the silicone particles is at most the above upper limit, the tensile elongation at low temperature of the vinyl chloride resin molded product can be sufficiently secured. In particular, if the content of the silicone particles is 0.3 parts by mass or less with respect to 100 parts by mass of the vinyl chloride resin, the tensile elongation of the vinyl chloride resin molded product at a low temperature can be further increased.

The content of silicone particles is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and less than 1 part by mass with respect to 100 parts by mass of the plasticizer. The amount is preferably 0.5 part by mass or less, more preferably 0.3 part by mass or less. In general, a plasticizer tends to cause stickiness on the surface of a molded article, and if silicone particles having a content of the above lower limit or more are used in combination with an ether-modified silicone oil, the occurrence of voids in a laminated foamed polyurethane molded article will occur. This is because it is possible to satisfactorily reduce the stickiness of the surface of the vinyl chloride resin molded product while sufficiently suppressing it, and further improve the surface slipperiness. Further, if the content of the silicone particles is not more than the above upper limit, the tensile elongation at low temperature of the vinyl chloride resin molded product can be sufficiently secured. In particular, when the content of silicone particles is 0.3 parts by mass or less based on 100 parts by mass of the plasticizer, the tensile elongation of the vinyl chloride resin molded product at low temperature can be further increased.

Furthermore, the content of the silicone particles is, in terms of mass, preferably 0.5 times or more, more preferably 1 time or more, more preferably 1.3 times or more the content of the ether-modified silicone oil. Is more preferable, 10 times or less is preferable, 5 times or less is more preferable, and 3 times or less is further preferable. This is because if the content of the silicone particles relative to the content of the ether-modified silicone oil is at least the above lower limit, the stickiness of the surface of the vinyl chloride resin molded article can be further reduced and the surface slipperiness can be further enhanced. .. When the content of the silicone particles relative to the content of the ether-modified silicone oil is not more than the above upper limit, the generation of voids in the laminated polyurethane foam molded article is further suppressed and the vinyl chloride resin molded article is stretched at low temperature. This is because it is possible to secure sufficient growth.

<Additive>
The vinyl chloride resin composition of the present invention may further contain various additives in addition to the components described above. The additives are not particularly limited, and stabilizers such as perchloric acid-treated hydrotalcite, zeolite, β-diketone, and fatty acid metal salt; mold release agents; dusting agents other than the vinyl chloride resin fine particles; and Other additives; and the like.

<<Perchloric acid treated hydrotalcite>>
The perchloric acid-treated hydrotalcite that may be contained in the vinyl chloride resin composition is, for example, hydrotalcite is added to a dilute aqueous solution of perchloric acid and stirred, and then, if necessary, filtered, dehydrated or dried. By replacing at least a part of the carbonate anion (CO ₃ ²⁻ ) in the hydrotalcite with the perchlorate anion (ClO ₄ ⁻ ) (2 mol of the perchlorate anion is replaced per 1 mol of the carbonate anion). It can be easily manufactured as perchloric acid-introduced hydrotalcite. The molar ratio of the hydrotalcite to the perchloric acid can be set arbitrarily, but in general, 0.1 mol or more and 2 mol or less of perchloric acid is preferable with respect to 1 mol of hydrotalcite.

Here, the substitution ratio of the carbonate anion to the perchlorate anion in the untreated (unsubstituted with no perchlorate anion introduced) hydrotalcite is preferably 50 mol% or more, more preferably 70 mol%. More preferably, it is 85 mol% or more. The substitution rate of carbonate anions in untreated (non-substituted with no perchlorate anion introduced) hydrotalcites to perchlorate anions is preferably 95 mol% or less. The substitution ratio of carbonate anion to perchlorate anion in untreated (unsubstituted with no perchlorate anion introduced) hydrotalcite is within the above range, which makes it easier to form a vinyl chloride resin molded article. Because it can be manufactured.

Hydrotalcite is a nonstoichiometric compound represented by the general formula: [Mg _1-x Al _x (OH) ₂ ] ^x+ [(CO ₃ ) _x/2 ·mH ₂ O] ^x− , and is positively charged. inorganic materials with the base layer and the _{[Mg 1-x Al x (} OH) 2] x +, an intermediate layer which is negatively charged the _{[(CO 3) x / 2} · mH 2 O] x- and layered crystal structure consisting of Is. Here, in the above general formula, x is a number in the range of more than 0 and 0.33 or less. Natural hydrotalcite is a _{Mg 6 Al 2 (OH) 16} CO 3 · 4H 2 O. As the synthesized hydrotalcite, Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ .3.5H ₂ O is commercially available. A method for synthesizing synthetic hydrotalcite is described in, for example, JP-A-61-174270.

Here, the content of the perchloric acid-treated hydrotalcite is not particularly limited, and is preferably 0.5 part by mass or more, more preferably 1 part by mass or more, relative to 100 parts by mass of the vinyl chloride resin. It is preferably 7 parts by mass or less, and more preferably 6 parts by mass or less. When the content of the perchloric acid-treated hydrotalcite is within the above range, the vinyl chloride resin molded product obtained by molding the vinyl chloride resin composition can better maintain the tensile elongation at low temperature. Is.

<< Zeolite >>
The vinyl chloride resin composition may contain zeolite as a stabilizer. Zeolites are represented by the general formula: M _x/n ·[(AlO ₂ ) _x ·(SiO ₂ ) _y ]·zH ₂ O (in the general formula, M is a metal ion having a valence of n, and x+y is a tetrahedral surface per unit lattice. Body number, z is the number of moles of water). Examples of M in the general formula include monovalent or divalent metals such as Na, Li, Ca, Mg, and Zn, and mixed types thereof.

Here, the content of the zeolite is not particularly limited and is preferably 0.1 part by mass or more and preferably 5 parts by mass or less with respect to 100 parts by mass of the vinyl chloride resin.

<<β-diketone>>
The β-diketone is used to more effectively suppress the fluctuation of the initial color tone of the vinyl chloride resin molded product obtained by molding the vinyl chloride resin composition. Specific examples of the β-diketone include dibenzoylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane and the like. These β-diketones may be used alone or in combination of two or more.

The content of β-diketone is not particularly limited and is preferably 0.01 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the vinyl chloride resin.

<<Fatty acid metal salt>>
The fatty acid metal salt that can be contained in the vinyl chloride resin composition is not particularly limited and can be any fatty acid metal salt. Among them, monovalent fatty acid metal salts are preferable, monovalent fatty acid metal salts having 12 to 24 carbon atoms are more preferable, and monovalent fatty acid metal salts having 15 to 21 carbon atoms are further preferable. 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, and 2-ethyl. Examples thereof include barium hexanoate, zinc 2-ethylhexanoate, barium ricinoleate, and zinc ricinoleate. As the metal constituting the fatty acid metal salt, a metal capable of generating a polyvalent cation is preferable, a metal capable of generating a divalent cation is more preferable, and a divalent cation of Period 3 to Period 6 of the periodic table. Is more preferable, and a metal capable of generating a divalent cation of the 4th period of the periodic table is particularly preferable. The most preferred fatty acid metal salt is zinc stearate.

Here, the content of the fatty acid metal salt is not particularly limited, and is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, and 5 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. The amount is preferably 1 part by mass or less, more preferably 1 part by mass or less, still more preferably 0.5 part by mass or less. This is because when the content of the fatty acid metal salt is within the above range, the value of the color difference of the vinyl chloride resin molded product obtained by molding the vinyl chloride resin composition can be reduced.

<<Release agent>>
The release agent is not particularly limited, and examples thereof include 12-hydroxystearic acid-based lubricants such as 12-hydroxystearic acid, 12-hydroxystearic acid ester, and 12-hydroxystearic acid oligomer. Here, the content of the release agent is not particularly limited and can be 0.01 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the vinyl chloride resin.

<<Other dusting agents>>
Other dusting agents other than the above vinyl chloride resin fine particles that can be contained in the vinyl chloride resin composition include inorganic fine particles such as calcium carbonate, talc and aluminum oxide; polyacrylonitrile resin fine particles, poly(meth)acrylate resin fine particles. , Polystyrene resin particles, polyethylene resin particles, polypropylene resin particles, polyester resin particles, polyamide resin particles, and other organic particles. Among them, inorganic fine particles having an average particle diameter of 10 nm or more and 100 nm or less are preferable.

Here, the content of the other dusting agent is not particularly limited, and is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less with respect to 100 parts by mass of the vinyl chloride resin. The other dusting agents may be used alone or in combination of two or more, and may be used in combination with the above-mentioned vinyl chloride resin fine particles.

<<Other additives>>
Other additives that may be contained in the vinyl chloride resin composition are not particularly limited, and examples thereof include colorants (pigments), impact modifiers, perchloric acid compounds other than perchloric acid-treated hydrotalcite. (Sodium perchlorate, potassium perchlorate, etc.), antioxidants, antifungal agents, flame retardants, antistatic agents, fillers, light stabilizers, foaming agents and the like.

Specific examples of the colorant (pigment) 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-phenylenedianthranilic 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-based pigment is obtained by a condensation reaction between perylene-3,4,9,10-tetracarboxylic acid anhydride and an aromatic primary amine, and exhibits red to reddish purple and brown hues. Specific examples of the perylene pigments are perylene red, perylene orange, perylene maroon, perylene vermillion, and perylene bordeaux.
The polyazo condensed pigment is obtained by condensing an azo dye in a solvent to have a high molecular weight, and exhibits a hue of a yellow or red pigment. Specific examples of polyazo condensation pigments 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 greenish yellow to red and brown hues. A specific example of the isoindolinone-based pigment is isoindolinone yellow.
The copper phthalocyanine-based pigment is a pigment in which copper is coordinated to phthalocyanines and exhibits a yellowish green to a vivid blue hue. Specific examples of the copper phthalocyanine-based 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 are 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, one or more impact modifiers can be used. The impact resistance improver is dispersed in the vinyl chloride resin composition as a non-uniform phase of fine elastic particles. In the vinyl chloride resin composition, the chains and polar groups graft-polymerized on the elastic particles are compatible with the vinyl chloride resin, and the impact resistance of the vinyl chloride resin molded product obtained by molding the vinyl chloride resin composition is improved.

Specific examples of the antioxidant include a phenolic antioxidant, a sulfur antioxidant, and a phosphorus antioxidant such as phosphite.

Specific examples of the antifungal agent include aliphatic ester antifungal agents, hydrocarbon antifungal agents, organic nitrogen antifungal agents, organic nitrogen sulfur antifungal agents and the like.

Specific examples of the flame retardant are halogen-based flame retardants; phosphorus-based flame retardants such as phosphoric acid 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; and the like.

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 foaming 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 CFCs, carbon dioxide gas, water and pentane; and gas-based foaming agents such as microcapsules containing these.

<Method for preparing vinyl chloride resin composition>
The vinyl chloride resin composition of the present invention is not particularly limited and can be prepared by mixing the above-mentioned components.
Here, the mixing method of the vinyl chloride resin, a plasticizer, an ether-modified silicone oil, silicone particles, and various additives that are further used in combination as necessary is not particularly limited, and examples thereof include: Examples include a method in which components other than the dusting agent containing vinyl chloride resin particles are mixed by dry blending, and then the dusting agent is added and mixed. Here, it is preferable to use a Henschel mixer for the dry blending. The temperature during dry blending is not particularly limited and is preferably 50°C or higher, more preferably 70°C or higher, and preferably 200°C or lower.

<Use of vinyl chloride resin composition>
And the obtained vinyl chloride resin composition can be suitably used for powder molding, and can be suitably used by powder slush molding.

(Vinyl chloride resin molding)
The vinyl chloride resin molded product of the present invention is characterized by being obtained by molding the above-mentioned vinyl chloride resin composition by an arbitrary method. Since the vinyl chloride resin molded product of the present invention is obtained by molding the vinyl chloride resin composition of the present invention, while realizing good surface slipperiness, for example, it is chlorinated while suppressing voids in the foamed polyurethane molded product. The foamed polyurethane molded product can be favorably lined with the vinyl resin molded product. Therefore, the vinyl chloride resin molded product of the present invention is suitably used as an automobile interior member, specifically, as a skin of an automobile interior part such as an automobile instrument panel and a door trim, and particularly, an automobile instrument. It is preferably used for the epidermis of panels.

<< Molding method of vinyl chloride resin molding >>
Here, the mold temperature at the time of powder slush molding is not particularly limited and is preferably 200° C. or higher, more preferably 220° C. or higher, preferably 300° C. or lower, and 280° C. The following is more preferable.

When the vinyl chloride resin molded body is manufactured, the following method can be used without any particular limitation. That is, the vinyl chloride resin composition of the present invention is sprinkled on a mold in the above temperature range and left for 5 seconds or more and 30 seconds or less, then the excess vinyl chloride resin composition is shaken off, and further at an arbitrary temperature. Leave for 30 seconds or more and 3 minutes or less. Then, the mold is cooled to 10° C. or higher and 60° C. or lower, and the obtained vinyl chloride resin molded body is released from the mold. Then, the demolded vinyl chloride resin molded body is obtained, for example, as a sheet-shaped molded body having a shape of a mold.

(Laminate)
The laminate of the present invention has a foamed polyurethane molded body and the above-mentioned vinyl chloride resin molded body. The foamed polyurethane molded body is usually lined with a vinyl chloride resin molded body, and the foamed polyurethane molded body and the vinyl chloride resin molded body are adjacent to each other in the laminating direction. Since the laminate of the present invention has a vinyl chloride resin molded product obtained by molding the vinyl chloride resin composition of the present invention, the stickiness of the surface is sufficiently reduced, and the vinyl chloride resin molding is performed. A foamed polyurethane molded article is satisfactorily laminated on the body while suppressing voids. Therefore, the laminate of the present invention is suitably used as an automobile interior material for automobile interior parts such as an automobile instrument panel and a door trim, and particularly preferably used for an automobile instrument panel.

Here, the stacking method is not particularly limited, and the following method can be used, for example. That is, a vinyl chloride resin molded body is obtained by reacting isocyanates, which are a raw material for a foamed polyurethane molded body, with a polyol on the vinyl chloride resin molded body to carry out polymerization, and foaming polyurethane by a known method. A polyurethane foam molding is directly formed on the top.

Hereinafter, the present invention will be specifically described based on Examples, but the present invention is not limited to these Examples. In the following description, "%" and "parts" representing amounts are based on mass unless otherwise specified.
Then, the average degree of polymerization of the vinyl chloride resin particles and the vinyl chloride resin fine particles, the average particle diameter of the vinyl chloride resin particles and the vinyl chloride resin fine particles; the HLB value and viscosity of various silicone oils; The tensile elongation at a low temperature after the aging test), the surface slipperiness (dynamic friction coefficient) of the vinyl chloride resin molding, and the degree of generation of voids in the polyurethane foam molding were measured and evaluated by the following methods.

<Average degree of polymerization>
The average degree of polymerization of the vinyl chloride resin particles and the vinyl chloride resin fine particles was calculated by dissolving each of the vinyl chloride resin particles and the vinyl chloride resin fine particles in cyclohexanone and measuring the viscosity in accordance with JIS K6720-2. ..

<Average particle size>
The average particle diameter (volume average particle diameter (μm)) of the vinyl chloride resin particles and the vinyl chloride resin fine particles was measured according to JIS Z8825. Specifically, vinyl chloride resin particles and vinyl chloride resin fine particles are dispersed in a water tank, and the diffraction/scattering intensity distribution of light is measured and analyzed using the following apparatus, and the particle diameter and volume-based It was calculated by measuring the particle size distribution.
・Device: Laser diffraction type particle size distribution measuring device (Shimadzu Corporation, 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)

<HLB value>
The HLB values of various silicone oils are calculated by the following formula (1) by the Griffin method:
HLB value = 20 x
(Sum of Formula Weights of Chain Ethylene Oxide Structure/Molecular Weight) (1)
Was calculated according to
A higher HLB value (closer to 20) indicates that the silicone oil has higher polarity and hydrophilicity, and a lower HLB value (closer to 0) indicates that the silicone oil has lower polarity and lipophilicity.

<Viscosity>
The viscosities of various silicone oils were measured as a kinematic viscosity η ^CS/25 (unit: mm ² /s=cs) at a temperature of 25° C. using a Ubbelohde viscometer according to ASTM D 445-46T.

<Tensile elongation at low temperature>
The tensile elongation of the vinyl chloride resin molded product was evaluated by measuring the tensile elongation at break (%) at low temperature in each of the initial (unheated) state and the heated (heat aging test) state as follows.
<< initial >>
The obtained vinyl chloride resin molded sheet was punched with a No. 1 dumbbell described in JIS K6251 and measured for tensile elongation at break (%) at a low temperature of -35°C at a tensile speed of 200 mm/min in accordance with JIS K7113. did. The larger the value of tensile elongation at break, the better the ductility at low temperature of the initial (unheated) vinyl chloride resin molded product.
<<After heating (heat aging test)>>
A laminated body lined with a foamed polyurethane molded body was used as a sample. The sample was placed in an oven and heated at a temperature of 130° C. for 100 hours. Next, the foamed polyurethane molded body was peeled off from the heated laminate to prepare only the vinyl chloride resin molded sheet. Then, under the same conditions as in the initial case, the tensile breaking elongation (%) of the vinyl chloride resin molded sheet after heating for 100 hours was measured. The larger the value of the tensile elongation at break, the more excellent the ductility at low temperature of the vinyl chloride resin molded product after heating (heat aging test).

<Surface slipperiness>
The surface slipperiness of the vinyl chloride resin molded product was evaluated by measuring the dynamic friction coefficient as follows.
Specifically, using a texture tester (manufactured by Trinity Lab, product name “TL201Ts”), under a measurement environment of temperature 23° C. and relative humidity 50%, load: 50 g, speed: 10 mm/sec, test range: Under the conditions of 50 mm, measurement range: 30 mm excluding 10 mm before and after the test range, the tactile contactor is brought into contact with the vinyl chloride resin molded sheet before forming the laminate to determine the dynamic friction coefficient of the sheet surface. It was measured. The smaller the value of the dynamic friction coefficient, the better the surface slipperiness of the vinyl chloride resin molded product, and the better the suppression of surface stickiness.

<Degree of void formation>
The degree of generation of voids in the polyurethane foam molding was evaluated as follows.
That is, the vinyl chloride resin molded sheet was peeled from the laminate to prepare only a foamed polyurethane molded body (200 mm×300 mm×10 mm), which was used as a sample. Then, the sample was cut (divided into 6) in the lateral direction at intervals of 50 mm, and the state of the cross section was visually confirmed. Specifically, the voids having a diameter of 3 mm or more were regarded as voids, and the total number of voids (N ₁ ) existing in 6 sections divided into 6 was counted.
On the other hand, except that the vinyl chloride resin molded sheet was not placed in the mold, a foamed polyurethane molded body was produced by the same procedure as in “Formation of laminate” of Example 1, and the foamed polyurethane molded body was also prepared as described above. The sample was divided into 6 in the same manner as in, and the total number of voids (N ₀ ) existing in the 6 cross sections was counted. It should be noted that N ₀ is not the voids derived from the vinyl chloride resin molded product, but is merely the number of voids derived from the operating procedure for forming the foamed polyurethane molded product.
Then, in each sample, the void generation rate (%)=N ₁ /N ₀ ×100 with N ₀ as a reference (100%) was calculated, and the degree of void generation was evaluated according to the following criteria. The lower the void generation rate (closer to 100%), the less likely voids are generated in the foamed polyurethane molded article adjacent to the vinyl chloride resin molded article.
A: Occurrence rate of voids is less than 120% B: Occurrence rate of voids is 120% or more and less than 150% C: Occurrence rate of voids is 150% or more In addition, if the incidence rate of voids is less than 100%, it is regarded as a measurement error. , Included in the above A evaluation.

(Example 1)
<Preparation of vinyl chloride resin composition>
Among the compounding ingredients shown in Table 1, the ingredients except the plasticizer (trimellitic acid ester and epoxidized soybean oil) and the vinyl chloride resin fine particles as the dusting agent were put into a Henschel mixer and mixed. Then, when the temperature of the mixture rises to 80° C., all of the above plasticizers are added, and the temperature is further raised to dry up (the plasticizer is absorbed by the vinyl chloride resin particles that are vinyl chloride resin, It means that the mixture has become even smoother.). Then, when the dried mixture was cooled to a temperature of 100° C. or lower, vinyl chloride resin fine particles as a dusting agent were added to prepare a vinyl chloride resin composition.

<Formation of vinyl chloride resin molding>
The vinyl chloride resin composition obtained above is sprinkled on a wrinkled mold heated to a temperature of 250° C., left standing for 8 seconds to 20 seconds to melt, and then the excess vinyl chloride resin composition is added. Shaken off. Thereafter, the embossed metal mold sprinkled with the vinyl chloride resin composition was allowed to stand still in an oven set at a temperature of 200° C., and the embossed metal mold was cooled with cooling water when 60 seconds had elapsed from the standing. .. When the mold temperature was cooled to 40° C., a vinyl chloride resin molded sheet of 200 mm×300 mm×1 mm as a vinyl chloride resin molded body was released from the mold.
Then, with respect to the obtained vinyl chloride resin molded sheet, the tensile elongation and the surface slipperiness (dynamic friction coefficient) at an initial (unheated) low temperature were measured and calculated according to the method described above. The results are shown in Table 1.

<Formation of laminated body>
The obtained vinyl chloride resin molded sheet was allowed to stand in an oven set to a temperature of 100° C. for 2 hours, and then laid in a mold of 200 mm×300 mm×10 mm with a grained surface facing down.
Separately, 50 parts of propylene glycol PO (propylene oxide)/EO (ethylene oxide) block adduct (hydroxyl value 28, content of terminal EO unit=10%, content of internal EO unit 4%), PO of glycerin 50 parts of EO block adduct (hydroxyl value 21, content of terminal EO unit=14%), 2.5 parts of water, ethylene glycol solution of triethylenediamine (trade name "TEDA-L33" manufactured by Tosoh Corporation) )), 0.2 parts of triethanolamine, 0.5 parts of triethylamine, and 0.5 parts of a foam stabilizer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "F-122"). , A polyol mixture was obtained. In addition, a mixed solution was prepared in which the obtained polyol mixture and polymethylene polyphenylene polyisocyanate (polymeric MDI) were mixed at a ratio of 98. Then, the prepared mixed liquid was poured onto the vinyl chloride resin molding sheet laid in the mold as described above. Then, the mold was covered with an aluminum plate of 348 mm×255 mm×10 mm, and the mold was sealed. By closing the mold and leaving it for 5 minutes, a molded polyurethane foam (thickness: 9 mm, density: 0.18 g/cm ³ ) is formed on the vinyl chloride resin molding sheet (thickness: 1 mm) as a skin. The lined laminate was formed in the mold.
Then, the formed laminate was taken out from the mold, and the tensile elongation and the degree of void formation at low temperature after heating (heat aging test) were measured and evaluated according to the method described above. The results are shown in Table 1.

(Example 2)
In the preparation of the vinyl chloride resin composition, the vinyl chloride resin composition and the vinyl chloride resin were prepared in the same manner as in Example 1 except that the blending amount of the silicone particles was changed to 0.3 parts as shown in the blending components shown in Table 1. Molded sheets and laminates were produced.
Then, measurement and calculation were performed by the same method as in Example 1. The results are shown in Table 1.

(Comparative example 1)
No silicone oil or silicone particles were used in the preparation of the vinyl chloride resin composition. Further, as shown in Table 1, the amount of the vinyl chloride resin fine particles A was changed from 8 parts to 10 parts, and 10 parts of the vinyl chloride resin fine particles C were used instead of 8 parts of the vinyl chloride resin fine particles B. It was used. Further, the amount of trimellitic acid ester as a plasticizer was changed to 110 parts and the amount of epoxidized soybean oil was changed to 5 parts. Further, the amount of hydrotalcite treated with perchloric acid as an additive was 4.56 parts, the amount of zeolite was 2.42 parts, the amount of β-diketone was 0.49 parts, and zinc stearate. Was changed to 0.20 parts. A vinyl chloride resin composition, a vinyl chloride resin molded sheet, and a laminate were produced in the same manner as in Example 1 except for the above.
Then, measurement and calculation were performed by the same method as in Example 1. The results are shown in Table 1.

(Comparative example 2)
A vinyl chloride resin composition, a vinyl chloride resin molded sheet, and a laminate were produced in the same manner as in Example 1 except that the ether-modified silicone oil was not used in the preparation of the vinyl chloride resin composition.
Then, measurement and calculation were performed by the same method as in Example 1. The results are shown in Table 1.

(Comparative example 3)
In the preparation of the vinyl chloride resin composition, the ether-modified silicone oil and the silicone particles were not used, and 0.4 part of the unmodified silicone oil was used. Further, as shown in Table 1, the amount of the vinyl chloride resin fine particles A was changed from 8 parts to 10 parts, and 10 parts of the vinyl chloride resin fine particles C were used instead of 8 parts of the vinyl chloride resin fine particles B. It was used. Further, the amount of trimellitic acid ester as a plasticizer was changed to 110 parts and the amount of epoxidized soybean oil was changed to 5 parts. Further, the amount of hydrotalcite treated with perchloric acid as an additive was 4.56 parts, the amount of zeolite was 2.42 parts, the amount of β-diketone was 0.49 parts, and zinc stearate. Was changed to 0.20 parts. A vinyl chloride resin composition, a vinyl chloride resin molded sheet, and a laminate were produced in the same manner as in Example 1 except for the above.
Then, measurement and calculation were performed by the same method as in Example 1. The results are shown in Table 1.

(Comparative example 4)
In the preparation of the vinyl chloride resin composition, 0.4 part of silanol modified silicone oil was used without using ether modified silicone oil and silicone particles. Further, as shown in Table 1, the amount of the vinyl chloride resin fine particles A was changed from 8 parts to 10 parts, and 10 parts of the vinyl chloride resin fine particles C were used instead of 8 parts of the vinyl chloride resin fine particles B. It was used. Further, the amount of trimellitic acid ester as a plasticizer was changed to 110 parts and the amount of epoxidized soybean oil was changed to 5 parts. Further, the amount of hydrotalcite treated with perchloric acid as an additive was 4.56 parts, the amount of zeolite was 2.42 parts, the amount of β-diketone was 0.49 parts, and zinc stearate. Was changed to 0.20 parts. A vinyl chloride resin composition, a vinyl chloride resin molded sheet, and a laminate were produced in the same manner as in Example 1 except for the above.
Then, measurement and calculation were performed by the same method as in Example 1. The results are shown in Table 1.

1) New Dai-ichi PVC Co., Ltd., product name "ZEST (registered trademark) 1700ZI" (suspension polymerization method, average degree of polymerization: 1700, average particle size: 130 μm)
2) Product name “ZEST PQLTX” manufactured by Shin-Daiichi PVC Co., Ltd. (emulsion polymerization method, average degree of polymerization: 800, average particle size: 1.8 μm)
3) Tosoh Corporation, product name "Leuron Paste (registered trademark) 860" (emulsion polymerization method, average degree of polymerization: 1600, average particle diameter: 1.6 μm)
4) Tosoh Corporation, product name "Luron Paste (registered trademark) 761" (emulsion polymerization method, average degree of polymerization: 2100, average particle diameter: 1.6 μm)
5) Product name "Trimex N-08" manufactured by Kao Corporation
6) Product name "ADEKA CIZER O-130S" manufactured by ADEKA
7) manufactured by Shin-Etsu Chemical Co., Ltd., product name “X-50-1039A” (ether-modified silicone oil [formed by introducing an ether group having a chain ethylene oxide structure and a chain propylene oxide structure into a side chain], HLB value : 2, viscosity at 25°C: 500 cs)
8) Product name “KF-96” manufactured by Shin-Etsu Chemical Co., Ltd. (unmodified silicone oil, HLB value: 0, viscosity at 25° C.: 5000 cs)
9) Product name “KF-9701” manufactured by Shin-Etsu Chemical Co., Ltd. (silanol-modified silicone oil, HLB value: 0, viscosity at 25° C.: 60 cs)
10) manufactured by Shin-Etsu Chemical Co., Ltd., product name "X-22-8171" (acrylic modified silicone particles, spherical)
11) Product name "Alkamizer (registered trademark) 5" manufactured by Kyowa Chemical Industry Co., Ltd.
12) Product name "MIZUKALIZER DS" manufactured by Mizusawa Chemical Industry Co., Ltd.
13) Showa Denko KK, product name "Karenzu DK-1"
14) Sakai Chemical Industry Co., Ltd., product name "SAKAI SZ2000"
15) Product name "ADEKA STAB LS-12" manufactured by ADEKA
16) Product name "DA PX 1720 (A) Black" manufactured by Dainichi Seika Co., Ltd.

From Table 1, it was found that in Comparative Example 1 in which no silicone oil or silicone particles were used, the surface slipperiness of the vinyl chloride resin sheet was remarkably inferior.
Further, in Comparative Examples 3 to 4 in which only the silicone oil other than the ether-modified silicone oil was used, it was found that voids were easily generated in the foamed polyurethane molded body laminated adjacent to the vinyl chloride resin sheet.
Furthermore, in Comparative Example 2 using only silicone particles, it was found that there is room for improvement in further improving the surface slipperiness of the vinyl chloride resin sheet.
On the other hand, in Examples 1 and 2 using the vinyl chloride resin, the plasticizer, the ether-modified silicone oil, and the silicone particles, the generation of voids in the foamed polyurethane molded article was satisfactorily suppressed while the vinyl chloride resin molded article It was found that the surface slipperiness was further improved, and both the surface slipperiness and the suppression of the generation of voids in the polyurethane foam molding could be achieved at a higher level.
In addition, in Example 2 in which the blending amount of silicone particles was relatively small, it was found that the tensile elongation at low temperature of the vinyl chloride resin molded product can be remarkably improved as compared with Example 1 in which the blending amount of silicone particles is relatively large. It was

According to the present invention, a vinyl chloride resin molded article having excellent surface slipperiness and capable of suppressing the occurrence of voids in a laminated polyurethane foam molded article, and the vinyl chloride resin molded article can be produced. A vinyl chloride resin composition can be provided.
Further, according to the present invention, it is possible to provide a laminate having a foamed polyurethane molded body and a vinyl chloride resin molded body, which has excellent surface slipperiness and in which generation of voids is suppressed.

Claims (12)

It is seen containing a vinyl chloride resin, a plasticizer, a polyether-modified silicone oil, and silicone particles, and,
A vinyl chloride resin composition in which the viscosity of the ether-modified silicone oil is 300 cs or more and 1000 cs or less at a temperature of 25°C . The vinyl chloride resin composition according to claim 1, wherein the silicone particles are acrylic-modified silicone particles. The vinyl chloride resin composition according to claim 1 or 2, wherein the content of the silicone particles is 0.3 part by mass or less based on 100 parts by mass of the vinyl chloride resin. The vinyl chloride resin composition according to any one of claims 1 to 3, wherein the content of the silicone particles is 0.3 part by mass or less based on 100 parts by mass of the plasticizer. The vinyl chloride resin composition according to any one of claims 1 to 4, wherein the content of the silicone particles is 0.5 times or more and 10 times or less the content of the ether-modified silicone oil in terms of mass. .. The vinyl chloride resin composition according to any one of claims 1 to 5, wherein the ether-modified silicone oil has an HLB value of 1.5 or more. The vinyl chloride resin composition according to any one of claims 1 to 6, wherein the ether-modified silicone oil has an ether group having a chain ethylene oxide structure and a chain propylene oxide structure introduced into a side chain . Used in the powder molding, the vinyl chloride resin composition according to any one of claims 1-7. The vinyl chloride resin composition according to claim 8 , which is used for powder slush molding. A vinyl chloride resin molded body obtained by molding the vinyl chloride resin composition according to any one of claims 1 to 9 . The vinyl chloride resin molded product according to claim 10 , which is used for a skin of an automobile instrument panel. A foamed polyurethane molded body,
A vinyl chloride resin molding according to claim 10 or 11 ,
A laminate having.