JP2018053095A - Vinyl chloride resin composition, vinyl chloride resin molded body, and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vinyl chloride resin composition capable of producing a vinyl chloride resin molded body which is excellent in surface slipperiness and can prevent a void from generated in a laminated foamed polyurethane molded body.SOLUTION: A vinyl chloride resin composition contains a vinyl chloride resin, a plasticizer, polyether-modified silicone oil and silicone particles. In the vinyl chloride resin composition, the silicone particles are acrylic modified silicone particles.SELECTED DRAWING: None

Description

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

Vinyl chloride resins are generally used in various applications because they are excellent in properties such as cold resistance, heat resistance, and oil resistance.
Specifically, for example, conventionally, for the formation of automobile interior parts such as automobile instrument panels, a foam made of foamed polyurethane or the like is lined with a skin made of a vinyl chloride resin molded body or a skin made of a vinyl chloride resin molded body. Automotive interior materials such as laminates are used. The vinyl chloride resin molded body constituting the skin of automotive interior parts such as automotive instrument panels is required to have various performances such as good surface slipperiness that suppresses stickiness of the molded body surface. Yes.

  In recent years, therefore, attempts have been made to improve vinyl chloride resin compositions and vinyl chloride resin molded bodies that can be suitably used for the production of automobile interior parts such as automobile instrument panels.

Specifically, for example, in Patent Document 1, a vinyl chloride resin molded body 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 blended. . And in the vinyl chloride resin molding of patent document 1, the bleeding property of a plasticizer (ease of exuding to the surface) and the fluffiness property (easiness of fiber residue when the surface is wiped with a cloth, surface stickiness) (Attachability) is reduced.
Further, for example, Patent Document 2 discloses a vinyl chloride resin composition comprising a specific amount of vinyl chloride resin particles, a plasticizer, vinyl chloride resin fine particles, and acrylic-modified polyorganosiloxane particles. Is disclosed. And in the vinyl chloride resin sheet obtained by using the vinyl chloride resin composition described in Patent Document 2, fibers are difficult to adhere to the sheet surface rubbed with gauze, and the non-adhesiveness (surface slipperiness) of the surface Is good.

JP 2012-7026 A JP, 2015-117314, A

  However, as a result of repeated studies by the present inventor, a laminate comprising a foamed polyurethane molded product lined on a vinyl chloride resin molded product formed using the conventional vinyl chloride resin composition described in Patent Document 1 is produced. Then, although the surface slipperiness of the vinyl chloride resin molded article was improved, it was revealed that relatively large voids (voids) were generated in the foamed polyurethane molded article. Further, in the vinyl chloride resin molded article formed using the conventional vinyl chloride resin composition described in Patent Document 2, there is no noticeable problem that voids are generated in the foamed polyurethane molded article. There was room for improvement in further improving the surface slipperiness of the molded body.

Therefore, the present invention is capable of producing a vinyl chloride resin molded article that has excellent surface slipperiness and that can suppress the generation 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.
Another object of the present invention is to provide a laminate having a foamed polyurethane molded product and a vinyl chloride resin molded product, which has excellent surface slipperiness and generation of voids.

  The present inventor has intensively studied for the purpose of solving the above problems. And, when the present inventors use ether-modified silicone oil and silicone particles in combination, the good surface slipperiness of the vinyl chloride resin molded article and voids in the foamed polyurethane molded article laminated on the vinyl chloride resin molded article. The present inventors have found that it is possible to achieve both suppression of occurrence and complete the present invention.

  That is, the present invention aims to advantageously solve the above problems, and the vinyl chloride resin composition of the present invention comprises a vinyl chloride resin, a plasticizer, an ether-modified silicone oil, 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 formed by molding the composition has excellent surface slipperiness, and Generation of voids in the foamed polyurethane molded product when laminated with the foamed polyurethane molded product can be suppressed.

  Here, in the vinyl chloride resin composition of the present invention, the silicone particles are preferably acrylic-modified silicone particles. If acrylic modified silicone particles are used, the surface of the vinyl chloride resin molded product is suppressed while suppressing the generation of voids in the polyurethane foam molded product laminated on the vinyl chloride resin molded product formed by molding the vinyl chloride resin composition. This is because the slipperiness can be improved.

  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 with respect to 100 parts by mass of the vinyl chloride resin. This is because if the content of the silicone particles is not more than the above upper limit, the tensile elongation at a low temperature of the vinyl chloride resin molded article can be increased.

  Moreover, it is preferable that content of the said silicone particle is 0.3 mass part or less with respect to 100 mass parts of said plasticizers in the vinyl chloride resin composition of this invention. This is because if the content of the silicone particles is not more than the above upper limit, the tensile elongation at a low temperature of the vinyl chloride resin molded article can be increased.

  In the vinyl chloride resin composition of the present invention, the content of the silicone particles is preferably 0.5 to 10 times the content of the ether-modified silicone oil in terms of mass. This is because if the content of the silicone particles relative to the content of the ether-modified silicone oil is not less than the above lower limit, the surface slipperiness of the vinyl chloride resin molded article can be further improved. Further, if 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 polyurethane foam molded body laminated on the vinyl chloride resin molded body is further suppressed, and This is because the tensile elongation at a low temperature of the vinyl resin molded article can be sufficiently secured.

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 if an ether-modified silicone oil having an HLB value equal to or higher than the above lower limit is used, it is possible to further suppress the generation of voids in the polyurethane foam molded body laminated on the vinyl chloride resin molded body.
In the present invention, the “HLB value” refers to the Drophile-Lipophile Balance, and the following formula (1) according to the Griffin method:
HLB value = 20 ×
(Sum of formula weight of chain ethylene oxide structure / molecular weight) (1)
It is an index showing 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.

  Furthermore, the vinyl chloride resin composition of the present invention is preferably used for powder molding. If 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 article used for automobile interior parts such as an automobile instrument panel. Because you can.

  And it is preferable that the vinyl chloride resin composition of this invention is 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 article used for automobile interior parts such as automobile instrument panels. Because you can.

  Further, the present invention aims to advantageously solve the above-mentioned problems, and the vinyl chloride resin molded article of the present invention is formed by molding any of the above-described vinyl chloride resin compositions. And If a vinyl chloride resin molded product is formed using the above-mentioned vinyl chloride resin composition, the generation of voids in the polyurethane foam molded product laminated on the vinyl chloride resin molded product can be improved while realizing good surface slipperiness. Can be suppressed.

  Here, the vinyl chloride resin molded article of the present invention is preferably for an automotive instrument panel skin. When the vinyl chloride resin molded article of the present invention is used as the skin of an automobile instrument panel, an automotive instrument panel having a good surface stickiness and a well-lined polyurethane polyurethane molded article is produced. Because you get.

  Furthermore, this invention aims at solving the said subject advantageously, and the laminated body of this invention has a foaming polyurethane molding and one of the vinyl chloride resin moldings mentioned above. Features. When a foamed polyurethane molded body and the above-described vinyl chloride resin molded body are used as a laminate, for example, a foamed polyurethane molded body and a vinyl chloride resin molded body suitable for automobile interior materials are satisfactorily laminated, and surface slipperiness is achieved. Can be obtained.

ADVANTAGE OF THE INVENTION According to this invention, it is excellent in surface slip property, and can manufacture the vinyl chloride resin molded object which can suppress generation | occurrence | production of a space | gap in the laminated polyurethane polyurethane molded object, and the said vinyl chloride resin molded object can be manufactured. A vinyl chloride resin composition can be provided.
Moreover, according to this invention, the laminated body which has the foaming polyurethane molded object and the vinyl chloride resin molded object which were excellent in surface slipperiness and generation | occurrence | production of the space | gap was suppressed can be provided.

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, when obtaining the vinyl chloride resin molded article of the present invention. Moreover, the vinyl chloride resin molded object formed by shape | molding the vinyl chloride resin composition of this invention can be used for manufacture of the laminated body of this invention which has the said vinyl chloride resin molded object, for example. The vinyl chloride resin molded body 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 since the vinyl chloride resin composition of this invention contains the said predetermined | prescribed component, if the vinyl chloride resin composition of this invention is used, the vinyl chloride resin molded object which is excellent in surface slipperiness | liquidity can be obtained. Further, when the foamed polyurethane molded product is laminated on the vinyl chloride resin molded product obtained by molding the vinyl chloride resin composition of the present invention, the generation of voids in the foamed polyurethane molded product is suppressed, and the vinyl chloride resin The laminated body which has a molded object and a urethane foam molded object can be manufactured favorably.

<Vinyl chloride resin>
Here, as the vinyl chloride resin contained in the vinyl chloride resin composition, for example, one type or two or more types of vinyl chloride resin particles can be contained, and optionally one type or two or more types of vinyl chloride resin particles. Can further be contained. 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, one kind of vinyl chloride resin particles and two kinds of vinyl chloride resins. More preferably, it contains fine particles.
In the present specification, “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 vinyl chloride resin can be produced by any conventionally known production method such as suspension polymerization method, emulsion polymerization method, solution polymerization method, bulk polymerization method and the like.

<< Composition >>
As the vinyl chloride resin, in addition to a homopolymer composed of vinyl chloride monomer units, vinyl chloride copolymers containing vinyl chloride monomer units are preferably 50% by mass or more, more preferably 70% by mass or more. Can be mentioned. Specific examples of a monomer (comonomer) copolymerizable with a vinyl chloride monomer that can constitute a vinyl chloride copolymer include olefins such as ethylene and propylene; allyl chloride, vinylidene chloride, Halogenated olefins such as vinyl fluoride and ethylene trifluorochloride; 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, maleic anhydride, Its esters or acid anhydrides; Unsaturated nitriles such as acrylonitrile and methacrylonitrile; acrylamides such as acrylamide, N-methylolacrylamide, acrylamide-2-methylpropanesulfonic acid, (meth) acrylamidepropyltrimethylammonium chloride; allylamine benzoate, diallyldimethylammonium And allylamine such as chloride and derivatives thereof. 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. These comonomer may use only 1 type and may use 2 or more types. The vinyl chloride resin includes ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, chlorinated polyethylene, and other resins such as (1) vinyl chloride or ( 2) A resin obtained by graft polymerization of 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 polymerization degree]
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, preferably 5000 or less, more preferably 3000 or less, still more preferably 2500 or less, and 2000 or less. Even more preferred. If the average degree of polymerization of the vinyl chloride resin particles is equal to or higher than the above lower limit, for example, the vinyl chloride resin molded article is used in an automobile while ensuring the physical strength of the vinyl chloride resin molded article formed by molding the vinyl chloride resin composition. This is because the tensile elongation at a low temperature, which is suitable for use as the skin of an instrument panel, can be improved. Moreover, 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 the present invention, the “average polymerization degree” can be measured according to JIS K6720-2.

[Average particle size]
The average particle diameter 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 equal to or greater than the above lower limit, the powder flowability of the vinyl chloride resin composition is further improved. Further, if 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 body formed using the composition is improved. It is because it can improve more.
In the present invention, the “average particle diameter” can be measured as a volume average particle diameter by a laser diffraction method in accordance with 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 more preferably 100% by mass with respect to 100% by mass of the total vinyl chloride resin. It is preferable that it is 95 mass% or less, and it is more preferable that it is 90 mass% or less. If the content ratio of the vinyl chloride resin particles in the vinyl chloride resin is equal to or higher than the above lower limit, the tensile strength at a low temperature is ensured while sufficiently securing the physical strength of the vinyl chloride resin molded article formed by molding the vinyl chloride resin composition. This is because the elongation can be improved. Moreover, it is because the powder fluidity | liquidity of a vinyl chloride resin composition will further improve if the content rate of the vinyl chloride resin particle in a vinyl chloride resin is below the said upper limit.

<< Vinyl chloride resin fine 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 polymerization degree]
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 even more preferably 2500 or less. For example, when two kinds of vinyl chloride resin fine particles having different average polymerization degrees are used in combination as the dusting agent, the average value of the average polymerization degree of the combined dusting agent is preferably 1000 or more, and less than 1500 It is preferable that If the average degree of polymerization of the vinyl chloride resin fine particles as the dusting agent is not less than the above lower limit, the powder flowability of the vinyl chloride resin composition becomes better, and the molded article obtained using the composition has a low temperature. This is because the tensile elongation at is improved. Further, if 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 article formed by molding the composition is more It is because it improves.

[Average particle size]
The average particle diameter of the vinyl chloride resin fine particles is usually less than 30 μm, preferably 10 μm or less, and preferably 0.1 μm or more. This is because, if the average particle diameter of the vinyl chloride resin fine particles is not less than the above lower limit, for example, the powder fluidity of the vinyl chloride resin composition can be further improved without excessively reducing the size as a dusting agent. . Moreover, if 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 more preferably 30% by mass or less with respect to 100% by mass of the vinyl chloride resin. Preferably, it is 20 mass% or less, and may be 0 mass%. This is because the powder flowability of the vinyl chloride resin composition is further improved if the content ratio of the vinyl chloride resin fine particles in the vinyl chloride resin is not less than the above lower limit. Further, if 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 of the vinyl chloride resin molded article formed by molding the vinyl chloride resin composition and the tensile elongation at low temperature are further increased. 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. Preferably, it is 200 parts by mass or less, more preferably 150 parts by mass or less, still more preferably 100 parts by mass or less, and still more preferably 95 parts by mass or less. If the content of the plasticizer is at least the above lower limit, the vinyl chloride resin composition is provided with excellent flexibility, for example, it can be easily processed into a vinyl chloride resin molded article, and the resulting vinyl chloride resin molded article can be obtained. This is because good tensile elongation at low temperatures can be imparted. Moreover, if content of a plasticizer is below the said upper limit, it is because the stickiness of the surface of the obtained vinyl chloride resin molding can be suppressed more and surface slipperiness can be improved more.

<<< Type >>>
Here, specific examples of the plasticizer include the following primary plasticizer and secondary plasticizer.
As so-called primary plasticizers, trimethyl trimellitic acid, triethyl trimellitic acid, tri-n-propyl trimellitic acid, tri-n-butyl trimellitic acid, tri-n-pentyl trimellitic acid, tri-n trimellitic acid -Hexyl, tri-n-heptyl trimellitic acid, tri-n-octyl trimellitic acid, tri-n-nonyl trimellitic acid, tri-n-decyl trimellitic acid, tri-n-undecyl trimellitic acid, trimellitic Tri-n-dodecyl acid, tri-n-tridecyl trimellitic acid, tri-n-tetradecyl trimellitic acid, tri-n-pentadecyl trimellitic acid, tri-n-hexadecyl trimellitic acid, tri-n-trimellitic acid Heptadecyl, trimellitic acid tri-n-stearyl, trimellitic acid tri-n-a The alkyl group constituting the ester such as a kill ester (wherein the carbon number of the alkyl group of the trimellitic acid tri-n-alkyl ester may be different in one molecule) is linear. Linear trimellitic acid ester [Note that these trimellitic acid esters may be composed of a single compound or a mixture thereof. ];
Trimellitic acid tri-i-propyl, trimellitic acid tri-i-butyl, trimellitic acid tri-i-pentyl, trimellitic acid tri-i-hexyl, trimellitic acid tri-i-heptyl, trimellitic acid 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 trimethyl -I-octadecyl, trimellitic acid trialkyl ester (where trimellitic acid Branched trimellitic acid esters in which the alkyl group constituting the ester is branched, such as the carbon number of the alkyl group in the alkyl ester may be different from each other in one molecule. The ester may be a single compound or a mixture. ];
Pyromellitic acid 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 Tetra-n-heptyl, pyromellitic acid 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 -N-stearyl, pyromellitic acid tet The alkyl group constituting the ester such as -n-alkyl ester (wherein the carbon number of the alkyl group of the pyromellitic acid tetra-n-alkyl ester may be different in one molecule) is linear Linear pyromellitic acid ester [These pyromellitic acid esters may be composed of a single compound or a mixture. ];
Pyromellitic acid 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- i-octyl, pyromellitic acid 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 -I-octadecyl, pyromellitic acid tetraalkyl Branched pyromellitic acid in which the alkyl group constituting the ester is branched, such as an ester (wherein the carbon number of the alkyl group of the pyromellitic acid tetraalkyl ester may be different from each other in one molecule) Esters [These pyromellitic acid esters may be composed of a single compound or a mixture thereof. ];
Dimethyl phthalate, diethyl phthalate, dibutyl phthalate, di- (2-ethylhexyl) phthalate, di-n-octyl phthalate, diisobutyl phthalate, diheptyl phthalate, diphenyl phthalate, diisodecyl phthalate, ditridecyl phthalate, diundecyl phthalate, dibenzyl phthalate, Phthalic acid derivatives such as butylbenzyl phthalate, dinonyl phthalate, dicyclohexyl phthalate;
Isophthalic acid derivatives such as dimethyl isophthalate, di- (2-ethylhexyl) isophthalate, diisooctyl isophthalate;
Tetrahydrophthalic acid derivatives such as di- (2-ethylhexyl) tetrahydrophthalate, di-n-octyltetrahydrophthalate, diisodecyltetrahydrophthalate;
Adipic acid derivatives such as di-n-butyl adipate, di- (2-ethylhexyl) adipate, diisodecyl adipate, diisononyl adipate;
Azelaic acid derivatives such as di- (2-ethylhexyl) azelate, diisooctylazelate, di-n-hexylazelate;
Sebacic acid derivatives such as di-n-butyl sebacate, di- (2-ethylhexyl) sebacate, diisodecyl sebacate, di- (2-butyloctyl) sebacate;
Maleic acid derivatives such as di-n-butyl maleate, dimethyl maleate, diethyl maleate, di- (2-ethylhexyl) maleate;
Fumaric acid derivatives such as di-n-butyl fumarate, di- (2-ethylhexyl) fumarate;
Citric acid derivatives such as triethyl citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tri- (2-ethylhexyl) citrate;
Itaconic acid derivatives such as monomethyl itaconate, monobutyl itaconate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, di- (2-ethylhexyl) itaconate;
Oleic acid derivatives such as butyl oleate, glyceryl monooleate, diethylene glycol monooleate;
Ricinoleic acid derivatives such as methylacetylricinoleate, butylacetylricinoleate, glycerylmonoricinoleate, diethylene glycol monoricinoleate;
stearic acid derivatives such as n-butyl stearate and diethylene glycol distearate (excluding 12-hydroxystearic acid and its esters);
Other fatty acid derivatives such as diethylene glycol monolaurate, diethylene glycol dipelargonate, pentaerythritol fatty acid ester;
Phosphoric acid derivatives such as triethyl phosphate, tributyl phosphate, tri- (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (chloroethyl) phosphate;
Diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, triethylene glycol di- (2-ethylbutyrate), triethylene glycol di- (2-ethylhexoate), dibutylmethylene bisthioglycolate, etc. A glycol derivative of
Glycerol derivatives such as glycerol monoacetate, glycerol triacetate, glycerol tributyrate;
Epoxy derivatives such as epoxy hexahydrophthalate diisodecyl, epoxy triglyceride, epoxidized octyl oleate, epoxidized decyl oleate;
Polyester plasticizers such as adipic acid polyester, sebacic acid polyester, phthalic acid polyester;
Etc.

  In addition, so-called secondary plasticizers include epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil; fatty acid esters of glycols such as chlorinated paraffin and triethylene glycol dicaprylate, butyl epoxy stearate, phenyl oleate And methyl dihydroabietate.

  In addition, these plasticizers may use only 1 type, for example, may use together 2 or more types, such as a primary plasticizer and a secondary plasticizer. Moreover, when using a secondary plasticizer, it is preferable to use together the said primary plasticizer and the primary plasticizer of equal mass or more.

  Among the plasticizers described above, 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, and use trimellitic acid ester. 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. Moreover, it is preferable that carbon number of the said alkyl group is 8-10, and it is more preferable that the said alkyl group is n-octyl group and n-decyl group. And it is preferable to further use an 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 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 can be obtained while improving the surface slipperiness of the vinyl chloride resin molded article obtained by molding the vinyl chloride resin composition containing a plasticizer. It is possible to satisfactorily suppress the generation of voids in the foamed polyurethane molded product laminated.
In addition, when the content of the plasticizer is relatively large, the compatibility between the improvement of the surface slipperiness and the suppression of the generation of voids due to the inclusion of the ether-modified silicone oil together with the silicone particles, specifically, the vinyl chloride resin 100 mass. This is more effectively realized when the content of the plasticizer with respect to the part 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 a terminal 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. In addition, when an ether group is introduced at the terminal, it may be introduced at one end or at both ends. Further, the ether-modified silicone oil may be further introduced with other substituents other than the ether group at the main chain, the side chain of the main chain, and / or the terminal of the main chain.
The ether-modified silicone oil is preferably formed by introducing an ether group into at least the 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 Formula (2), x is a natural number of 1 or more. ] A substituent having only a chain ethylene oxide structure represented by the formula (in the formula (2), when x is a natural number of 2 or more, also referred to as “polyethylene oxide group”); General formula (3):
[Chemical formula 2]
_{- (C 3 H 6 O)} y - (3)
[In Formula (3), y is a natural number of 1 or more. A substituent having an arbitrary ratio of a chain propylene oxide structure represented by the formula (in the formula (3), when y is a natural number of 2 or more, also referred to as “polypropylene oxide group”); In addition to the structure, a substituent (for example, —R— (C ₂ H ₄ O) _x — further having an arbitrary organic structure other than the chain alkylene oxide structure (hereinafter, referred to as “R” and “R ′”). R ′); in addition to the chain alkylene oxide structures such as the chain ethylene oxide structure and the chain propylene oxide structure, the substituent further includes 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, from the viewpoint of further suppressing the generation of voids in the foamed polyurethane molded product adjacent to the vinyl chloride resin molded product while improving the surface slipperiness of the vinyl chloride resin molded product, the ether group is not clear. , Preferably having at least a chain ethylene oxide structure, more preferably having a chain ethylene oxide structure and a chain propylene oxide structure, more preferably having a plurality of chain ethylene oxide structures and chain propylene oxide structures, Furthermore, it is more preferable not to have an unsaturated bond from the viewpoint of excellent heat aging resistance.

[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} ; a is an arbitrary natural number), an aralkyl group (for example, — CH ₂ —CH (CH ₃ ) —C ₆ H ₅ ; where C ₆ H ₅ is a phenyl group).

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

<< Viscosity >>
The viscosity of the ether-modified silicone oil is preferably 65 cs or more, more preferably 100 cs or more, further preferably 300 cs or more, more preferably 4000 cs or less, at a temperature of 25 ° C. More preferably, it is 3000 cs or less, and still more preferably 1000 cs or less. If the viscosity of the ether-modified silicone oil is not less than the above lower limit, foaming polyurethane molding while reducing the defoaming effect and maintaining the surface slipperiness of the vinyl chloride resin molded article formed by molding the vinyl chloride resin composition is better. It is because it can suppress more that a space | gap generate | occur | produces in the lamination | stacking process of a body. 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, “viscosity” can be measured in accordance with ASTM D 445-46T at a temperature of 25 ° C. as 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 with respect to 100 parts by mass of the vinyl chloride resin. Preferably, it is 0.5 part by mass or less, and more preferably 0.4 part by mass or less. If an ether-modified silicone oil having a content exceeding the above lower limit is used in combination with silicone particles, the stickiness of the surface of the vinyl chloride resin molded body can be sufficiently reduced, the surface slipperiness can be further improved, and the adjacent foamed polyurethane molding This is because voids in the body can be sufficiently suppressed. Further, if the content of the ether-modified silicone oil is not more than the above upper limit, for example, even when the vinyl chloride resin molded body is continuously molded, a mold for molding due to an excessive amount of the ether-modified silicone oil This is because it is possible to suppress contamination of the surface such as.

  Further, 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 with respect to 100 parts by mass of the plasticizer, and 1 part by mass or less. It is preferably 0.5 parts by mass or less, and more preferably 0.4 parts by mass or less. In general, plasticizers tend to cause stickiness of the surface of the molded body. However, if ether-modified silicone oil having a content higher than the above lower limit is used in combination with silicone particles, the surface of the vinyl chloride resin molded body is sufficiently sticky. This is because the surface slipperiness can be further improved and the voids in the foamed polyurethane molded product to be laminated can be sufficiently suppressed. Further, if the content of the ether-modified silicone oil is not more than the above upper limit, for example, even when the vinyl chloride resin molded body is continuously molded, a mold for molding due to 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 usually has fluidity at normal temperature. In the present invention, “normal temperature” refers to 23 ° C.

<Silicone particles>
The vinyl chloride resin composition of the present invention is characterized by further containing silicone particles in addition to the above-described vinyl chloride resin, plasticizer and ether-modified silicone oil. When the vinyl chloride resin composition further contains silicone particles together with the ether-modified silicone oil described above, a plasticizer can be added while suppressing the generation of voids in the foamed polyurethane molded product laminated with the vinyl chloride resin molded product. The surface slipperiness of the vinyl chloride resin molded article formed by molding the vinyl chloride resin composition containing the resin composition can be improved.
In addition, when the content of the plasticizer is relatively large, the compatibility of the improvement of the surface slipping property and the suppression of the generation of voids due to the inclusion of the silicone particles together with the ether-modified silicone oil is specifically 100 parts by mass of the vinyl chloride resin. This is realized more effectively when the content of the plasticizer with respect to is 70 parts by mass or more.

<< 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 randomly polymerized random structure; a ladder structure polymerized by forming a two-dimensional repeating structure; a cage structure polymerized by forming a three-dimensional repeating three-dimensional structure; Can have a structure.
Further, the silicone particle is preferably a methyl group (—CH ₃ ) and / or an ethyl group other than the oxygen atom (O) in the silicon atom (Si) forming the main skeleton in the polysiloxane main skeleton. (—C ₂ H ₅ ) is bonded, and more preferably, an oxygen atom and a methyl group are bonded. Furthermore, the silicone particle is preferably a polyorganosiloxane (organic modified silicone particle) having a structure in which a silicon atom (Si) is bonded to any one or more organic groups R ″, where R ″ is − More preferably, it is a (meth) acryl-modified silicone particle represented by OCOCH═CH ₂ or —OCOC (CH ₃ ) ═CH ₂ , and the above R ″ is —OCOCH═CH _2. More preferably, it is a particle. This is because the use of (meth) acryl-modified silicone particles, especially acrylic-modified silicone particles, can further improve the surface slipperiness of the vinyl chloride resin molded article.
For example, the acrylic-modified silicone particles are a silicone-acrylic graft copolymer introduced by graft polymerization of —OCOCH═CH ₂ groups on a polysiloxane main skeleton.

<< Shape >>
Further, the shape of the silicone particles is not particularly limited, and may be any shape such as a spherical shape; a spherical shape with a protrusion having a protruding portion on a spherical body; an indefinite shape; Among these, from the viewpoint of giving excellent surface slipperiness to the vinyl chloride resin molded article, the shape of the silicone particles is preferably spherical.

<< Content >>
And it is preferable that it is 0.01 mass part or more with respect to 100 mass parts of vinyl chloride resin, and, as for content of a silicone particle, it is more preferable that it is 0.1 mass part or more, and it is less than 1 mass part. Is preferably 0.5 parts by mass or less, and more preferably 0.3 parts by mass or less. If silicone particles with a content of the above lower limit or more are used in combination with ether-modified silicone oil, the surface of the vinyl chloride resin molded article is satisfactorily suppressed while sufficiently suppressing the generation of voids in the laminated foamed polyurethane molded article. This is because the surface slipperiness can be further increased. Moreover, it is because the tensile elongation in the low temperature of a vinyl chloride resin molded object can fully be ensured if content of a silicone particle is below the said upper limit. 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 at a low temperature of the vinyl chloride resin molded body can be further increased.

  Moreover, it is preferable that content of a silicone particle is 0.01 mass part or more with respect to 100 mass parts of plasticizers, it is more preferable that it is 0.1 mass part or more, and it is less than 1 mass part. Preferably, it is 0.5 parts by mass or less, and more preferably 0.3 parts by mass or less. In general, plasticizers tend to cause stickiness on the surface of the molded body. However, if silicone particles having a content exceeding the above lower limit are used in combination with an ether-modified silicone oil, voids in the laminated foamed polyurethane molded body are generated. This is because the stickiness of the surface of the vinyl chloride resin molded article can be satisfactorily reduced and the surface slipperiness can be further enhanced while being sufficiently suppressed. Moreover, it is because the tensile elongation in the low temperature of a vinyl chloride resin molded object can fully be ensured if content of a silicone particle is below the said upper limit. 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 plasticizer, the tensile elongation at a low temperature of the vinyl chloride resin molded body can be further increased.

  Further, the content of the silicone particles is preferably 0.5 times or more, more preferably 1 or more times, and 1.3 times or more of the content of the ether-modified silicone oil in terms of mass. Is more preferably 10 times or less, more preferably 5 times or less, and still more preferably 3 times or less. This is because if the content of the silicone particles relative to the content of the ether-modified silicone oil is not less than the above lower limit, the stickiness of the surface of the vinyl chloride resin molded body can be further reduced and the surface slipperiness can be further enhanced. . In addition, if the content of the silicone particles relative to the content of the ether-modified silicone oil is less than the above upper limit, the generation of voids in the laminated foamed polyurethane molded product is further suppressed, and the tensile strength of the vinyl chloride resin molded product at low temperature is further reduced. This is because sufficient elongation can be secured.

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

<< Perchloric acid-treated hydrotalcite >>
The perchloric acid-treated hydrotalcite that can be contained in the vinyl chloride resin composition is, for example, added to a dilute aqueous solution of perchloric acid and stirred, and then filtered, dehydrated or dried as necessary. By substituting at least a part of the carbonate anion (CO ₃ ²⁻ ) in the hydrotalcite with a perchlorate anion (ClO ₄ ⁻ ) (2 mol of the perchlorate anion is substituted for 1 mol of the carbonate anion). It can be easily produced as a perchloric acid-introduced hydrotalcite. The molar ratio of the hydrotalcite and the perchloric acid can be arbitrarily set, but generally 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 rate of the carbonate anion to the perchlorate anion in the untreated (unsubstituted without introducing the perchlorate anion) is preferably 50 mol% or more, more preferably 70 mol%. As mentioned above, More preferably, it is 85 mol% or more. Further, the substitution rate of the carbonate anion to the perchlorate anion in the untreated (unsubstituted without introducing a perchlorate anion) is preferably 95 mol% or less. The replacement rate of carbonate anion to perchlorate anion in untreated (unsubstituted without introduced perchlorate anion) is within the above range, making it easier to mold vinyl chloride resin This is because it can be manufactured.

Hydrotalcite is a non _- stoichiometric compound represented by the general formula: [Mg _1-x Al _x (OH) ₂ ] ^{x +} [(CO ₃ ) _{x / 2} · mH ₂ O] ^x- , and is positively charged. Inorganic material having a layered crystal structure consisting of a basic layer [Mg _1-x Al _x (OH) ₂ ] ^{x +} and a negatively charged intermediate layer [(CO ₃ ) _{x / 2} · mH ₂ O] ^x- It is. Here, in the above general formula, x is a number in the range of greater than 0 and less than or equal to 0.33. The natural hydrotalcite is Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O. The synthetic _{hydrotalcite, Mg 4.5 Al 2 (OH)} 13 CO 3 · 3.5H 2 O are commercially available. A method for synthesizing synthetic hydrotalcite is described in, for example, Japanese Patent Application Laid-Open No. 61-174270.

  Here, the content of the perchloric acid-treated hydrotalcite is not particularly limited, and is preferably 0.5 parts by mass or more and more preferably 1 part by mass or more with respect to 100 parts by mass of the vinyl chloride resin. 7 parts by mass or less is preferable, and 6 parts by mass or less is more preferable. If the content of the perchloric acid-treated hydrotalcite is within the above range, the tensile elongation at low temperature can be better maintained in the vinyl chloride resin molded article formed by molding the vinyl chloride resin composition. It is.

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

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

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

  In addition, content of (beta) -diketone is not restrict | limited in particular, 0.01 mass part or more is preferable with respect to 100 mass parts of vinyl chloride resin, and 5 mass parts or less are preferable.

<< 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 these, 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 still more preferable. Specific examples of fatty acid metal salts include lithium stearate, magnesium stearate, aluminum stearate, calcium stearate, strontium stearate, barium stearate, zinc stearate, calcium laurate, barium laurate, zinc laurate, 2-ethyl Examples thereof include barium hexanoate, zinc 2-ethylhexanoate, barium ricinoleate, and zinc ricinoleate. 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.

  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, with respect to 100 parts by mass of the vinyl chloride resin. Part or less, preferably 1 part by weight or less, more preferably 0.5 part by weight or less. This is because, if 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 article formed by molding the vinyl chloride resin composition can be reduced.

<< Releasing agent >>
The release agent is not particularly limited, and examples thereof include 12-hydroxystearic acid type 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 , Organic fine particles such as polystyrene resin fine particles, polyethylene resin fine particles, polypropylene resin fine particles, polyester resin 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.

  Here, the content of the other dusting agent is not particularly limited, and is preferably 30 parts by mass or less, more preferably 25 parts by mass or less with respect to 100 parts by mass of the vinyl chloride resin. Other dusting agents may be used alone or in combination of two or more, or may be used in combination with the above-described 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 resistance improvers, and perchloric acid compounds other than perchloric acid-treated hydrotalcite. (Sodium perchlorate, potassium perchlorate, etc.), antioxidants, fungicides, 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-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 reddish purple and brown. Specific examples of the perylene pigment are perylene red, perylene orange, perylene maroon, perylene vermilion, and perylene bordeaux.
The polyazo condensation pigment is obtained by condensing an azo dye in a solvent to obtain a high molecular weight, and exhibits a hue of a yellow or red pigment. Specific examples of the polyazo condensation pigment are polyazo red, polyazo yellow, chromophthal orange, chromophthal red, and chromophthal scarlet.
The isoindolinone-based pigment is obtained by a condensation reaction of 4,5,6,7-tetrachloroisoindolinone and an aromatic primary diamine, and exhibits a hue from greenish yellow to red and brown. A specific example of the isoindolinone pigment is isoindolinone yellow.
The copper phthalocyanine pigment is a pigment in which copper is coordinated to phthalocyanines, and exhibits a hue of yellowish green to vivid blue. Specific examples of the copper phthalocyanine pigment are phthalocyanine green and phthalocyanine blue.
Titanium white is a white pigment made of titanium dioxide and has a large hiding power, and there are anatase type and rutile type.
Carbon black is a black pigment containing carbon as a main component and containing oxygen, hydrogen, and nitrogen. Specific examples of carbon black are thermal black, acetylene black, channel black, furnace black, lamp black, and bone black.

  Specific examples of the impact 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, one or more impact modifiers can be used. The impact resistance improver is dispersed as a heterogeneous phase of fine elastic particles in the vinyl chloride resin composition. In the vinyl chloride resin composition, the chain and the polar group graft-polymerized on the elastic particles are compatible with the vinyl chloride resin, and the impact resistance of the vinyl chloride resin molded article formed by molding the vinyl chloride resin composition is improved.

  Specific examples of the antioxidant include phenolic antioxidants, sulfur antioxidants, phosphorus antioxidants such as phosphites, and the like.

  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; 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, pentane, and gas-based foaming agents such as microcapsules encapsulating 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 components described above.
Here, the mixing method of the vinyl chloride resin, the plasticizer, the ether-modified silicone oil, the silicone particles, and various additives further used as necessary is not particularly limited, for example, A method may be mentioned in which the components excluding the dusting agent containing the vinyl chloride resin fine 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. Moreover, the temperature at the time of dry blending is not specifically limited, 50 degreeC or more is preferable, 70 degreeC or more is more preferable, and 200 degreeC or less is preferable.

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

(Vinyl chloride resin molding)
The vinyl chloride resin molded article of the present invention is obtained by molding the above-described vinyl chloride resin composition by an arbitrary method. Since the vinyl chloride resin molded article of the present invention is formed by molding the vinyl chloride resin composition of the present invention, for example, while achieving good surface slipperiness, for example, while suppressing voids in the foamed polyurethane molded article, The foamed polyurethane molded product can be satisfactorily lined with the vinyl resin molded product. Therefore, the vinyl chloride resin molded article of the present invention is suitably used as an automobile interior member, specifically, for example, as a skin of an automobile interior part such as an automobile instrument panel and a door trim, and in particular, an automobile instrument. It is suitably used for the panel skin.

<< Method of molding 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, and preferably 300 ° C. or lower, and 280 ° C. More preferably, it is as follows.

  And when manufacturing a vinyl chloride resin molding, it is not specifically limited, For example, the following methods can be used. 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 to 30 seconds, and then the excess vinyl chloride resin composition is shaken off, and further, at an arbitrary temperature. Leave for 30 seconds to 3 minutes. Thereafter, the mold is cooled to 10 ° C. or more and 60 ° C. or less, and the obtained vinyl chloride resin molded body is removed from the mold. The demolded vinyl chloride resin molded body is obtained, for example, as a sheet-shaped molded body shaped like a mold.

(Laminate)
The laminate of the present invention has a foamed polyurethane molded product and the vinyl chloride resin molded product described above. Normally, the foamed polyurethane molded body is 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 stacking direction. And since the laminated body of this invention has a vinyl chloride resin molded object formed by shape | molding the vinyl chloride resin composition of this invention, the stickiness of the surface is fully reduced and vinyl chloride resin molding The foamed polyurethane molding 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 is particularly preferably used for an automobile instrument panel.

  Here, the lamination method is not particularly limited, and for example, the following method can be used. That is, polymerization is carried out by reacting isocyanates, which are raw materials of a foamed polyurethane molded body, and polyols on the vinyl chloride resin molded body, and polyurethane is foamed by a known method, whereby a vinyl chloride resin molded body is obtained. A foamed polyurethane molding is directly formed thereon.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the following description, “%” and “part” 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; HLB values and viscosities of various silicone oils; The tensile elongation at low temperature after the aging test), the surface slipperiness (dynamic friction coefficient) of the vinyl chloride resin molded article, and the degree of void formation in the foamed polyurethane molded article were measured and evaluated by the following methods.

<Average polymerization degree>
The average polymerization degree 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 apparatus shown below. It was calculated by measuring the particle size distribution.
・ Apparatus: Laser diffraction type particle size distribution measuring machine (manufactured by 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 value of various silicone oils is expressed by the following formula (1) by the Griffin method:
HLB value = 20 ×
(Sum of formula weight of chain ethylene oxide structure / molecular weight) (1)
According to the calculation.
A higher HLB value (closer to 20) indicates that the polarity of the silicone oil is higher and hydrophilic, and a lower HLB value (closer to 0) indicates that the polarity of the silicone oil is lower and lipophilic.

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

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

<Slip property>
The surface slipperiness of the vinyl chloride resin molded body was evaluated by measuring the dynamic friction coefficient as follows.
Specifically, using a texture tester (manufactured by Trinity Labs, product name “TL201Ts”), in a measurement environment at a temperature of 23 ° C. and a relative humidity of 50%, load: 50 g, speed: 10 mm / second, test range: 50 mm, measurement range: 30 mm excluding 10 mm before and after the test range, by contacting the tactile contact with the vinyl chloride resin molded sheet before forming the laminate, 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 surface stickiness is better suppressed.

<Degree of void formation>
The degree of void formation in the foamed polyurethane molded product 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. And the said sample was cut | disconnected in the transversal direction by 50 mm space | interval (6 divisions), and the state of the cross section was confirmed visually. Specifically, a void having a diameter of 3 mm or more was regarded as a void, and the total number of voids (N ₁ ) existing in six divided six sections was counted.
On the other hand, except that the vinyl chloride resin molded sheet is not placed in the mold, a foamed polyurethane molded body is produced by the same procedure as that of “Formation of laminate” in Example 1, and the foamed polyurethane molded body is also described above. The total number of voids (N ₀ ) existing in the six cross sections was counted. Incidentally, N ₀ is not a void resulting from the vinyl chloride resin molded body, strictly, in which counted voids derived from the operation procedure at the time of forming the foamed polyurethane moldings.
Then, in each sample, the void generation rate (%) = N ₁ / N ₀ × 100 with N ₀ as the reference (100%) was calculated, and the degree of void generation was evaluated according to the following criteria. As the void generation rate is lower (closer to 100%), voids are less likely to be generated in the polyurethane foam molded body adjacent to the vinyl chloride resin molded body.
A: The generation rate of voids is less than 120% B: The generation rate of voids is 120% or more and less than 150% C: The generation rate of voids is 150% or more Note that if the generation rate of voids is less than 100%, a measurement error is assumed. Included in the A evaluation above.

Example 1
<Preparation of vinyl chloride resin composition>
Among the blending components shown in Table 1, components other than the plasticizer (trimellitic acid ester and epoxidized soybean oil) and vinyl chloride resin fine particles as a dusting agent were placed in a Henschel mixer and mixed. Then, when the temperature of the mixture rises to 80 ° C., all of the plasticizer is added, and the temperature is further raised to dry up (the plasticizer is absorbed by the vinyl chloride resin particles, which are vinyl chloride resins, The mixture was further improved.) Thereafter, when the dried-up mixture was cooled to a temperature of 100 ° C. or less, 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 mold with a texture heated to a temperature of 250 ° C., left to melt for an arbitrary time of about 8 seconds to 20 seconds, and then an excess vinyl chloride resin composition. 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 the embossed mold was cooled with cooling water when 60 seconds had elapsed after 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 removed from the mold.
Then, with respect to the obtained vinyl chloride resin molded sheet, the initial (unheated) low-temperature tensile elongation and surface slipperiness (dynamic friction coefficient) were measured and calculated according to the above-described method. The results are shown in Table 1.

<Formation of laminate>
The obtained vinyl chloride resin molded sheet was allowed to stand in an oven set at a temperature of 100 ° C. for 2 hours, and then laid in a 200 mm × 300 mm × 10 mm mold with the surface with a textured side 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 (trade name “F-122” manufactured by Shin-Etsu Chemical Co., Ltd.) A polyol mixture was obtained. Moreover, the liquid mixture which mixed the obtained polyol mixture and polymethylene polyphenylene polyisocyanate (polymeric MDI) in the ratio from which the index becomes 98 was prepared. And the prepared liquid mixture was poured on the vinyl chloride resin molded sheet laid in the metal mold | die as above-mentioned. Thereafter, the mold was covered with an aluminum plate of 348 mm × 255 mm × 10 mm, and the mold was sealed. When the mold is sealed and left for 5 minutes, a foamed polyurethane molded product (thickness: 9 mm, density: 0.18 g / cm ³ ) is formed on the vinyl chloride resin molded sheet (thickness: 1 mm) as the skin. A lined laminate was formed in the mold.
And the formed laminated body was taken out from the metal mold | die, and according to the above-mentioned method, the tensile elongation in low temperature after a heating (heat aging test) and the generation | occurrence | production degree of a space | gap were measured and evaluated. 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 obtained in the same manner as in Example 1 except that the blending amount of the silicone particles was changed to 0.3 part as shown in the blending components shown in Table 1. Molded sheets and laminates were produced.
Measurement and calculation were performed in the same manner 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 compounding 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 substituted for the 8 parts of the vinyl chloride resin fine particles B. It was used. The blending amount of trimellitic acid ester as a plasticizer was changed to 110 parts, and the blending amount of epoxidized soybean oil was changed to 5 parts. Furthermore, the amount of perchloric acid-treated hydrotalcite as an additive is 4.56 parts, the amount of zeolite is 2.42 parts, the amount of β-diketone is 0.49 parts, and zinc stearate. Was changed to 0.20 part. A vinyl chloride resin composition, a vinyl chloride resin molded sheet, and a laminate were produced in the same manner as Example 1 except for the above.
Measurement and calculation were performed in the same manner 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.
Measurement and calculation were performed in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 3)
In the preparation of the vinyl chloride resin composition, 0.4 parts of unmodified silicone oil was used without using ether-modified silicone oil and silicone particles. Further, as shown in Table 1, the compounding 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 substituted for the 8 parts of the vinyl chloride resin fine particles B. It was used. The blending amount of trimellitic acid ester as a plasticizer was changed to 110 parts, and the blending amount of epoxidized soybean oil was changed to 5 parts. Furthermore, the amount of perchloric acid-treated hydrotalcite as an additive is 4.56 parts, the amount of zeolite is 2.42 parts, the amount of β-diketone is 0.49 parts, and zinc stearate. Was changed to 0.20 part. A vinyl chloride resin composition, a vinyl chloride resin molded sheet, and a laminate were produced in the same manner as Example 1 except for the above.
Measurement and calculation were performed in the same manner 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 parts of silanol-modified silicone oil was used without using ether-modified silicone oil and silicone particles. Further, as shown in Table 1, the compounding 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 substituted for the 8 parts of the vinyl chloride resin fine particles B. It was used. The blending amount of trimellitic acid ester as a plasticizer was changed to 110 parts, and the blending amount of epoxidized soybean oil was changed to 5 parts. Furthermore, the amount of perchloric acid-treated hydrotalcite as an additive is 4.56 parts, the amount of zeolite is 2.42 parts, the amount of β-diketone is 0.49 parts, and zinc stearate. Was changed to 0.20 part. A vinyl chloride resin composition, a vinyl chloride resin molded sheet, and a laminate were produced in the same manner as Example 1 except for the above.
Measurement and calculation were performed in the same manner as in Example 1. The results are shown in Table 1.

1) Product name “ZEST (registered trademark) 1700ZI” (manufactured by Shin Daiichi PVC Co., Ltd.) (suspension polymerization method, average degree of polymerization: 1700, average particle size: 130 μm)
2) Product name “ZEST PQLTX” (Emulsion polymerization method, average degree of polymerization: 800, average particle size: 1.8 μm)
3) Product name “Lyuron Paste (registered trademark) 860” manufactured by Tosoh Corporation (emulsion polymerization method, average degree of polymerization: 1600, average particle size: 1.6 μm)
4) Product name “Lyuron Paste (registered trademark) 761” manufactured by Tosoh Corporation (emulsion polymerization method, average degree of polymerization: 2100, average particle size: 1.6 μm)
5) Product name “Trimex N-08” manufactured by Kao Corporation
6) Product name "Adekasizer O-130S" manufactured by ADEKA
7) Product name “X-50-1039A” manufactured by Shin-Etsu Chemical Co., Ltd. (ether-modified silicone oil [an ether group having a chain ethylene oxide structure and a chain propylene oxide structure is introduced into the 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) Product name “X-22-8171” manufactured by Shin-Etsu Chemical Co., Ltd. (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) Product name “Karenz DK-1” manufactured by Showa Denko KK
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 significantly inferior.
In Comparative Examples 3 to 4 using only silicone oil other than ether-modified silicone oil, it was found that voids were likely to occur in the foamed polyurethane molded product 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 a vinyl chloride resin, a plasticizer, an ether-modified silicone oil, and silicone particles, the occurrence of voids in the foamed polyurethane molded article was satisfactorily suppressed, while the vinyl chloride resin molded article was It was found that the surface slipperiness was further improved, and the surface slipperiness and suppression of the generation of voids in the foamed polyurethane molded product can be achieved at a higher level.
In addition, in Example 2 where the blending amount of the silicone particles is relatively small, it was found that the tensile elongation at low temperature of the vinyl chloride resin molded article can be remarkably improved as compared with Example 1 where the blending amount of the silicone particles is relatively large. It was.

ADVANTAGE OF THE INVENTION According to this invention, it is excellent in surface slip property, and can manufacture the vinyl chloride resin molded object which can suppress generation | occurrence | production of a space | gap in the laminated polyurethane polyurethane molded object, and the said vinyl chloride resin molded object can be manufactured. A vinyl chloride resin composition can be provided.
Moreover, according to this invention, the laminated body which has the foaming polyurethane molded object and the vinyl chloride resin molded object which were excellent in surface slipperiness and generation | occurrence | production of the space | gap was suppressed can be provided.

Claims (11)

  A vinyl chloride resin composition comprising a vinyl chloride resin, a plasticizer, an ether-modified silicone oil, and silicone particles.   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 a 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 vinyl chloride resin composition according to any one of claims 1 to 3, wherein a content of the silicone particles is 0.3 parts by mass or less with respect to 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 to 10 times 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, which is used for powder molding.   The vinyl chloride resin composition according to claim 7, which is used for powder slush molding.   A vinyl chloride resin molded article obtained by molding the vinyl chloride resin composition according to claim 7 or 8.   The vinyl chloride resin molded article according to claim 9, which is used for an automobile instrument panel skin. A foamed polyurethane molding,
A vinyl chloride resin molded article according to claim 9 or 10,
A laminate having