JPH02310047A - Vinyl chloride resin sheet - Google Patents

Abstract

PURPOSE:To integrally bond a polyurethane resin layer and a vinyl chloride resin layer without using an adhesive and to obtain a sheet excellent in hydrolysis resistance by forming a polyurethane resin layer based on a polycarbonate type polyurethane resin on a releasable carrier. CONSTITUTION:Polycarbonate type polyurethane used on a releasable carrier is a polymer of polycarbonate type polyol, isocyanate and a chain extender and a polyvinyl chloride paste resin layer is formed on this polyurethane resin layer without interposing an adhesive layer and the releasable carrier is released to obtain a vinyl chloride resin sheet. By this manufacturing method using no adhesive, the vinyl chloride resin sheet excellent in the adhesiveness between the polyurethane resin layer and the vinyl chloride paste resin layer can be obtained in an extremely efficient manner. Therefore, this sheet generates no deterioration of feeling due to an adhesive and has excellent hydrolysis resis tance and can be used as a material for shoes, a bag or clothing and is extreme ly effective in a case used over a long period of time.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a vinyl chloride resin sheet 1-, and more particularly to a vinyl chloride resin sheet used for a car seat shade.

[Prior art and Problem that the invention attempts to solve]

Conventionally, vinyl chloride leather has been used for car seats, etc., which is a base fabric laminated with a layer of foamed or non-foamed vinyl chloride resin and embossed on the surface, but the temperature inside the car is extremely high in the summer. However, the plasticizer blended into the vinyl chloride resin volatilizes and adheres to car window glass, causing fogging, and it is extremely hard in winter.
Moreover, not only does it give a cold feeling, but it also has the disadvantage that it tends to get stiff in the summer.

In order to improve this, a vinyl chloride resin sheet with a polyurethane resin layer formed on the surface of the vinyl chloride resin layer was tested, but the adhesion between the vinyl chloride resin and polyurethane was poor, and the polyurethane resin layer and the vinyl chloride resin layer An adhesive layer must be interposed between the layers, and the presence of this adhesive layer significantly impairs the feel of the vinyl chloride resin sheet on which the polyurethane resin layer is laminated. In addition, when the polyurethane used is polyester polyurethane, it has poor hydrolyzability and poor durability, and cannot be used for applications that are used under harsh conditions for a long period of time, such as car seat notebooks. It was something.

(Means for Solving the Problems) The present invention solves the above-mentioned drawbacks of the prior art, integrates a polyurethane resin layer and a vinyl chloride resin layer without using an adhesive, and provides moisture resistance. The purpose of this invention is to provide a polyurethane resin-coated vinyl chloride resin sheet with slanted corner T properties, and is constructed as follows.

(1) A polyurethane resin layer mainly composed of polycarbonate-based polyurethane resin is formed on the if-type carrier, and a polyvinyl chloride paste I resin layer is formed on the polyurethane resin layer without using an adhesive layer. , vinyl chloride resin sort made by peeling off the releasable carrier.

(2) The vinyl chloride resin sheet according to claim 1, wherein the polyvinyl chloride paste resin layer is a non-foamed polyvinyl chloride base resin layer.

(3) Claim 1, wherein the polyvinyl chloride paste resin layer is a foamed polyvinyl chloride paste resin layer.
The vinyl chloride resin sheet described in Section 1.

(4) The vinyl chloride resin sheet according to claim 1, wherein the polyvinyl chloride paste resin layer is a composite layer of an unfoamed polyvinyl chloride paste resin layer and a foamed polyvinyl chloride paste resin layer.

(5) The vinyl chloride resin sheet according to any one of claims 1 to 4, wherein a base fabric is further laminated on the polyvinyl chloride paste resin layer.

(6) Claims 1 to 5, wherein a surface treatment layer is formed by applying a surface treatment liquid made of a polyurethane resin on a polyurethane resin layer whose main component is a polycarbonate polyurethane resin. The vinyl chloride resin sheet according to any one of the items.

(7) Applying polycarbo-based polyurethane resin solution to a releasable carrier, drying it, applying polyvinyl chloride paste sol, and peeling off the dosage form carrier after heating and gelling. Characteristic method for manufacturing vinyl chloride resin sheets.

(8), B+) The method for producing a vinyl chloride resin sheet according to claim 7, wherein the vinyl chloride paste sol is a foamable polyvinyl chloride paste sol containing a foaming agent, and the vinyl chloride paste sol is foamed after heating and gelling.

(9) Production of a vinyl chloride resin sheet according to any one of claims 7 to 8, in which after peeling off the M-type carrier, a surface treatment liquid made of a polyurethane resin is applied to the surface and dried. Method.

As a release carrier, in addition to release paper such as silicone paper whose surface is treated with silicone, silicone gel, etc.
Any carrier that is generally used as a releasable carrier can be used.

In the present invention, the polyurethane resin mainly composed of polycarbonate-based polyurethane refers to not only a polycarbonate-based polyurethane resin alone, but also a mixture of a polycarbonate-based polyurethane resin and another polyurethane resin. = Polyurethane resin containing at least 50% or more.

The polycarbonate polyurethane used in the present invention is a polymer of a polycarbonate polyol, an isocyanate, and a chain extender, and the polycarbonate polyol has the following general formula (where R-(CH,)p- Yes, P≧2.

It is also a polyalkylene polycarbonate-1 polyol represented by n=5 to 200). As a specific example, 1,6-hexylcarbonate=1 polyol is preferred.

Also usable are mixtures in which the - part of the polyalkylene polycarpo un-1-based polyol is replaced with polyoxyalgylene-modified polycarbonate.

In addition, as the isocyanate, tetramethylene diisosoa:
, 2,2.4-1-methyl-1,6-hexane diisocyanate, 1-methylchlorohexane 2,4-diisocyanate, 3.3'-dimethyl-4,4'-diisocyanate dicyclohexylmethane, 4,4° - Aliphatic or cycloaliphatic diisocyanates such as dicyclohexylmethane diisocyanate and trilene isocyanate-1
・, diphenylmethane diisocyanate-1-1, hydrogenated diphenylmethane diisocyanate-1-1, aromatic diisocyanates such as xylylene diisocyanate-1, etc. can be used, but aliphatic or alicyclic diisocyanate-1. Polycarbonate polyurethane using hydrogenated diphenylmethane diisocyanate is non-yellowing type.
Particularly preferred.

Examples of polyurethanes that can be used in combination with polycarbonate-based polyurethane include polyether-based polyurethane containing polytetramethylene glycol or polypropylene glycol as the polyol component, and polyester obtained by reacting a hydroxyl compound from carbon t & 4 with a dibasic acid as a polyol component. There are polyester-based polyurethanes containing ε-caprolactone-based polyester as a polyol component, and the like.

The vinyl chloride paste sol used in the present invention includes vinyl chloride homopolymer, vinyl chloride and other monomers, such as ethylene, vinyl acetate, vinyl needle, maleic acid ester, (meth)acrylic acid, and (meth)acrylic acid ester. A plastisol prepared by dispersing a vinyl chloride resin such as a copolymer in a plasticizer can be used.

As the plasticizer, any plasticizer that is normally used in vinyl chloride paste sol can be used.

For example, di-2-ethylhexyl phthalate, di-n-
Phthalic acid derivatives such as ocdyl phthalate, didodecyl phthalate, butylbenzyl phthalate, dibutyl phthalate, dilauryl phthalate, didodecyl phthalate, diisodecyl phthalate; diisodecyl phthalate,
Isophthalic acid derivatives such as diisononyl tucrate; Adipic acid derivatives such as n-butyl adipate and dioctyl adipate; 1 Maleic acid derivatives such as di-butyl maleate; citric acid derivatives such as nitri-butyl citrate; monobutyl itacone-1 Itaconic acid derivatives such as ・;
Oleic acid derivatives such as butyl oleate; Glycerin monocitrate Sinoleic acid derivatives; Other tricresyl phosphate (TCP), tricylyl phosphate (T
χP), dixylyl monocresyl phosphate (DXM
CP), monoxylyl dicresyl phosphate l-(MX
Examples include phosphoric acid ester plasticizers such as DCP), epoxy group-containing fucuric acid ester plasticizers, evolvated soybean oil, and evoluted resin plasticizers. These can be used alone or in combination of two or more.

In the present invention, commonly used additives are added to the vinyl chloride paste sol, such as foaming agents, ultraviolet absorbers, stabilizers, light stabilizers, antioxidants, colorants, fillers, weather resistance agents, It is possible to add a heat initial discoloration prevention agent.

Examples of the blowing agent include azone carphonamide 1, Abhis isobutyl IJ21 lyl, N,N'-dutrobencumethylamine, Hensensulponyl storadi, 1, and the like.

As a UV absorber, consider the UV absorbing ability of the UV absorber and its compatibility with the chlorinated heel resin used.
Appropriate selections can be made from a wide range of types. Usable Shiyu 1-ray absorbers include H+'ll:) quinone, H10 quinone Noririchi-1, etc.
'l = 1-non-purple 1-ray absorber, phenyllyrylate-1, lilycylic acid-based ultraviolet absorber such as Baraoff (Luso T7 nyllylythyre 1), 2-human 1: +-1-cy 4-methoxy Jihenzufenon, 2 Hi (Roshishi 4-n
--Octo4shihenzosoenone, 2-L ILl-
1-U・-4-Methoxy 2゛ Nlylphoxyhenpazov Jnon, 2,2゛ Dipyll: l-1-So4,4
Dimetho-1 cyhenzophenone, 2 human n:l
l 4-hensoinol-1-shi ＼nzophenone)-sunsof J, non-based ultraviolet absorber, 2-(2”
-Hitorow 1- i, -・5'-Methyl bow feuille,・[
) Henzo lriazur, 2-(2'-hydroxy-5'
-methyleney-Q/shi)-5-carphonic acid butyl ester, 2(2'hydroxo-
5゛-methylphenyl)-5,6'-'riY-Jru＼
[
In addition to ray absorbers such as +1 azole and others, there are also oxidized anilide series, etc. It can be used using i().

Stabilizers include halium stearate I1, zinc stearate, calcium stearate J1, barium ricinoleate, dibutylsumalet I, dibutylsumalet-1
ester, triphenyl phosphite di-I ctyl phosphite, cyphenylua, /no I bosphite, 1-li-n-1 decyl phosphite 1,
l-so n-1 denru 1 richi'bosfaei[,,fa,nil-,,-'n-decylpossoai 1-,cy n-4ktade/le-pentaerythritol diphospha. Ito etc. can be mentioned.

Examples of the light stabilizer include binder-1 amine light stabilizers.

IJ, 2.6-di-1-butyl-4 as an antioxidant
-Methylphenol, 2.2'-methylenehis (6-1zotyl-4-edylphenol), 2.6-so1 butyl p-cresol, 4.4'-thiobis(3
phenolic antioxidants such as -methyl-6-L-butylfuninol), thiodib I copionate esters such as di-n-1+den-thiodibrobio-1-, thiodib-I'l-occudecyl-thiodibutybide+bionate, G-n-
Examples include dodecyl sulfide, G-n-octadecyl sulfide 1'', G-n-octadenyl sulfide 1'I'', etc., and 2'N-octadecyl sulfide (1).

As fillers, Noriyoku, talc, Carbonated Luciu J,...
Magnesium carbonate J., feldspar, quartz, high rotal (neu 1 compound, aluminum hydroxide J, magnesium sulfate, phosphoric acid 11, magnesium hydroxide L, cross-linked vinyl chloride resin, cross-linked 4 pieces of acrylic resin etc. are produced.

Of course, compounds other than those exemplified here may also be added.

As the base fabric used in the present invention, any fabric such as knitted fabric, woven fabric, or nonwoven fabric can be used.

The surface treatment liquid made of polyurethane resin includes polycarbonate polyurethane, polyether polyurethane whose polyol component is polytetramethylene glycol or polypropylene gelylcol, a cycloxyl compound having 4 or more carbon atoms, and a dibasic acid. Solvent solutions of polyester-based polyurethane containing the polyester obtained by the reaction as the polyol component, polyester-based polyurethane containing the polyester obtained by the reaction as the polyol component, and urethane-modified polyamino acid resin are used. can.

[Examples] Hereinafter, examples of the present invention will be described, but the present invention is not limited to these examples.

Example 1 A solvent solution of 1,6-hexane polycarboxylic polyurethane was applied to the surface of silicone vapor to a dry thickness of 15μ, and this was heated and dried to form a polyurethane resin layer. On the polyurethane resin layer, a dinyl chloride base tosol having the following composition was applied to 0.1 mm of Pl.
Heat at 0°C for 2 minutes and chloride 2) 1 resin (E' 1 bottle 7 1
) Manufactured by: Geon131)
00Q-') "Black 1ner
First, apply vinyl chloride paste Izuru of the following composition to 0.2 mm of 17,
on12+) 100 N Mechnalphthale-1・70 Stabilizer (77 Calcium Co., Ltd.: fL 21)
Riazodicarbonami I2 black toner 1 this 13
After heating at 0°C for 2 minutes, pasting fabric 79 (j, 1. cloth) with an enclosing agent for 1q, heat at 200°C for 2 minutes.

Then, the foamed hardened adhesive paper was separated by 2/1J and then the chloride chloride resin was used.

The adhesion, texture, and hydrolysis resistance of the polyurethane resin layer of this vinyl chloride resin No. 1 and the polyurethane resin layer of the polyvinyl chloride resin layer were measured. The measurement results are shown in Table 1.

(Adhesiveness test) 1m11 was applied to the polyurethane resin layer of the chlorinated Higol resin sheet.
Make 11 cuts in each side of fi at 1 interval (1mIf
Form 100 bind-off seams on each side) and apply adhesive tape (
After applying the adhesive on the adhesive-coated surface of the 1-3 tape), remove the adhesive tape 211 and remove the polyurethane resin skin 11 remaining on the surface of the vinyl chloride resin sheet (film on all sides of Inon).
The reason for this was investigated and those with 100 remaining were considered good, and all those with a bundle height of 100 were judged to be defective.

(Texture) Judgment was made based on the feel when the vinyl chloride resin sheet was rubbed with hands.

◎・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・A hard, rough texture, or a feeling where the polyurethane resin layer lifts (hydrolysis resistance)] Test sample of hinyl chloride resin JJ'+ was left for 4 weeks at a humidity of 95-6 and a temperature of 70°C, and then the resin layer of the specimen was subjected to a load of 1k using a Taber type abrasion tester.
g, Pγ After 500 scratches, a degree of surface abrasion was observed.

The blank test was carried out using a (11) vinyl chloride resin sheet as it was, a load of 1. kg using a Taber type abrasion tester.
This is the result of observing the degree of surface wear after 500 frictions.

Example 2 A polyurethane tree JJ! made by mixing the polycarbonate-based Polyurekne used in Example 1 and Bolite 1 lamethylene ether glycol-based Polyurethane L/Tan in a ratio of 50 + 50. f
A hinyl chloride resin sheet was obtained in the same manner as in Example 1, except that the following was used. The same measurements as in Example 1 were performed on the vinyl chloride resin sheet obtained by fjff, and the results are shown in Table 1.

Comparative Example 1 The polycarbonate polyurethane and polypropylene ether glycol polyurethane used in Example 1 were
Polyurethane resin I fi mixed at 0:60
- 1. A vinyl chloride resin sheet I was obtained in the same manner as in Example 1. The obtained vinyl chloride resin sheet 1 was subjected to the same measurements as in Example 1, and the results are shown in Table 1.

Comparative Example 2 A vinyl chloride resin sheet was obtained in the same manner as in Example 1, except that polypropylene ether glycol polyurethane was used in place of the polycarbonate polyurethane used in Example 1. The obtained vinyl chloride resin sheet was subjected to the same measurements as in Example 1, and the results are shown in Table 1.

Comparative Example 3 The same vinyl chloride base 1 sol used in Example 1 was applied to the surface of silicone paper in the same order, and after pasting Suffu 79 (base fabric) with adhesive, After heating for 2 minutes, the "C foam cured adhesive pattern paper was peeled off, and the polyvinyl chloride resin foam sheet 1" was obtained.

- Apply polyurethane polyurethane glycol to another silicone paper to a dry thickness of 15μ, heat and dry the dirt to form a polyurethane resin layer, and adhere two-wave polyurethane onto the polyurethane resin layer. The polyvinyl chloride resin foamed sheet I was bonded to the vinyl chloride resin foamed sheet I, where the vinyl chloride paste resin layer was in contact with the adhesive (31), to obtain a vinyl chloride resin sheet. The same measurements as in Example 1 were performed on the rounded vinyl chloride resin sheet, and the results are shown in Table 1.

Comparative Example 4 The same vinyl chloride paste used in Example 1 was applied to the surface of the silicone vapor in the same order, and after pasting Sufu 79 (base fabric) with adhesive, it was heated at 200°C for 2 minutes. After foaming and curing by heating, the release paper was peeled off to obtain a vinyl chloride resin foam sheet.

On the other hand, a solvent solution of a polyester polyurethane obtained by reacting another silicone paper, ethylene glycol, and adipic acid with diphenylmethane diisonanate and 1,4-butanediol, was dried. -) Coating so that t is 15μ, heating and drying this to form a polyurethane resin layer, coating the polyurethane resin layer with a two-wave type polyurethane adhesive, and applying the previously obtained vinyl chloride resin The vinyl chloride paste l-resin layer of the foamed sheet I was bonded together so that it was in contact with the adhesive to obtain a vinyl chloride resin sheet. The obtained vinyl chloride resin sheet was subjected to the same measurements as in Example 1,
The results are shown in Table 1.

(The following is a blank space) Table 1 As is clear from Table 1, the vinyl chloride resin sheet of Example 1 has excellent adhesion between the polyurethane resin layer and the vinyl chloride paste resin layer, texture, and hydrolysis resistance.
Comparative Example 1.2, which does not use polyurethane resin mainly composed of polycarbonate-based polyurethane and does not use adhesive for adhesion to the vinyl chloride paste resin layer.
The adhesiveness between the polyurethane resin layer and the vinyl chloride paste resin layer is poor, and the texture is such that the polyurethane resin layer lifts up, which is not desirable. In addition, Comparative Example 3.4, in which an adhesive was used to bond to the vinyl chloride paste resin layer without using a polyurethane resin mainly composed of polycarbonate-based polyurethane, had good adhesion, but had a hard texture and a stiff texture. It has a bad texture. Comparative Example 4 uses a polyester polyurethane whose polyol component is a polyester obtained by reacting a hydroxyl compound with 2 carbon atoms and a dibasic acid, so an adhesive must be used.
Therefore, the texture is poor, and the durability and hydrolysis resistance are also extremely poor.

〔Effect of the invention〕

Since the present invention is configured as described above, the adhesiveness between the polyurethane resin layer and the vinyl chloride-based resin layer is excellent even without the use of an adhesive, and therefore, there is no deterioration in texture due to the adhesive. Moreover, since it has excellent hydrolysis resistance, it is extremely effective for applications that are used for a long period of time, such as furniture and vehicle seats. Moreover, 5! of the vinyl chloride resin sheet of the present invention! Since the manufacturing method does not use a contact agent, one or two steps can be omitted compared to the conventional manufacturing method, so it is extremely efficient and allows for close contact between the polyurethane resin layer and the vinyl chloride paste resin layer. The 4HB vinyl chloride calendar sheet is perfect.

Patent Applicant Axis Co., Ltd. Procedural Amendment (Voluntary) 1998, Month, Day 1, Indication of Case Patent Application No. 1-132410 2, Title of Invention Vinyl Chloride Resin Sheet 36 Person Who Makes Amendment Relationship to Case Application Person (◎160) 22-5 Daikyomachi, Shinjuku-ku, Tokyo Telephone 03 (225) 2143 4 Date of amendment order Voluntary 5, Subject of amendment 6, Contents of amendment as follows (1), Specification No. 3 Insert the following sentence between "...car seat" and "etc..." on the fourth line of the page.

", vR2 shoes, bags, clothing" (2) Insert the following sentence between "...because it is excellent" and "furniture..." on page 23, line 7 of the specification.

[It can be used as a material for bags, clothing, etc., especially] that's all

Claims (9)

[Claims] (1) A polyurethane resin layer mainly composed of polycarbonate-based polyurethane resin is formed on a releasable carrier, and a polyvinyl chloride paste resin layer is formed on the polyurethane resin layer without an adhesive layer, and the mold releasability is improved. A vinyl chloride resin sheet made by peeling off the carrier. (2) The vinyl chloride resin sheet according to claim 1, wherein the polyvinyl chloride paste resin layer is a non-foamed polyvinyl chloride paste resin layer. (3) The vinyl chloride resin sheet according to claim 1, wherein the polyvinyl chloride paste resin layer is a foamed polyvinyl chloride paste resin layer. (4) The vinyl chloride resin sheet according to claim 1, wherein the polyvinyl chloride paste resin layer is a composite layer of an unfoamed polyvinyl chloride paste resin layer and a foamed polyvinyl chloride paste resin layer. (5) The vinyl chloride resin sheet according to any one of claims 1 to 4, wherein a base fabric is further laminated on the polyvinyl chloride paste resin layer. (6) Claims 1 to 5, wherein a surface treatment layer is formed by applying a surface treatment liquid made of a polyurethane resin on a polyurethane resin layer whose main component is a polycarbonate polyurethane resin. The vinyl chloride resin sheet according to any one of the items. (7) A chlorination method characterized by applying a polycarbonate-based polyurethane resin solution to a releasable carrier, drying it, applying a polyvinyl chloride paste sol, and peeling off the releasable carrier after gelling by heating. A method for manufacturing vinyl resin sheets. (8) The method for producing a vinyl chloride resin sheet according to claim 7, wherein the polyvinyl chloride paste sol is a foamable polyvinyl chloride paste sol containing a foaming agent, and the polyvinyl chloride paste sol is foamed after heating and gelling. (9) Production of a vinyl chloride resin sheet according to any one of claims 7 to 8, which comprises peeling off the releasable carrier and then applying and drying a surface treatment liquid made of a polyurethane resin on the surface. Method.