WO2020066950A1

WO2020066950A1 - Laminated polyvinyl chloride resin sheet, method for producing laminated polyvinyl chloride resin sheet, and laminate

Info

Publication number: WO2020066950A1
Application number: PCT/JP2019/037128
Authority: WO
Inventors: 峻之中村; 翔太西村
Original assignee: 日本ゼオン株式会社
Priority date: 2018-09-25
Filing date: 2019-09-20
Publication date: 2020-04-02
Also published as: JP7334740B2; JPWO2020066950A1

Abstract

The purpose of the present invention is to provide a laminated polyvinyl chloride resin sheet enabling favorable prevention of migration of plasticizer from a polyvinyl chloride resin molding sheet, and offering excellent adhesiveness of a resin layer to the polyvinyl chloride resin molding sheet. This laminated polyvinyl chloride resin sheet comprises: a polyvinyl chloride resin molding sheet containing a polyvinyl chloride resin and a plasticizer; and a resin layer L containing a resin A and a binder. The resin layer L is arranged on at least one side of the thickness direction of the polyvinyl chloride resin molding sheet. The laminated polyvinyl chloride resin sheet is characterized in that: the SP value of the resin A is 14 (cal/cm³)^1/2 or greater; the classification of the adhesiveness of the resin A to the polyvinyl chloride resin molding sheet as assessed by cross-cut in accordance with JIS K 5600-5-6 is 5; and the classification of the adhesiveness of the binder to the polyvinyl chloride resin molding sheet as assessed by cross-cut is any of 0 to 4.

Description

Vinyl chloride resin laminated sheet, method for producing vinyl chloride resin laminated sheet, and laminate

The present invention relates to a vinyl chloride resin laminated sheet, a method for producing a vinyl chloride resin laminated sheet, 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, for forming an automobile interior part such as an automobile instrument panel, a vinyl chloride resin molded article (hereinafter, referred to as a “vinyl chloride resin molded sheet”) obtained by molding a vinyl chloride resin composition into a sheet is used. Automotive interior materials such as a laminate in which a foam such as foamed polyurethane is lined with a skin made of the vinyl chloride resin molded sheet.

ビニル As a material of the vinyl chloride resin molded sheet, a vinyl chloride resin composition containing a vinyl chloride resin and a plasticizer is used (for example, see Patent Documents 1 and 2).

JP 2011-173974 A JP 2012-7026 A

Here, when a laminate formed by lining a foam such as polyurethane foam on the skin made of a vinyl chloride resin molded sheet is used as an automobile interior material, the plasticizer contained in the vinyl chloride resin molded sheet migrates to the foam. When the amount of the plasticizer in the vinyl chloride resin molded sheet decreases, deterioration such as a decrease in flexibility of the vinyl chloride resin molded sheet (that is, the skin) may occur. Therefore, in the laminated body used as the interior material of the automobile described above, it is required that the transfer of the plasticizer from the vinyl chloride resin molded sheet to the foam be properly suppressed.

Therefore, the present inventor has developed a vinyl chloride resin laminate comprising a resin layer having a resin having an SP value within a predetermined range as a main component, on at least one side in the thickness direction of a vinyl chloride resin molded sheet containing a plasticizer. It has been found that such a problem can be solved by using a sheet. Specifically, the present inventors lined the foamed polyurethane molded article on the surface of the vinyl chloride resin laminated sheet on the side where the resin layer is disposed (that is, the vinyl chloride resin molded sheet via the resin layer). And the foamed polyurethane molded article are adhered to each other), and it was found that the transfer of the plasticizer from the vinyl chloride resin molded sheet can be favorably suppressed when the laminate is produced.

However, as a result of further study by the present inventor, when a laminate was produced using the above-described vinyl chloride resin laminated sheet, the resin layer having a resin whose SP value was within a predetermined range as a main component was formed of vinyl chloride. Since the adhesiveness to the resin molded sheet was low, it was found that there was room for improvement in the adhesive strength between the vinyl chloride resin molded sheet and the foamed polyurethane molded article in the laminate.

Therefore, an object of the present invention is to provide a vinyl chloride resin laminated sheet that can favorably suppress the migration of a plasticizer from a vinyl chloride resin molded sheet and that has excellent adhesion of a resin layer to the vinyl chloride resin molded sheet. I do.
Still another object of the present invention is to provide a laminate which can favorably suppress the transfer of a plasticizer from a vinyl chloride resin molded sheet and has excellent adhesive strength between the vinyl chloride resin molded sheet and the foamed polyurethane molded article. I do.

(4) The present inventors have conducted intensive studies with the aim of solving the above problems. The inventor of the present invention has disclosed that, on at least one side of a vinyl chloride resin molded sheet containing a plasticizer, a resin having an SP value in a predetermined range and a binder, and a vinyl chloride resin molded sheet of the resin and the binder. If the vinyl chloride resin laminated sheet is formed by arranging resin layers whose adhesiveness to each is classified into a predetermined classification, the migration of the plasticizer from the vinyl chloride resin molded sheet can be suppressed well, and The present inventors have found that the adhesiveness to a vinyl resin molded sheet is also excellent, and have completed the present invention.

That is, an object of the present invention is to advantageously solve the above-described problems, and a vinyl chloride resin laminated sheet of the present invention includes a vinyl chloride resin molded sheet containing a vinyl chloride resin and a plasticizer; A resin layer L containing a binder, wherein the resin layer L is disposed on at least one side in the thickness direction of the vinyl chloride resin molded sheet, wherein the SP value of the resin A Is 14 (cal / cm ³ ) ^1/2 or more, and the classification of the adhesion of the resin A to the vinyl chloride resin molded sheet is 5 as evaluated by a cross-cut method according to JIS K5600-5-6. Wherein the classification of the adhesiveness of the binder to the vinyl chloride resin molded sheet evaluated by the cross-cut method is any of 0 to 4. As described above, at least one side of the vinyl chloride resin molded sheet containing a plasticizer contains a resin and a binder having an SP value within a predetermined range, and the adhesiveness of the resin and the binder to the vinyl chloride resin molded sheet is each If it is a vinyl chloride resin laminated sheet in which the resin layer L evaluated in a predetermined classification is arranged, the transfer of the plasticizer from the vinyl chloride resin molded sheet can be suppressed well, and the vinyl chloride resin molded sheet of the resin layer Excellent adhesion to

Here, the SP value means a solubility parameter.
Then, the SP value can be calculated by using a method introduced in Hansen Solubility Parameters A User's Handbook, 2nd Ed (CRCPPress).
Further, the SP value of an organic compound can also be estimated from the molecular structure of the organic compound. Specifically, the calculation can be performed using simulation software (for example, “HSPiP” (http://www.hansen-solubility.com)) that can calculate the SP value from the SMILE equation. In this simulation software, Hansen SOLUBLEITY PARAMETERS A User's Handbook Second Edition, Charles M.S. The SP value is determined based on the theory described in Hansen.

Here, in the vinyl chloride resin laminated sheet of the present invention, it is preferable that the resin layer L further includes a plasticizer for the resin layer L. When the resin layer L further contains a plasticizer for the resin layer L, the vinyl chloride resin laminated sheet can exhibit excellent flexibility.

Further, in the vinyl chloride resin laminated sheet of the present invention, the mass ratio of the content of the binder to the content of the resin A in the resin layer L (binder / resin A) is 1/40 by dry mass ratio. It is preferably at least 1/4 or less. If the mass ratio of the content of the binder to the content of the resin A in the resin layer L (binder / resin A) is within the above-mentioned predetermined range in terms of a dry mass ratio, the vinyl chloride resin laminated sheet is In addition, the transfer of the plasticizer from the vinyl chloride resin molded sheet can be more favorably suppressed, and the adhesiveness of the resin layer L to the vinyl chloride resin molded sheet can be further increased.

Further, in the vinyl chloride resin laminated sheet of the present invention, the binder preferably contains at least one of a urethane-based binder and an acrylic ester-based binder. When the binder contains at least one of a urethane-based binder and an acrylic ester-based binder, the adhesiveness of the resin layer L to the vinyl chloride resin molded sheet can be further enhanced.

ビニル Further, the vinyl chloride resin laminated sheet of the present invention is preferably used for the skin of an automobile instrument panel. When the vinyl chloride resin laminated sheet of the present invention is used as a skin of an automobile instrument panel, the migration of the plasticizer from the vinyl chloride resin molded sheet can be favorably suppressed, and the deterioration of the skin can be prevented.

Further, the method for producing a vinyl chloride resin laminated sheet of the present invention includes a step of forming a resin layer L containing a resin A and a binder on at least one side in the thickness direction of a vinyl chloride resin molded sheet containing a vinyl chloride resin and a plasticizer. Wherein the SP value of the resin is 14 (cal / cm ³ ) ^1/2 or more, and the adhesion of the resin to the vinyl chloride resin molded sheet is evaluated by a cross-cut method according to JIS K5600-5-6. The classification of the property is 5, and the classification of the adhesiveness of the binder to the vinyl chloride resin molded sheet evaluated by the cross-cut method is any of 0 to 4. As described above, on at least one side in the thickness direction of the vinyl chloride resin molded sheet containing a plasticizer, a resin and a binder having an SP value within a predetermined range are included, and the resin and the binder adhere to the vinyl chloride resin molded sheet. The vinyl chloride resin laminated sheet manufactured by forming the resin layer L whose property is evaluated to a predetermined classification can suppress the migration of the plasticizer from the vinyl chloride resin molded sheet satisfactorily. Excellent adhesion to resin molded sheet.

Furthermore, an object of the present invention is to advantageously solve the above-mentioned problem, and a laminate of the present invention is a laminate including a foamed polyurethane molded article and any one of the above-described vinyl chloride resin laminate sheets. Wherein the resin layer L is disposed between the foamed polyurethane molded article and the vinyl chloride resin molded sheet. As described above, the laminate including the foamed polyurethane molded article and any one of the vinyl chloride resin laminated sheets described above, wherein the resin layer L is disposed between the foamed polyurethane molded article and the vinyl chloride resin molded sheet. In the case of a molded article, the transfer of the plasticizer from the vinyl chloride resin molded sheet can be suppressed well, and the adhesive strength between the vinyl chloride resin molded sheet and the foamed polyurethane molded article is excellent.

Advantageous Effects of Invention According to the present invention, it is possible to provide a vinyl chloride resin laminated sheet that can favorably suppress the transfer of a plasticizer from a vinyl chloride resin molded sheet and has excellent adhesion of a resin layer to the vinyl chloride resin molded sheet.
Further, according to the present invention, it is possible to provide a laminate that can favorably suppress migration of a plasticizer from a vinyl chloride resin molded sheet and has excellent adhesive strength between the vinyl chloride resin molded sheet and the foamed polyurethane molded article. it can.

Hereinafter, embodiments of the present invention will be described in detail.
Here, the vinyl chloride resin laminate sheet of the present invention can be used, for example, for producing the laminate of the present invention. And, the vinyl chloride resin laminated sheet 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. Furthermore, the vinyl chloride resin laminated sheet of the present invention can be produced by the method for producing a vinyl chloride resin laminated sheet of the present invention.

(Vinyl chloride laminated sheet)
The vinyl chloride resin laminated sheet of the present invention comprises a vinyl chloride resin molded sheet containing a vinyl chloride resin and a plasticizer, a resin A and a binder having an SP value within a predetermined range, and the resin A and the vinyl chloride of the binder. And a resin layer L whose adhesion to the resin molded sheet is evaluated in a predetermined classification, wherein the resin layer L is disposed on at least one side in the thickness direction of the vinyl chloride resin molded sheet. I do.

Further, the vinyl chloride resin laminated sheet of the present invention includes, on at least one side in the thickness direction of the vinyl chloride resin molded sheet, a resin A and a binder having an SP value within a predetermined range, Since the resin layer L whose adhesiveness to the vinyl resin molded sheet is evaluated in each of the predetermined classifications is disposed, the migration of the plasticizer from the vinyl chloride resin molded sheet can be suppressed well, and the resin layer L Excellent adhesion to vinyl chloride resin molded sheet.

Therefore, the vinyl chloride resin laminated sheet of the present invention is suitably used as an automobile interior member, specifically, for example, as a skin of an automobile interior panel such as an automobile instrument panel and a door trim. It is suitably used for the skin of a panel.

<Vinyl chloride resin molded sheet>
A vinyl chloride resin molded sheet containing a vinyl chloride resin and a plasticizer is obtained by molding a vinyl chloride resin composition containing a vinyl chloride resin and a plasticizer into a sheet.

<<< vinyl chloride resin composition >>>
The vinyl chloride resin composition contains a vinyl chloride resin and a plasticizer, and may optionally further contain various additives.

[Vinyl chloride resin]
Here, as the vinyl chloride resin contained in the vinyl chloride resin composition, for example, one or two or more kinds of vinyl chloride resin particles can be contained, and optionally, one or more kinds of vinyl chloride resin fine particles Can be further contained. Above all, the vinyl chloride resin preferably contains at least vinyl chloride resin particles, and more preferably contains vinyl chloride resin particles and vinyl chloride resin fine particles.
In this specification, “resin particles” refer to particles having a particle size of 30 μm or more, and “resin fine particles” refer to particles having a particle size of less than 30 μm. The vinyl chloride resin particles usually function as a matrix resin (substrate), and the vinyl chloride resin fine particles usually function as a dusting agent (powder fluidity improver). The vinyl chloride resin particles are preferably produced by a suspension polymerization method, and the vinyl chloride resin fine particles are preferably produced by an emulsion polymerization method.
Further, the vinyl chloride resin can be produced by any conventionally known production method such as a suspension polymerization method, an emulsion polymerization method, a solution polymerization method, and a bulk polymerization method.

-composition-
As the vinyl chloride resin, besides a homopolymer composed of vinyl chloride monomer units, a vinyl chloride copolymer containing preferably at least 50% by mass, more preferably at least 70% by mass of vinyl chloride monomer units is used. No. Specific examples of monomers (comonomers) that can constitute a vinyl chloride copolymer and can be copolymerized 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 Ethers, allyl ethers such as 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, acrylamide-2-methylpropanesulfonic acid and (meth) acrylamidopropyltrimethylammonium chloride; allylamine benzoate and diallyldimethylammonium Allylamine such as chloride and derivatives thereof; and the like. The monomers exemplified above are only a part of the comonomers, and examples of the comonomers include “polyvinyl chloride”, edited by Kinki Chemical Association Vinyl Subcommittee, Nikkan Kogyo Shimbun (1988), No. 75- Various monomers exemplified on page 104 can be used. One of these comonomers may be used alone, or two or more thereof may be used. The above vinyl chloride resins include resins 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 polymerization of vinyl chloride and the above comonomer is also included.
Here, in the present specification, “(meth) acryl” means acryl and / or methacryl.

-SP value-
The SP value of the polymer used as the vinyl chloride resin is preferably 8 (cal / cm ³ ) ^1/2 or more, more preferably 9 (cal / cm ³ ) ^1/2 or more, and 11 (Cal / cm ³ ) ^1/2 or less, and more preferably 10 (cal / cm ³ ) ^1/2 or less. When the SP value of the polymer used as the vinyl chloride resin is within the above-mentioned predetermined range, the migration of the plasticizer from the vinyl chloride resin molded sheet can be more favorably suppressed.

[Plasticizer]
The vinyl chloride resin composition further contains a plasticizer. If the vinyl chloride resin composition does not contain a plasticizer, a vinyl chloride resin molded sheet cannot be favorably obtained using the vinyl chloride resin composition.

The “plasticizer” used in the vinyl chloride resin composition is a component different from the “plasticizer for the resin layer L” that can be used for the resin layer L described below. In this specification, what is simply referred to as “plasticizer” does not refer to “plasticizer for resin layer L” that can be used for resin layer L, but refers to “plasticizer” used for the vinyl chloride resin composition. Agent ", that is, the" plasticizer "contained in the vinyl chloride resin molded sheet.

-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 92 parts by mass or more based on 100 parts by mass of the vinyl chloride resin. It is more preferably at least 97 parts by mass, preferably at most 200 parts by mass, more preferably at most 150 parts by mass, even more preferably at most 100 parts by mass. When the content of the plasticizer is equal to or more than the above lower limit, excellent flexibility is imparted to the vinyl chloride resin composition, and for example, it can be easily processed into a vinyl chloride resin molded sheet, and the obtained vinyl chloride resin molded sheet has a low temperature. This is because good tensile elongation can be imparted below. Further, when the content of the plasticizer is equal to or less than the above upper limit, stickiness of the surface of the obtained vinyl chloride resin molded sheet can be further suppressed, and surface slipperiness can be further improved.

-type-
Here, specific examples of the plasticizer include the following primary plasticizer and secondary plasticizer.
So-called primary plasticizers include trimethyl trimellitate, triethyl trimellitate, tri-n-propyl trimellitate, tri-n-butyl trimellitate, tri-n-pentyl trimellitate, and tri-n trimellitate -Hexyl, tri-n-heptyl trimellitate, tri-n-octyl trimellitate, di-n-octyl-mono-n-decyl trimellitate, mono-n-octyl-di-n-decyl trimellitate Tri-n-nonyl trimellitate, tri-n-decyl trimellitate, tri-n-undecyl trimellitate, tri-n-dodecyl trimellitate, tri-n-tridecyl trimellitate, tri trimellitate -N-tetradecyl, tri-n-pentadecyl trimellitate, tri-n-hexadecyl trimellitate, Tri-n-heptadecyl rimellitate, tri-n-stearyl trimellitate, and tri-n-alkyl trimellitate (where the alkyl group of the tri-n-alkyl trimellitate has one carbon atom May be different from each other.) [In addition, these trimellitic esters are composed of a single compound, and the alkyl groups constituting the ester are linear. Or a mixture. ];
Tri-i-propyl trimellitate, tri-i-butyl trimellitate, tri-i-pentyl trimellitate, tri-i-hexyl trimellitate, tri-i-heptyl trimellitate, tri-trimellitate i-octyl, tri- (2-ethylhexyl) trimellitate, tri-i-nonyl trimellitate, tri-i-decyl trimellitate, tri-i-undecyl trimellitate, tri-i-dodecyl trimellitate Tri-i-tridecyl trimellitate, tri-i-tetradecyl trimellitate, tri-i-pentadecyl trimellitate, tri-i-hexadecyl trimellitate, tri-i-heptadecyl trimellitate, tri trimellitate -I-octadecyl, trimellitic acid trialkyl ester (where trimellitic acid The alkyl group of the alkyl ester may have a different number of carbon atoms in one molecule), such as a branched trimellitate ester in which the alkyl group constituting the ester is branched [these trimellitic acids The ester may consist 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 pyromellitate, tetra-n-tetradecyl pyromellitate, tetra-n-pentadecyl pyromellitate, tetra-n-hexadecyl pyromellitate, tetra-n-heptadecyl pyromellitate, tetrapyromellitic acid -N-stearyl, tetro pyromellitic acid An alkyl group constituting the ester, such as an -n-alkyl ester (where the carbon number of the alkyl group of the pyromellitic acid tetra-n-alkyl ester may be different from each other in one molecule); Linear pyromellitic acid ester [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 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 -I-octadecyl, tetraalkyl pyromellitic acid A branched pyromellitic acid in which the alkyl group constituting the ester is branched, such as an ester (here, the number of carbon atoms in the alkyl group of the tetraalkyl pyromellitic acid ester may be different in one molecule). Ester [These pyromellitic 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, 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, di- (2-ethylhexyl) itaconate;
Oleic acid derivatives such as butyl oleate, glyceryl monooleate, diethylene glycol monooleate;
Ricinoleic acid derivatives such as methyl acetyl ricinolate, butyl acetyl ricinolate, glyceryl monoricinolate, diethylene glycol monoricinolate;
Stearic acid derivatives such as n-butyl stearate and diethylene glycol distearate (excluding 12-hydroxystearic acid and esters thereof);
Other fatty acid derivatives such as diethylene glycol monolaurate, diethylene glycol diperargonate, 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), dibutylmethylenebisthioglycolate, etc. Glycol derivatives of
Glycerin derivatives such as glycerol monoacetate, glycerol triacetate and glycerol tributyrate;
Epoxy derivatives such as epoxy diisodecyl hexahexahydrophthalate, epoxy triglyceride, epoxidized octyl oleate, and epoxidized decyl oleate;
Polyester plasticizers such as adipic acid polyester, sebacic polyester, and phthalic polyester;
And the like.

いわゆる Examples of the so-called secondary plasticizer include chlorinated paraffins, fatty acid esters of glycols such as triethylene glycol dicaprylate, butyl epoxy stearate, phenyl oleate, and methyl dihydroabietic acid.

In addition, only one of these plasticizers may be used, and for example, two or more of a primary plasticizer and a secondary plasticizer may be used in combination. When a secondary plasticizer is used, it is preferable to use the secondary plasticizer in combination with a primary plasticizer of equal mass or more.

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

-SP value-
In addition, the SP value of the plasticizer used in the vinyl chloride resin composition is preferably 7 (cal / cm ³ ) ^1/2 or more, more preferably 8 (cal / cm ³ ) ^1/2 or more. , 12 (cal / cm ³ ) ^1/2 or less, and more preferably 10 (cal / cm ³ ) ^1/2 or less. When the SP value of the plasticizer used as the vinyl chloride resin is within the above-mentioned predetermined range, the migration of the plasticizer from the vinyl chloride resin molded sheet can be more favorably suppressed.

[Additive]
The vinyl chloride resin composition may further contain various additives in addition to the components described above. Examples of the additive include, but are not limited to, a lubricant such as silicone oil; a stabilizer such as perchloric acid-treated hydrotalcite, zeolite, β-diketone, or a metal salt of a fatty acid; a release agent; And other additives; and the like.

－Silicone oil－
Examples of the silicone oil that can be contained in the vinyl chloride resin composition include ether-modified silicone oil, fatty acid amide-modified silicone oil, and unmodified silicone oil.

Here, the content of the silicone oil is preferably at least 0.01 part by mass, more preferably at least 0.1 part by mass, and preferably at least 0.15 part by mass, based on 100 parts by mass of the vinyl chloride resin. More preferably, it is preferably 1.5 parts by mass or less, more preferably 1.0 part by mass or less, still more preferably 0.5 part by mass or less, and more preferably 0.4 part by mass or less. Parts or less is more preferable. If the content of the silicone oil is equal to or more than the above lower limit, the stickiness of the surface of the vinyl chloride resin molded sheet can be sufficiently reduced and the surface slipperiness can be improved. Further, when the content of the silicone oil is equal to or less than the upper limit, for example, even when a vinyl chloride resin molded sheet is continuously molded, the surface of a molding die or the like due to an excessive amount of silicone oil may be formed. This is because contamination can be suppressed.

－Hydrotalcite treated with perchloric acid－
The vinyl chloride resin composition may contain, perchloric acid-treated hydrotalcite, for example, hydrotalcite is added to a dilute aqueous solution of perchloric acid and stirred, and then, if necessary, filtered, dehydrated or dried. As a result, at least a part of the carbonate anion (CO ₃ ²⁻ ) in the hydrotalcite is replaced with a perchlorate anion (ClO ₄ ⁻ ) (2 moles of perchlorate anion are substituted for 1 mole of carbonate anion). It can be easily produced as a perchloric acid-introduced hydrotalcite. The molar ratio between the hydrotalcite and the perchloric acid can be set arbitrarily. In general, the molar ratio of the perchloric acid is preferably 0.1 mol or more and 2 mol or less per 1 mol of the hydrotalcite.

Here, the substitution rate of the carbonate anion to the perchlorate anion in the untreated (unsubstituted perchlorate anion-introduced) hydrotalcite is preferably 50 mol% or more, more preferably 70 mol%. It is more preferably at least 85 mol%. The substitution rate of the carbonate anion to the perchlorate anion in the untreated (unsubstituted perchlorate anion-introduced) hydrotalcite is preferably 95 mol% or less. A vinyl chloride resin molded sheet can be more easily formed because the substitution rate of the carbonate anion to the perchlorate anion in the untreated (unsubstituted perchlorate anion-introduced) hydrotalcite is within the above range. This is because it can be manufactured in a short time.

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 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 It is. Here, in the above general formula, x is a number in a range from greater than 0 to 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 at least 0.5 part by mass, more preferably at least 1 part by mass, based on 100 parts by mass of the vinyl chloride resin. It is preferably at most 7 parts by mass, more preferably at most 6 parts by mass. When the content of the perchloric acid-treated hydrotalcite is in the above range, the vinyl chloride resin molded sheet obtained by molding the vinyl chloride resin composition can more preferably maintain tensile elongation at a low temperature. It is.

－Zeolite－
The vinyl chloride resin composition may contain zeolite as a stabilizer. The zeolite has a general formula: M _{x / n} · [(AlO ₂ ) _x · (SiO ₂ ) _y ] · zH ₂ O (where M is a metal ion having a valence of n, and x + y is four faces per singleton lattice) And z is the number of moles of water). Examples of the type 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 zeolite is not particularly limited, and is preferably 0.1 part by mass or more, and more preferably 5 parts by mass or less based on 100 parts by mass of the vinyl chloride resin.

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

The content of β-diketone is not particularly limited, and is preferably 0.01 parts by mass or more, and more preferably 5 parts by mass or less based on 100 parts by mass of the vinyl chloride resin.

-Fatty acid metal salts-
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 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 Barium hexanoate, zinc 2-ethylhexanoate, barium ricinoleate, zinc ricinoleate and the like. The metal constituting the fatty acid metal salt is preferably a metal capable of generating a polyvalent cation, more preferably a metal capable of generating a divalent cation, and a divalent cation in the third to sixth cycles 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, and more preferably 5 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. Or less, more preferably 1 part by mass or less, even more preferably 0.5 part by mass or less. If the content of the fatty acid metal salt is in the above range, the value of the color difference of the vinyl chloride resin molded sheet formed by molding the vinyl chloride resin composition can be reduced.

-Release agent-
The release agent is not particularly limited, and includes, for example, 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 may be 0.01 to 5 parts by mass based on 100 parts by mass of the vinyl chloride resin.

－Other dusting agents－
Other dusting agents other than the above-mentioned vinyl chloride resin fine particles that the vinyl chloride resin composition may contain include inorganic fine particles such as calcium carbonate, talc, and aluminum oxide; polyacrylonitrile resin fine particles, and 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 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, more preferably 25 parts by mass or less based on 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-mentioned vinyl chloride resin fine particles.

-Other additives-
Other additives that can be contained in the vinyl chloride resin composition are not particularly limited, and include, for example, colorants (pigments), impact resistance improvers, perchlorate compounds other than perchlorate-treated hydrotalcite (Such as sodium perchlorate and potassium perchlorate), epoxidized vegetable oil-based heat stabilizers such as epoxidized soybean oil and epoxidized linseed oil; antioxidants, fungicides, flame retardants, antistatic agents, fillers , Light stabilizers, foaming agents and the like.

Specific examples of the colorant (pigment) include quinacridone pigments, perylene pigments, polyazo condensed 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 acids with concentrated sulfuric acid, and exhibits a yellowish red to reddish purple hue. Specific examples of the quinacridone pigments include quinacridone red, quinacridone magenta, and quinacridone violet.
The perylene pigment is obtained by a condensation reaction between perylene-3,4,9,10-tetracarboxylic anhydride and an aromatic primary amine, and exhibits a red to reddish purple and brown hue. Specific examples of 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 increase the molecular weight, and exhibits a hue of a yellow or red pigment. Specific examples of the polyazo condensed pigment include polyazo red, polyazo yellow, chromophthal orange, chromophthal red, and chromophthal scarlet.
The isoindolinone pigment is obtained by a condensation reaction between 4,5,6,7-tetrachloroisoindolinone and an aromatic primary diamine, and exhibits a hue from greenish yellow to red to 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 from yellowish green to vivid blue. Specific examples of the copper phthalocyanine pigment include phthalocyanine green and phthalocyanine blue.
Titanium white is a white pigment made of titanium dioxide and has a large hiding power, and is classified into an anatase type and a 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 include thermal black, acetylene black, channel black, furnace black, lamp black, and bone black.

具体 Specific examples of impact modifiers 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 modifier is dispersed in the vinyl chloride resin composition as a heterogeneous phase of fine elastic particles. In the vinyl chloride resin composition, the chains and polar groups graft-polymerized to the elastic particles are compatible with the vinyl chloride resin, and the impact resistance of the vinyl chloride resin molded sheet obtained by molding the vinyl chloride resin composition is improved.

具体 Specific examples of the antioxidant include a phenolic antioxidant, a sulfuric antioxidant, and a phosphorus-based antioxidant such as phosphite.

具体 Specific examples of the fungicide include an aliphatic ester-based fungicide, a hydrocarbon-based fungicide, an organic nitrogen-based fungicide, and an organic nitrogen-sulfur-based fungicide.

具体 Specific examples of flame retardants 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;

具体 Specific examples of the filler include silica, talc, mica, calcium carbonate, clay and the like.

Specific examples of light stabilizers include benzotriazole-based, benzophenone-based, nickel chelate-based ultraviolet absorbers, and hindered amine-based light stabilizers.

Specific examples of the foaming agent include azo compounds such as azodicarbonamide and azobisisobutyronitrile, nitroso compounds such as N, N'-dinitrosopentamethylenetetramine, p-toluenesulfonylhydrazide, p, p-oxybis (benzene Organic blowing agents such as sulfonyl hydrazide compounds such as sulfonyl hydrazide); volatile hydrocarbon compounds such as chlorofluorocarbon, carbon dioxide, water, and pentane; and gas-based blowing agents such as microcapsules containing these.

[Method for Preparing Vinyl Chloride Resin Composition]
The vinyl chloride resin composition can be prepared by mixing the above-mentioned components without any particular limitation.
Here, the method of mixing the vinyl chloride resin, the plasticizer, and various additives that are further used as necessary is not particularly limited, for example, a dusting agent containing vinyl chloride resin fine particles. The components to be removed are mixed by dry blending, and then a dusting agent is added and mixed. Here, it is preferable to use a Henschel mixer for the dry blending. The temperature at the time of 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.

<<< Molding method of vinyl chloride resin molded sheet >>>
The vinyl chloride resin molded sheet is obtained by molding the above-mentioned vinyl chloride resin composition into a sheet. The method for molding the vinyl chloride resin composition is not particularly limited, and a known molding method can be used. However, it is preferable to use powder molding, and it is more preferable to use powder slush molding.
Here, the mold temperature during 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. It is more preferable to set the following.

Then, when manufacturing the vinyl chloride resin molded sheet, for example, the following method can be used without any particular limitation. That is, after spraying the vinyl chloride resin composition of the present invention on a mold having the above temperature range and leaving it for 5 seconds or more and 30 seconds or less, the excess vinyl chloride resin composition is shaken off, and further, at an arbitrary temperature. For 30 seconds or more and 3 minutes or less. Thereafter, the mold is cooled to 10 ° C or more and 60 ° C or less, and the obtained vinyl chloride resin molded sheet is released from the mold. Then, the demolded vinyl chloride resin molded sheet is obtained, for example, as a sheet-like molded body having the shape of a mold.

<Resin layer L>
The vinyl chloride resin laminated sheet of the present invention has a predetermined resin layer L disposed on at least one side in the thickness direction of the above-described vinyl chloride resin molded sheet. The predetermined resin layer L may be disposed on both sides in the thickness direction of the vinyl chloride resin molded sheet, or may be disposed on only one side in the thickness direction of the vinyl chloride resin molded sheet. Usually, it is arranged only on one side in the thickness direction of the vinyl chloride resin molded sheet.

The surface of one or both sides in the thickness direction of the vinyl chloride resin laminated sheet may be partially formed of the predetermined resin layer L, or may be entirely formed of the predetermined resin layer L. .

Here, the predetermined resin layer L is usually directly bonded to the vinyl chloride resin molded sheet.

{Circle around (2)} The predetermined resin layer L includes a resin A having a SP value within a predetermined range, and a binder. Further, the adhesiveness of the resin A and the binder to the above-mentioned vinyl chloride resin molded sheet is respectively evaluated in a predetermined classification. The resin layer L may contain other components other than the resin A and the binder as long as the desired effects of the present invention can be obtained.

Here, generally, when the vinyl chloride resin molded sheet is placed in a state of being in direct contact with another resin member such as a foamed urethane molded body, the plasticizer in the vinyl chloride resin molded sheet is transferred to another resin member. It is considered that the shift reduces the amount of the plasticizer in the vinyl chloride resin molded sheet and causes deterioration of the vinyl chloride resin molded sheet. However, in the case of the vinyl chloride resin laminated sheet of the present invention having the resin layer L containing the resin A having the above-mentioned SP value within a predetermined range, the resin is located between the vinyl chloride resin molded sheet and other resin members and the like. By interposing the layer L, it becomes difficult for the plasticizer to pass from the vinyl chloride resin molded sheet through the resin layer L to reach other resin members and the like. It can be supposed that the transition of can be favorably suppressed. In addition, although the adhesiveness of the resin A contained in the resin layer L is usually low, the adhesiveness of the resin layer L to the vinyl chloride resin molded sheet can be increased by further adding a binder to the resin layer L.

<< Resin A >>
The resin A contained in the resin layer L is a component capable of favorably suppressing migration of the plasticizer from the vinyl chloride resin molded sheet.
Here, the SP value of the resin A that can be included in the resin layer L needs to be 14 (cal / cm ³ ) ^1/2 or more, and 15 (cal / cm ³ ) ^1/2 or more. More preferably, it is 16 (cal / cm ³ ) ^1/2 or more. When the SP value of the resin A is at least 14 (cal / cm ³ ) ^1/2 , migration of the plasticizer from the vinyl chloride resin molded sheet can be favorably suppressed. Further, the SP value of the resin A is preferably 30 (cal / cm ³ ) ^1/2 or less, more preferably 25 (cal / cm ³ ) ^1/2 or less, and 22 (cal / cm ³ ). still more preferably ^1/2 or less, and particularly preferably 20 (cal / cm ³⁾ ^1/2 or less. When the SP value of the resin A is 30 (cal / cm ³ ) ^1/2 or less, the flexibility of the resin layer L can be further increased.

In addition, the resin A that can be contained in the resin layer L needs to have an adhesion classification of 5 to the above-mentioned vinyl chloride resin molded sheet, which is evaluated by a cross-cut method according to JIS K5600-5-6. .

As the resin A described above, for example, polyvinyl alcohol (also referred to as completely saponified product from polyvinyl acetate or partially saponified polyvinyl acetate. The degree of saponification from polyvinyl acetate is 60% or more and the SP value is 14 (cal / cm ³ ) ^1/2 or more), polyacrylic acid (SP value = 14.0 (cal / cm ³ ) ^1/2 ; hereinafter, the unit of the SP value in the present specification is the same), polymethacrylic acid (SP value = 14.0), polyacrylamide (SP value = 19.2), polymethacrylamide (SP value = 19.2), poly N-vinylformamide (SP value = 17.2), water-soluble starch ( SP value = 23.5), hydroxyethyl cellulose (SP value = 19.3), hydroxypropyl cellulose (SP value = 18.0), methylcellulose (SP value = 17.4), ethi Cellulose (SP value = 16.2), chitosan (SP value = 20.4) and the like can be used. Above all, it is preferable to use polyvinyl alcohol as the resin A from the viewpoint of further suppressing the migration of the plasticizer from the vinyl chloride resin molded sheet.

The degree of saponification of polyvinyl alcohol from polyvinyl acetate can be 60% or more, preferably 61% or more, more preferably 62% or more, and more preferably 63% or more. More preferably, it is more preferably 65% or more, can be 100%, is preferably less than 100%, is preferably 90% or less, is more preferably 80% or less, and is more preferably 70% or less. % Is more preferable. If the degree of saponification of polyvinyl alcohol from polyvinyl acetate is not less than the above lower limit, the vinyl chloride resin laminated sheet can more favorably suppress migration of the plasticizer from the vinyl chloride resin molded sheet. On the other hand, if the degree of saponification of polyvinyl alcohol from polyvinyl acetate is equal to or less than the upper limit, the flexibility of the resin layer L can be increased.
The degree of saponification of polyvinyl alcohol from polyvinyl acetate can be measured according to JIS K6726 (polyvinyl alcohol test method).

Specific examples of the polyvinyl alcohol that can be used as the resin A include those completely saponified from polyvinyl acetate (SP value = 23.4) and those having a degree of saponification from polyvinyl acetate of 90% (SP value = 19. 1), those having a saponification degree of 80% from polyvinyl acetate (SP value = 17.5), those having a saponification degree of 65% from polyvinyl acetate (SP value = 16.4), and the like. . Among them, from the viewpoint of further suppressing the migration of the plasticizer from the polyvinyl chloride resin molded sheet and enhancing the adhesion of the resin layer L to the vinyl chloride resin molded sheet, the degree of saponification from polyvinyl acetate is 65%. It is preferable to use one.

<< Binder >>
The binder contained in the resin layer L is a component that can enhance the adhesiveness of the resin layer L to the vinyl chloride resin molded sheet. The binder that can be included in the resin layer L has any of the classifications of the adhesiveness to the vinyl chloride resin molded sheet described above, which is evaluated by a cross-cut method according to JIS K5600-5-6, from 0 to 4. Is required, and is preferably 0 to 3, more preferably 0 to 2, and even more preferably 0 or 1. If the evaluation of the adhesiveness of the binder to the vinyl chloride resin molded sheet is any of the above-described predetermined classifications, the adhesiveness of the resin layer L to the vinyl chloride resin molded sheet can be increased.

として As the above-mentioned binder, it is preferable to use a urethane-based binder and an acrylic ester-based binder, and it is more preferable to use a urethane-based binder. When at least one of a urethane-based binder and an acrylic ester-based binder is used as the binder, the adhesiveness of the resin layer L to the vinyl chloride resin molded sheet can be further increased.

Here, the urethane-based binder is a polyurethane obtained by reacting an isocyanate and a polyol. As the urethane-based binder, a polyester-based polyurethane obtained by using a polyester polyol as a polyol; a polycarbonate-based polyurethane obtained by using a polycarbonate polyol as a polyol; a polyether-based obtained by using a polyether polyol as a polyol. Polyurethane; polycarbonate polyester-based polyurethane obtained by using a mixture of a polycarbonate polyol and a polyester polyol as a polyol; polyester-polyether-based polyurethane obtained by using a mixture of a polyester polyol and a polyether polyol as a polyol; Polyurethane whose adhesion to the resin molded sheet is one of the above-mentioned predetermined classifications It can be used down.
From the viewpoint of further improving the adhesiveness of the resin layer L to the vinyl chloride resin molded sheet, it is preferable to use a polyester-based polyurethane, a polycarbonate-based polyurethane, and a polycarbonate-polyester-based polyurethane as the urethane-based binder. It is more preferable to use a polyester-based polyurethane, and it is even more preferable to use a polyester-based polyurethane.

The polyurethane that can be used as the urethane-based binder is either a yellowing polyurethane obtained by using an aromatic polyisocyanate as an isocyanate or a non-yellowing polyurethane obtained by using an aliphatic polyisocyanate as an isocyanate. From the viewpoint of further increasing the adhesion of the resin layer L to the vinyl chloride resin molded sheet, a yellowing type polyurethane obtained by using an aromatic polyisocyanate as the isocyanate is more preferable.

市販 Commercial products can also be used as the urethane-based binder. Commercially available urethane-based binders include "Toutan S" (polycarbonate polyester-based polyurethane) manufactured by Toupe Co., Ltd., "Superflex (registered trademark) 460" (non-yellowing type polycarbonate-based polyurethane) manufactured by Daiichi Kogyo Seiyaku, and Daiichi Kogyo Co., Ltd. “Superflex (registered trademark) 740” (yellowing-type polyester-based polyurethane) manufactured by Pharmaceutical Co., Ltd. can be suitably used.

In addition, as the acrylic ester-based binder, among known acrylic ester-based polymers that can function as a binder, those having an evaluation of adhesion to a vinyl chloride resin molded sheet that falls in any of the above-described predetermined classes can be used. . Here, the acrylic ester polymer is a polymer containing a structural unit derived from a (meth) acrylate monomer. The acrylic ester polymer is composed of a (meth) acrylic ester monomer and optionally a monomer containing an acidic group-containing monomer, an α, β-unsaturated nitrile monomer, and other monomers. Obtained by polymerizing the composition. In addition, a known monomer can be used as each of the above monomers.

The mass ratio of the content of the binder to the content of the resin A in the resin layer L (binder / resin A: dry mass ratio) is preferably 1/40 or more, more preferably 1/30 or more. , More preferably 1/25 or more, particularly preferably 1/20 or more, preferably 1/4 or less, more preferably 1/5 or less, and more preferably 3/20 or less. More preferably, it is particularly preferably 1/10 or less, most preferably 3/40 or less. If the mass ratio of the content of the binder to the content of the resin A in the resin layer L (binder / resin A: dry mass ratio) is not less than the lower limit, the adhesiveness of the resin layer L to the vinyl chloride resin molded sheet is further improved. Can be enhanced. On the other hand, when the mass ratio of the content of the binder to the content of the resin A in the resin layer L (binder / resin A: dry mass ratio) is equal to or less than the upper limit, the transfer of the plasticizer from the vinyl chloride resin molded sheet is reduced. It is possible to further favorably suppress.

<< other components >>
The other components are not particularly limited, and include, for example, additives such as a plasticizer for the resin layer L and a dispersant.

[Plasticizer for resin layer L]
The resin layer L preferably further contains a plasticizer for the resin layer L. The resin layer L can exhibit excellent flexibility by further containing a plasticizer for the resin layer L. Therefore, the flexibility of the vinyl chloride resin laminated sheet provided with the resin layer L can be enhanced. Here, when polyvinyl alcohol is used as the resin A, the plasticizer for the resin layer L can impart particularly excellent flexibility to the resin layer L.

Examples of the plasticizer for the resin layer L include diol compounds having 1 to 4 carbon atoms, such as methylene glycol, ethylene glycol, n-propylene glycol, and n-butylene glycol; alkyl-modified poly, such as methyl polyglycol and ethyl polyglycol. It is preferable to use an alkylene oxide; and it is more preferable to use a terminal alkyl-modified polyalkylene oxide. If the above-mentioned compound is used as a plasticizer for resin, the flexibility of the resin layer L can be further increased.

Here, from the viewpoint of further increasing the flexibility of the resin layer L, the terminal alkyl group in the terminal alkyl-modified polyalkylene oxide is preferably an alkyl group having 1 to 4 carbon atoms, and is preferably a methyl group and / or an ethyl group. Is more preferable, and a methyl group is further preferable. The terminal alkyl-modified polyalkylene oxide may be either terminal-alkyl modified or terminal-alkyl modified, but is preferably terminal-alkyl modified.

Further, from the viewpoint of further increasing the flexibility of the resin layer L, the polyalkylene oxide used for preparing the terminal alkyl-modified polyalkylene oxide is preferably polyethylene oxide and / or polypropylene oxide, and more preferably polyethylene oxide. . The number average polymerization degree of the polyalkylene oxide is preferably 2 or more, more preferably 20 or less, and more preferably 10 or less.

Therefore, it is particularly preferable to use methyl polyglycol (also referred to as “polyethylene glycol monomethyl ether”), which is a methyl-modified polyethylene oxide at one end, as the alkyl-terminated polyalkylene oxide.

The mass ratio of the content of the plasticizer for the resin layer L to the content of the resin A in the resin layer L (plasticizer for the resin layer L / resin A) is preferably 1/40 or more, and more preferably 3/100 or more. Is more preferably, 7/200 or more, still more preferably 1/25 or more, particularly preferably 1/20 or more, and preferably 1/5 or less, It is more preferably 3/20 or less, further preferably 1/10 or less, further preferably 2/25 or less, and even more preferably 7/100 or less. If the mass ratio of the content of the plasticizer for the resin layer L to the content of the resin A in the resin layer L (the plasticizer for the resin layer L / the resin A) is not less than the lower limit, the flexibility of the resin layer L is further increased. Can be enhanced. On the other hand, when the mass ratio of the content of the plasticizer for the resin layer L to the content of the resin A in the resin layer L (plasticizer for the resin layer L / resin A) is equal to or less than the upper limit, the vinyl chloride resin molded sheet Of the plasticizer can be more favorably suppressed.

[Dispersant]
The dispersant is a component that can be contained in the resin layer L by being added to a liquid for forming the resin layer L used in a method for forming the resin layer L described below. Then, by adding a dispersant to the liquid for forming the resin layer L, the binder can be satisfactorily dispersed in the liquid for forming the resin layer L. Therefore, the stability and the preservability of the liquid for forming the resin layer L are improved, and the formed resin layer L can exhibit more excellent adhesion to the vinyl chloride resin molded sheet.

The dispersant is not particularly limited, and a known dispersant can be used. In particular, a surfactant can be suitably used as the dispersant. Examples of the surfactant include a nonionic surfactant such as a polyoxyalkylene alkyl ether; an anionic surfactant such as sodium dodecylbenzenesulfonate; a cationic surfactant such as dodecyl ammonium chloride; Among them, a nonionic surfactant is more preferable. In addition, the content of the dispersant in the resin layer L can be arbitrarily adjusted within a range in which a desired effect of the present invention can be obtained.

<< Thickness >>
The thickness of the resin layer L is preferably at least 0.1 μm, more preferably at least 1 μm, further preferably at least 5 μm, particularly preferably at least 10 μm, and at least 20 μm. Most preferably, it is 1000 μm or less, more preferably 100 μm or less, further preferably 50 μm or less, and particularly preferably 30 μm or less. When the thickness of the resin layer L is 0.1 μm or more, the migration of the plasticizer from the vinyl chloride resin molded sheet can be more favorably suppressed. On the other hand, if the thickness of the resin layer L is 1000 μm or less, the weight of the entire resin layer L can be reduced.

<< Method of Forming Resin Layer L >>
The resin layer L is formed on at least one side in the thickness direction of the vinyl chloride resin molded sheet.
Here, examples of a method for forming the resin layer L on at least one side in the thickness direction of the vinyl chloride resin molded sheet include the following methods.
1) A method of applying a liquid for forming a resin layer L containing a resin A and a binder to the surface of a vinyl chloride resin molded sheet, followed by drying;
2) a method of immersing a vinyl chloride resin molded sheet in a liquid for forming a resin layer L containing a resin A and a binder and drying the same; and 3) releasing a liquid for forming a resin layer L containing a resin A and a binder from a release substrate A method in which a resin layer L is prepared by applying the resin layer L on the upper side and drying, and the obtained resin layer L is transferred to the surface of a vinyl chloride resin molded sheet and laminated.
Among them, the method 1) is particularly preferable because the thickness of the resin layer L can be easily controlled. The method of the above 1) is, in detail, a step of applying a liquid for forming a resin layer L on a vinyl chloride resin molded sheet (application step), and a method of forming a resin layer L applied on a vinyl chloride resin molded sheet. Is dried to form a resin layer L (resin layer L forming step).

液 Here, the liquid for forming the resin layer L is obtained by dissolving or dispersing the resin A and the binder in an arbitrary solvent. As the solvent, a known solvent or a dispersion medium such as water, formic acid, acetic acid, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, diacetone alcohol, dimethyl ether, and diethyl ether may be used depending on the characteristics of the resin A and the binder. Can be used.

濃度 The concentration of the resin A in the liquid for forming the resin layer L can be arbitrarily adjusted within a range where the desired effects of the present invention can be obtained. Further, the mass ratio of the content of the binder to the content of the resin A in the liquid for forming the resin layer L is arbitrarily adjusted within the range of the mass ratio of the two in the resin layer L described above in the section of “Binder”. be able to.

液 The liquid for forming the resin layer L may include additives such as the plasticizer for the resin layer L and the dispersant described above in the section “Other components”.

<Coating process>
In the application step, the method for applying the liquid for forming the resin layer L onto the substrate is not particularly limited, and examples thereof include a bar coating method, a doctor blade method, a reverse roll method, a direct roll method, a gravure method, and an extrusion method. A method such as a lugation method, a brush coating method, and a spray coating method may be used. Among them, it is preferable to use the spray coating method because the vinyl chloride resin molded sheet can easily cope with a complicated structure such as a curved surface shape.

<Resin layer L forming step>
In the resin layer L forming step, the method for drying the resin layer L forming liquid applied on the vinyl chloride resin molded sheet includes, for example, hot air, hot air, low-humidity air drying, vacuum drying, infrared rays, Drying by irradiation with a line or the like is included. The drying conditions are not particularly limited, but the drying temperature is preferably from 10 ° C to 150 ° C. Further, the drying time can be arbitrarily adjusted within a range in which a desired effect of the present invention can be obtained.

(Production method of vinyl chloride resin laminated sheet)
The method for producing a vinyl chloride resin laminated sheet of the present invention includes a step of forming a resin layer L containing a resin and a binder on at least one side in the thickness direction of a vinyl chloride resin molded sheet containing a vinyl chloride resin and a plasticizer, The SP value of the resin is 14 (cal / cm ³ ) ^1/2 or more, and the classification of the adhesion of the resin to the vinyl chloride resin molded sheet evaluated by a cross-cut method according to JIS K5600-5-6 Is 5, and the classification of the adhesiveness of the binder to the vinyl chloride resin molded sheet evaluated by the cross-cut method is any one of 0 to 4. ADVANTAGE OF THE INVENTION According to the manufacturing method of the vinyl chloride resin laminated sheet of this invention, while the migration of the plasticizer from a vinyl chloride resin molded sheet can be suppressed well, the vinyl chloride which is excellent in the adhesiveness with respect to a vinyl chloride resin molded sheet of the resin layer L. A resin laminated sheet can be manufactured.

Here, as the vinyl chloride resin molded sheet, the resin, and the binder used in the method for producing the vinyl chloride resin laminated sheet, the vinyl chloride resin molded sheet, the resin A, and the binder described above in the section “Vinyl chloride resin laminated sheet” are respectively used. Can be used. The method for forming the resin layer L containing the resin A and the binder on at least one side in the thickness direction of the vinyl chloride resin molded sheet includes forming the resin layer L described above in the section of “Vinyl chloride resin laminated sheet”. A method can be used.

The method for producing a vinyl chloride resin laminated sheet of the present invention is not particularly limited as long as the above-described resin layer L is formed on at least one side in the thickness direction of the vinyl chloride resin molded sheet. The resin layer L may be formed on both sides in the thickness direction of the sheet, or the resin layer L may be formed only on one side in the thickness direction of the vinyl chloride resin molded sheet.

(Laminate)
The laminate of the present invention has a foamed polyurethane molded article and the above-mentioned vinyl chloride resin laminate sheet. The laminate of the present invention has a structure in which the above-mentioned predetermined resin layer L is interposed between the foamed polyurethane molded article and the vinyl chloride resin molded sheet. Usually, the foamed polyurethane molded article is lined with a resin layer L on one side of the vinyl chloride resin laminated sheet, and the foamed polyurethane molded article and the vinyl chloride resin laminated sheet are adjacent to each other in the laminating direction ( That is, the foamed polyurethane molded article and the vinyl chloride resin molded sheet are laminated in the laminating direction via the resin layer L).

In the laminate of the present invention, since the resin layer L is interposed between the urethane foam molded article and the vinyl chloride resin molded sheet, it is possible to favorably suppress the transfer of the plasticizer from the vinyl chloride resin molded sheet. And an excellent adhesive strength between the polyvinyl chloride resin molded sheet and the foamed polyurethane molded article. Therefore, the laminate of the present invention is suitably used as an automobile interior material of an automobile interior part such as an automobile instrument panel and a door trim, and is particularly suitably 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, on the surface of the vinyl chloride resin laminated sheet on the side where the resin layer L is provided, isocyanates and polyols, which are raw materials of the foamed polyurethane molded article, are reacted to carry out polymerization, and the polyurethane is produced by a known method. To form a foamed polyurethane molded article directly on the vinyl chloride resin laminated sheet.
The SP value of the polyurethane resin constituting the foamed polyurethane molded product is usually 8 (cal / cm ³ ) ^1/2 or more, preferably 9 (cal / cm ³ ) ^1/2 or more, and usually 12 (cal / cm ³ ) ^1/2 or more. cal / cm ³ ) ^1/2 or less, preferably 11 (cal / cm ³ ) ^1/2 or less.

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.
And the adhesion of the resin A and the binder to the vinyl chloride resin molded sheet; the thickness and flexibility of the resin layer L; the reduction rate of the plasticizer in the vinyl chloride resin molded sheet after heating; The adhesive strength to the body was measured or evaluated by the following method.

<Adhesion of Resin A and Binder to Vinyl Chloride Resin Molded Sheet>
In each of the examples and comparative examples, a 20% aqueous solution of the resin A used was prepared, applied to the surface of the produced vinyl chloride resin molded sheet opposite to the surface with the grain, using a bar coater, and left to stand for one day and dried. , About 20 μm. Thereafter, the adhesiveness of the resin A to the vinyl chloride resin molded sheet was evaluated in any one of classifications 0 to 5 by a cross-cut method according to JIS K5600-5-6.
In addition, in place of the 20% aqueous solution of the resin A, the binder used in each example was applied as it was to a surface opposite to the embossed surface of the vinyl chloride resin molded sheet with a bar coater, except that the above operation was performed. Similarly, the adhesiveness of the binder to the vinyl chloride resin molded sheet was evaluated in any of 0 to 5.

<Thickness of resin layer L>
The thickness of the resin layer L was measured by observing the cross section of the resin layer L included in the laminate obtained in each of the examples and comparative examples with a digital microscope (“VHX-900” manufactured by KEYENCE). The observation of the cross section and the measurement of the thickness were performed at a total of three points, one point each near both long sides of the laminate and one point near the center on the surface of the laminate, and the smallest numerical value was used as the measurement result.

<Flexibility of resin layer L>
Hold the vinyl chloride resin laminated sheet obtained in each of the examples and comparative examples from below with both hands so that the surface with the texture is downward (that is, the surface on which the resin layer L is formed is upward), and is substantially in the longitudinal direction. The central portion was folded in a valley, visually observed, and the degree of peeling of the resin layer L was evaluated according to the following criteria.
A: No peeling was observed.
B: Peeling is slightly observed.
C: Peeling is partially observed.
D: Almost complete peeling is confirmed.

<Reduction rate of plasticizer in vinyl chloride resin molded sheet before and after heating>
Only the vinyl chloride resin molded sheet was peeled off from the laminate obtained in each of the examples and comparative examples, and 50 ± 0.2 mg was collected from the vinyl chloride resin molded sheet and dissolved in tetrahydrofuran (THF). After the volume was further increased to 50 mL with methanol, the supernatant solution was analyzed by HPLC (High Performance Liquid Chromatography) under the following conditions to determine the content A (%) of the plasticizer in the vinyl chloride resin molded sheet before heating. It was measured.

High-performance liquid chromatograph analyzer: "LC1260-II" manufactured by Agilent
Column: "ZORBAX Eclipse XDB-C8" manufactured by Agilent
Column temperature: 40 ° C
Mobile phase A: acetonitrile Mobile phase B: ion-exchanged water Gradient conditions: 0 min (20 vol% mobile phase B), 2.5 min (0 vol% mobile phase B), 8.0 min (0 vol% mobile phase B)
Flow rate: 1.0 mL / min
Detector: Diode array detector (DAD)
Signal: 254 nm
Ref: 360 nm
Injection amount: 1 μm

Further, except that the laminates obtained in the respective Examples and Comparative Examples were placed in an oven and heated in an environment at a temperature of 130 ° C. for 100 hours, the vinyl chloride after heating was processed in the same manner as described above. The content B (%) of the plasticizer in the resin molded sheet was measured.

As described above, when a polyvinyl chloride resin molded sheet having a content of other components (eg, vinyl chloride resin) other than the plasticizer, which is W (g), is heated under the above-described conditions, the plasticity of the vinyl chloride resin molded sheet before and after heating is increased. The content (g) and content ratio (%) of the agent and other components are shown in Table 1 using A, B, and W described above. Then, the reduction rate X (%) of the plasticizer was calculated by the following calculation formula (I). The content W (g) of other components in the vinyl chloride resin molded sheet does not change before and after heating.

Reduction rate of plasticizer X (%)
= 100 x {(content of plasticizer before heating)-(content of plasticizer after heating)} / (content of plasticizer before heating)
= 100 × {W × A / (100-A) −W × B / (100-B)} / [W × A / (100-A)]
= 100 × [1- {B × (100-A)} / {A × (100-B)}] (I)

<Adhesive strength between vinyl chloride resin molded sheet and foamed polyurethane molded article>
The laminate obtained in each of the examples and comparative examples was cut to obtain a test piece having a size of 150 mm × 25 mm × 1.2 mm. Using an autograph (“AG-20kN IS” manufactured by Shimadzu Corporation), the vinyl chloride resin molded sheet part is peeled from the foamed polyurethane molded part along the longitudinal direction of the test piece using the obtained test piece 180 A peel test was performed to measure the peel strength (N / 25 mm). The measurement conditions at this time were a peeling speed of 200 mm / min and a temperature of 23 ° C. The larger the value of the obtained peel strength, the better the adhesive strength between the vinyl chloride resin molded sheet and the foamed polyurethane molded article in the laminate. Therefore, the larger the value of the obtained peel strength is, the more excellent the adhesiveness of the resin layer L interposed between the vinyl chloride resin molded sheet and the foamed polyurethane molded article is to the vinyl chloride resin molded sheet.

(Example 1)
<Preparation of vinyl chloride resin composition>
Of the components shown in Table 2, components except for a plasticizer (trimellitic acid ester), an epoxidized soybean oil as a stabilizer, and vinyl chloride resin fine particles as a dusting agent were put into a Henschel mixer and mixed. . When the temperature of the mixture rises to 80 ° C., all of the plasticizer and the epoxidized soybean oil as a stabilizer are added, and the temperature is further increased to dry up (the plasticizer is a vinyl chloride resin. The mixture was absorbed by the vinyl chloride resin particles, and the mixture was further solidified). Thereafter, 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 molded sheet>
The vinyl chloride resin composition obtained above is sprinkled on a mold with a grain heated to a temperature of 250 ° C., and is left to melt for an arbitrary time of about 8 to 20 seconds. Was shaken off. Thereafter, the mold with the grain onto which the vinyl chloride resin composition was sprinkled was allowed to stand in an oven set at a temperature of 200 ° C., and at the time when 60 seconds had passed from the standing, the mold with the grain was cooled with cooling water. . When the mold temperature was cooled to 40 ° C., the 200 mm × 300 mm × 1.2 mm molded sheet of vinyl chloride resin was released from the mold.

<Preparation of liquid for forming resin layer L>
In a container, 32 parts of water as a dispersion medium and 48 parts of isopropyl alcohol (manufactured by Kanto Kagaku); 2 parts of ethylene glycol (manufactured by Kanto Kagaku) as a plasticizer for the resin layer L; and polyoxy as a dispersant 2 parts of an alkylene alkyl ether (“Emulgen LS-114” manufactured by Kao Corporation) was charged, and stirring was started at room temperature (about 23 ° C.). Therein, polyvinyl alcohol (PVA, "JMR-10M" manufactured by Japan Vineyard Poval Co., Ltd.) as resin A, degree of saponification from polyvinyl acetate: 65%, SP value: 16.4 (cal / cm ³ ) ^1/2 ) 20 parts were charged, and heating was started while stirring. The mixture was heated to about 45 ° C., and when the PVA was dissolved, the heating was stopped, and the mixture was allowed to cool to around room temperature with stirring. Thereafter, while stirring, 2 parts of a polycarbonate polyester-based polyurethane ("Toutan S" manufactured by Toue Co., Ltd.) as a binder was added in terms of dry mass and mixed to prepare a liquid for forming a resin layer L.
When the adhesion of the resin A and the binder to the vinyl chloride resin molded sheet was evaluated, the classification of the adhesion of the polyvinyl alcohol as the resin A to the vinyl chloride resin molded sheet was 5, and the polycarbonate polyester-based polyurethane as the binder was used. Was 0. The classification of the adhesion to the vinyl chloride resin molded sheet was 0.

<Production of vinyl chloride resin laminated sheet (formation of resin layer L)>
The liquid for forming the resin layer L obtained by the above method was applied by spraying to the surface of the obtained vinyl chloride resin molded sheet opposite to the surface with the grain. Thereafter, by drying with warm air at 20 ° C. for one day, a vinyl chloride resin laminated sheet in which the resin layer L was formed on one surface of the vinyl chloride resin molded sheet was produced. The flexibility of the resin layer L was evaluated using the obtained vinyl chloride resin laminated sheet. Table 3 shows the results.

<Formation of laminate>
The produced vinyl chloride resin laminated sheet was allowed to stand in an oven set at a temperature of 100 ° C. for 2 hours, and then laid in a mold of 200 mm × 300 mm × 10 mm with the grained surface facing down.
Separately, 50 parts of PO (propylene oxide) / EO (ethylene oxide) block adduct of propylene glycol (hydroxyl value: 28, terminal EO unit content = 10%, internal EO unit content: 4%), glycerin PO 50 parts of an 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) )), 1.2 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.). To obtain a polyol mixture. Further, a mixed liquid was prepared by mixing the obtained polyol mixture and polymethylene polyphenylene polyisocyanate (polymeric MDI) at a ratio at which the isocyanate index became 98. Then, the prepared mixture was poured onto a vinyl chloride resin laminated sheet laid in a mold as described above. Thereafter, the mold was covered with an aluminum plate of 348 mm × 255 mm × 10 mm, and the mold was sealed. By leaving the mold closed and leaving it for 5 minutes, a foamed polyurethane molded article (thickness: 8.78 mm, density: 0.18 g) was placed adjacent to the vinyl chloride resin laminated sheet (thickness: 1.22 mm) as the skin. / Cm ³ , SP value: 10.0 (cal / cm ³ ) ^1/2 ) was backed (laminated) in a mold.
Then, the formed laminate is taken out of the mold, and the reduction rate of the plasticizer in the vinyl chloride resin molded sheet before and after heating, and the adhesion between the vinyl chloride resin molded sheet and the foamed polyurethane molded article according to the above-described method. The strength was measured and evaluated. Table 3 shows the results. In addition, when the thickness of the resin layer L was measured using the laminated body, it was 20 μm.

(Example 2)
In preparing the liquid for forming the resin layer L, 1 part of methyl polyglycol (number average polymerization degree: 4) was used as a plasticizer for the resin layer L instead of 2 parts of ethylene glycol, and a polycarbonate polyester-based polyurethane was used as a binder. Example 1 was repeated except that 1 part (in terms of dry mass) of a non-yellowing polycarbonate-based polyurethane (“Superflex (registered trademark) 460” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used instead of 2 parts (in terms of dry mass). In the same manner as in Example 1, a vinyl chloride resin composition, a vinyl chloride resin molded sheet, a vinyl chloride resin laminated sheet, and a laminate were produced.
Then, the measurement was performed in the same manner as in Example 1. Table 3 shows the results.
When the adhesion of the binder to the vinyl chloride resin molded sheet was evaluated, the classification of the adhesion of the non-yellowing polycarbonate-based polyurethane as the binder to the vinyl chloride resin molded sheet was 1. When the thickness of the resin layer L was measured, it was 20 μm.

(Example 3)
In preparing the liquid for forming the resin layer L, a yellowing-type polyester-based polyurethane ("Superflex (registered trademark) 740" manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used instead of 1 part (in terms of dry mass) of non-yellowing-type polycarbonate-based polyurethane as a binder ") A vinyl chloride resin composition, a vinyl chloride resin molded sheet, a vinyl chloride resin laminated sheet, and a laminate were produced in the same manner as in Example 2 except that 1 part (in terms of dry mass) was used.
Then, the measurement was performed in the same manner as in Example 1. Table 3 shows the results.
When the adhesion of the binder to the vinyl chloride resin molded sheet was evaluated, the classification of the adhesion of the yellowing type polyester-based polyurethane as the binder to the vinyl chloride resin molded sheet was 0. When the thickness of the resin layer L was measured, it was 20 μm.

(Example 4)
In the preparation of the liquid for forming the resin layer L, the same procedure as in Example 3 was carried out except that the amount of the yellowing-type polyester-based polyurethane used as the binder was changed from 1 part (in terms of dry mass) to 2 parts (in terms of dry mass). Thus, a vinyl chloride resin composition, a vinyl chloride resin molded sheet, a vinyl chloride resin laminated sheet, and a laminate were produced.
Then, the measurement was performed in the same manner as in Example 1. Table 3 shows the results.
When the thickness of the dried resin layer L was measured, it was 20 μm.

(Comparative Example 1)
In the production of the vinyl chloride resin laminated sheet, the resin layer L was not formed on the surface opposite to the embossed surface of the vinyl chloride resin molded sheet (that is, the vinyl chloride resin laminated sheet was not produced). Instead of using a vinyl chloride resin molded sheet having no resin layer L, a vinyl chloride resin composition, a vinyl chloride resin molded sheet, And the laminated body was manufactured.
And about the obtained laminated body, the reduction rate of the plasticizer in the vinyl chloride resin molded sheet before and after heating was measured. Table 1 shows the results.

(Comparative Example 2)
In the preparation of the liquid for forming the resin layer L, a vinyl chloride resin composition, a vinyl chloride resin molded sheet, and a vinyl chloride resin sheet were prepared in the same manner as in Example 1 except that 2 parts of a polycarbonate polyester-based polyurethane as a binder was not added. A resin laminate sheet and a laminate were manufactured.
Then, the measurement was performed in the same manner as in Example 1. Table 3 shows the results.
When the thickness of the resin layer L was measured, it was 20 μm.

1) Product name “ZEST (registered trademark) 1700ZI” manufactured by Shin-Daiichi PVC Co., Ltd. (suspension polymerization method, SP value: 9.6 (cal / cm ³ ) ^1/2 )
2) Product name “ZEST PQLTX” manufactured by Shin-Daiichi PVC Co., Ltd. (emulsion polymerization method, SP value: 9.6 (cal / cm ³ ) ^1/2 )
3) Product name “Ryuron Paste (registered trademark) 860” manufactured by Tosoh Corporation (emulsion polymerization method, SP value: 9.6 (cal / cm ³ ) ^1/2 )
4) Product name “TRIMEX N-08” manufactured by Kao Corporation (SP value: 9.0 (cal / cm ³ ) ^1/2 )
5) Product name “X-50-1039A” manufactured by Shin-Etsu Chemical Co., Ltd.
6) Product name “ADEKASIZER O-130S” manufactured by ADEKA
7) Product name “Alkamizer (registered trademark) 5” manufactured by Kyowa Chemical Industry Co., Ltd.
8) Product name "MIZUKALIZER DS" manufactured by Mizusawa Chemical Industry Co., Ltd.
9) Product name “Karenz DK-1” manufactured by Showa Denko KK
10) Sakai Chemical Industry Co., Ltd., product name "SAKAI SZ2000"
11) Product name “ADEKA STAB LS-12” manufactured by ADEKA
12) Product name “DA PX 1720 (A) Black” manufactured by Dainichi Seika

From Table 3, at least one side of the vinyl chloride resin molded sheet containing the plasticizer contains a resin having a SP value within a predetermined range and a binder, and the adhesion of the resin and the binder to the vinyl chloride resin molded sheet. In the vinyl chloride resin laminated sheets of Examples 1 to 4 in which the resin layers L each having a predetermined classification are arranged, the transfer of the plasticizer from the vinyl chloride resin molded sheet can be suppressed well, and It can be seen that L has excellent adhesiveness to the vinyl chloride resin molded sheet.
On the other hand, from Comparative Example 1, it can be seen that the vinyl chloride resin molded sheet alone without the predetermined resin layer L cannot sufficiently suppress the transfer of the plasticizer from the vinyl chloride resin molded sheet.
Furthermore, at least one side of the vinyl chloride resin molded sheet containing a plasticizer, the SP value is in a predetermined range, and, while containing a resin whose adhesion to the vinyl chloride resin molded sheet is evaluated to a predetermined classification, The vinyl chloride resin laminated sheet of Comparative Example 2 in which a resin layer not containing a predetermined binder is arranged, although the migration of the plasticizer from the vinyl chloride resin molded sheet can be suppressed well, the vinyl chloride resin molded sheet of the resin layer It can be seen that the adhesiveness to is poor.

Claims

A vinyl chloride resin molded sheet containing a vinyl chloride resin and a plasticizer,
A resin layer L containing a resin A and a binder,
A vinyl chloride resin laminated sheet in which the resin layer L is disposed on at least one side in the thickness direction of the vinyl chloride resin molded sheet,
The resin A has an SP value of 14 (cal / cm 3 ) 1/2 or more,
The classification of the adhesiveness of the resin A to the vinyl chloride resin molded sheet evaluated by a cross-cut method based on JIS K5600-5-6 is 5,
A vinyl chloride resin laminated sheet wherein the classification of the adhesiveness of the binder to the vinyl chloride resin molded sheet evaluated by the cross-cut method is any of 0 to 4.
The vinyl chloride resin laminated sheet according to claim 1, wherein the resin layer L further includes a plasticizer for the resin layer L.
The mass ratio of the content of the binder to the content of the resin A in the resin layer L (binder / resin A) is 1/40 or more and 1/4 or less in dry mass ratio. 3. The vinyl chloride resin laminated sheet according to 2.
(4) The vinyl chloride resin laminated sheet according to any one of (1) to (3), wherein the binder contains at least one of a urethane binder and an acrylic ester binder.
(5) The vinyl chloride resin laminated sheet according to any one of (1) to (4), which is used for a skin of an automobile instrument panel.
Forming a resin layer L containing a resin A and a binder on at least one side in the thickness direction of a vinyl chloride resin molded sheet containing a vinyl chloride resin and a plasticizer,
The SP value of the resin is 14 (cal / cm 3 ) 1/2 or more,
The classification of the adhesiveness of the resin to the vinyl chloride resin molded sheet evaluated by a cross cut method based on JIS K5600-5-6 is 5,
A method for producing a vinyl chloride resin laminated sheet, wherein the classification of the adhesiveness of the binder to the vinyl chloride resin molded sheet evaluated by the cross-cut method is 0 to 4.
Foamed polyurethane moldings,
A vinyl chloride resin laminated sheet according to any one of claims 1 to 5,
A laminate having
A laminate, wherein the resin layer L is disposed between the foamed polyurethane molded article and the vinyl chloride resin molded sheet.