JP2757015B2 - Vinyl chloride resin sheet and method for producing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a vinyl chloride resin sheet, and more particularly, to a vinyl chloride resin sheet used for automobile seats, furniture, shoes, bags, clothing, and the like.

[Problems to be solved by the prior art and the invention]

Conventionally, for automobile seats and the like, polyvinyl chloride leather with a foamed or non-foamed polyvinyl chloride resin layer laminated on a base cloth and embossed on the surface has been used, but the temperature inside a car is extremely high in summer. The plasticizer incorporated in the polyvinyl chloride resin volatilizes and adheres to the window glass of the vehicle, causing fogging.In winter, it is not only extremely hard and gives a cold feeling, but also in summer, There was a drawback that stickiness was easy.

In order to improve this, a polyvinyl chloride resin sheet with a polyurethane resin layer formed on the surface of the polyvinyl chloride resin layer was studied. However, the adhesion between the polyvinyl chloride resin and the polyurethane resin was poor, and the polyurethane resin layer and the polyvinyl chloride layer were not bonded together. An adhesive layer had to be interposed between the resin layer and the adhesive layer, and the presence of the adhesive layer significantly impaired the feeling of the vinyl chloride resin sheet on which the polyurethane resin layer was laminated. In addition, when the polyurethane used is a polyester-based polyurethane, the polyurethane is further poor in hydrolysis resistance and inferior in durability, and cannot be used for applications used under severe conditions for a long period of time, such as an automobile seat. Met.

The present invention solves the above-mentioned drawbacks of the prior art, and integrates a polyurethane resin layer and a polyvinyl chloride resin layer by bonding without using an adhesive, and has a polyurethane resin-coated vinyl chloride excellent in hydrolysis resistance. It is an object of the present invention to provide a resin sheet and a method for manufacturing the same.

[Means for solving the problem]

The vinyl chloride resin sheet of the present invention, which achieves the above object, has a polyurethane resin layer mainly composed of a polycarbonate-based polyurethane resin formed on a release carrier, and is formed on the polyurethane resin layer without interposing an adhesive layer. It is characterized in that a vinyl paste resin layer is formed and the release carrier is peeled off.

This polyvinyl chloride paste resin layer may be non-foamed or foamed, or may be a composite layer thereof.

The polyvinyl chloride resin sheet of the present invention may be formed by laminating a base cloth on a polyvinyl chloride paste resin layer, or by applying a surface treatment liquid composed of a polyurethane resin on a polyurethane resin layer mainly composed of a polycarbonate polyurethane resin. To form a surface treatment layer.

Further, the method for producing a vinyl chloride resin sheet of the present invention,
It is characterized by applying a polyurethane resin solution mainly composed of a polycarbonate-based polyurethane resin to a release carrier, drying it, applying a polyvinyl chloride paste sol, and peeling the release carrier after gelling by heating. Is what you do.

In the case where the polyvinyl chloride paste resin layer is foamed, the foamed polyvinyl chloride paste sol containing a foaming agent is heated and gelled, and then foamed. Further, in order to form a surface treatment layer, after the release carrier is peeled off, a surface treatment liquid composed of a polyurethane resin is applied to the surface and dried.

The release carrier used in the present invention includes, in addition to release paper such as silicon paper whose surface has been treated with silicon, any one that is generally used as a release carrier, such as a silicon belt. Anything can be used.

Polyurethane resin mainly composed of polycarbonate-based polyurethane resin includes not only polycarbonate-based polyurethane resin alone, but also a mixture of polycarbonate-based polyurethane resin and another polyurethane resin, wherein the polyurethane-based polyurethane resin contains at least 50% or more of polycarbonate-based polyurethane resin. Refers to resin.

The polycarbonate-based polyurethane resin used in the present invention is a polymer of a polycarbonate-based polyol, an isocyanate, and a chain extender. This polycarbonate-based polyol has the following general formula (Where R is-(CH ₂ ) _P- , P ≧ 2, and n is 5-200). As a specific example, 1,6-hexane polycarbonate polyol is preferable.

In addition, a mixture in which a part of the polyalkylene polycarbonate-based polyol is substituted with a polyoxyalkylene-modified polycarbonate can also be used.

Further, as the isocyanate, tetramethylene diisocyanate, 1,6-hexane diisocyanate, 2,2,4
-Trimethyl-1,6-hexanediisocyanate, 1-
Methylcyclohexane-2,4-diisocyanate, 3,3 '
-Dimethyl-4,4'-diisocyanate Dicyclohexylmethane, aliphatic or alicyclic diisocyanate such as 4,4'-dicyclohexylmethane diisocyanate, aromatic diisocyanate such as tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate And the like. However, a polycarbonate-based polyurethane resin using an aliphatic or alicyclic diisocyanate or hydrogenated diphenylmethane diisocyanate is a non-yellowing type resin, and is particularly preferable.

Examples of the polyurethane resin that can be used in combination with the polycarbonate polyurethane resin include polyether polyurethane containing polytetramethylene glycol or polypropylene glycol as a polyol component, and polyester obtained by reacting a hydroxyl compound having 4 or more carbon atoms with a dibasic acid. There is a polyester-based polyurethane as a component, a polyester-based polyurethane having an ε-caprolactone-based polyester as a polyol component, and the like.

Examples of the polyvinyl chloride paste sol used in the present invention include vinyl chloride homopolymer, vinyl chloride and other monomers such as ethylene, vinyl acetate, vinyl ether, maleic acid ester (meth) acrylic acid, and (meth) acrylic acid ester. A plastisol obtained by dispersing a vinyl chloride resin such as a copolymer in a plasticizer can be used.

As the plasticizer, any plasticizer can be used as long as it is generally used in a polyvinyl chloride paste sol. For example, phthalic acid derivatives such as di-2-ethylhexyl phthalate, di-n-octyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, dibutyl phthalate, dilauryl phthalate, didodecyl phthalate and diundecyl phthalate; diisodecyl phthalate, diisononyl phthalate and the like Isophthalic acid derivatives of
Adipic acid derivatives such as di-n-butyl adipate and dioctyl adipate; maleic acid derivatives such as di-n-butyl maleate; citric acid derivatives such as tri-n-butyl citrate; itaconic acid derivatives such as monobutyl itaconate Oleic acid derivatives such as butyl oleate; ricinoleic acid derivatives such as glycerin monocitrate; tricresyl phosphate (TCP);
XP), dixylyl monocresyl phosphate (DXMC
P), a phosphate ester plasticizer such as monoxylyl cresyl phosphate (MXDCP), an epoxy group-containing phthalate ester plasticizer, an epoxidized soybean oil, and an epoxy resin plasticizer. These can be used alone or in combination of two or more.

In the present invention, the polyvinyl chloride paste sol,
Commonly used additives, for example, foaming agents, ultraviolet absorbers, stabilizers, light stabilizers, antioxidants, coloring agents, fillers,
A weather resistance improver, a thermal initial coloring inhibitor, and the like can be added.

Examples of the foaming agent include azodicarbonamide, azobisisobutyronitrile, N, N'-dinitropentamethylenetetramine, benzenesulfonylhydrazide and the like.

The ultraviolet absorber can be appropriately selected from a wide variety of types in consideration of the ultraviolet absorption capacity of the ultraviolet absorber and the compatibility with the vinyl chloride resin used. Examples of usable ultraviolet absorbers include hydroquinone-based ultraviolet absorbers such as hydroquinone and hydroquinone disalicylate, salicylic acid-based ultraviolet absorbers such as phenyl salicylate and paraoctylphenyl salicylate, and 2-hydroxy-4-methoxybenzophenone. , 2-hydroxy-4
-N-octoxybenzophenone, 2-hydroxy-4
-Methoxy-2'-carboxybenzophenone, 2,2 '
Benzophenone-based ultraviolet absorbers such as -dihydroxy-4-4'-dimethoxybenzophenone, 2-hydroxy-4-benzoyloxybenzophenone, 2- (2'-
(Hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl)
-5-carboxylic acid butyl ester bezotriazole, 2
-(2'-hydroxy-5'-methylphenyl) -5,6
Benzotriazole-based ultraviolet absorbers such as -dichlorobenzotriazole and 2- (2'-hydroxy-5'-methylphenyl) -5-ethylsulfonebenzotriazole; Two or more can be used in combination.

Stabilizers include barium stearate, zinc stearate, calcium stearate, barium ricinoleate, dibutyltin laurate, dibutyltin maleate ester, triphenyl phosphite, tris (nonylphenyl) phosphite, dioctyl phenyl phosphite, diphenyl acid Phosphite, tri-n-dodecyl phosphite, tri-n-dodecyl trithiophosphite, phenyl-di-n-decyl phosphite, di-
n-octadecylpentaerythritol diphosphite and the like.

Examples of the light stabilizer include hindered amine light stabilizers.

Antioxidants include 2,6-di-t-butyl-4-methylphenol, 2,2'-methylenebis- (6-t-butyl-4-ethylphenol), 2,6-di-t-butyl -P-cresol, 4,4'-thiobis- (3-methyl-
Phenolic antioxidants such as 6-t-butylphenol), di-n-dodecylthiodipropionate, di-n-
Thiodipropionates such as octadecylthiodipropionate, di-n-dodecyl sulfide, di-n
And sulfides such as octadecyl sulfide and di-n-octadecyl disulfide, and disulfides.

As fillers, silica, talc, calcium carbonate,
Examples include magnesium carbonate, feldspar, quartz, hydrotalcite-based compounds, aluminum hydroxide, magnesium sulfate, calcium phosphate, magnesium hydroxide, crosslinked vinyl chloride resins, crosslinked acrylic resins, and the like.

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

The base fabric used in the present invention may be any of a knitted fabric, a woven fabric, and a nonwoven fabric.

Examples of the surface treatment solution composed of a polyurethane resin include polycarbonate polyurethane, polyether polyurethane having polytetramethylene glycol or polypropylene glycol as a polyol component, and a compound obtained by reacting a hydroxyl compound having 4 or more carbon atoms with a dibasic acid. Solvent solutions such as polyester-based polyurethane containing polyester as a polyol component, polyester-based polyurethane containing ε-caprolactone-based polyester as a polyol component, and urethane-modified polyamino acid resin can be used.

〔Example〕

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

(Example 1) A solvent solution of 1,6-hexanepolycarbonate-based polyurethane was applied to the surface of silicon paper so as to have a dry thickness of 15 μm, and was heated and dried to form a polyurethane resin layer. Then, a polyvinyl chloride paste sol having the following composition was applied to a thickness of 0.1 mm, and heated at 130 ° C. for 2 minutes.

100 parts by weight of polyvinyl chloride resin (manufactured by Zeon Corporation: Geon131) 70 parts by weight of dioctyl phthalate Stabilizer (BC-1000J, manufactured by Katsuta Kako Co., Ltd.) 3 parts by weight 1 part by weight of black toner thickness
Apply 0.2 mm, heat it at 130 ° C for 2 minutes, then attach a cloth 79 (base cloth) with an adhesive, heat it at 200 ° C for 2 minutes, and after foaming and hardening, peel off the silicone paper to remove vinyl chloride resin. I got a sheet.

100 parts by weight of polyvinyl chloride resin (manufactured by Zeon Corporation: Geon121) 70 parts by weight of dioctyl phthalate 2 parts by weight of stabilizer (FL-21 made by Adeka Argus) 2 parts by weight of azodicarbonamide 1 part by weight of black toner The adhesiveness, feeling, and hydrolysis resistance between the polyurethane resin layer and the polyvinyl chloride resin layer of the resin sheet were measured. Table 1 shows the measurement results.

<< Adhesion test >> 11 cuts were made in the polyurethane resin layer of the vinyl chloride resin sheet vertically and horizontally at 1 mm intervals.
After the adhesive tape (cellophane tape) was adhered to the adhesive-coated surface, the adhesive tape was peeled off, and the number of polyurethane resin films (1 mm square film) remaining on the surface of the vinyl chloride resin sheet was measured. Was checked, and the remaining number was determined to be good.

<< Hand >> Judgment was made based on the tactile sensation when the vinyl chloride resin sheet was rubbed by hand.

◎ ・ ・ ・ Smooth and soft touch ×× Hard and rough touch or feel that the polyurethane resin layer floats 《Hydrolysis resistance》 95% relative humidity and 95% relative humidity of a vinyl chloride resin sheet sample
This is a result of observing the degree of surface abrasion of the resin layer of the sample piece with a taper type abrasion tester at a load of 1 kg and a number of friction of 500 times, after being left at 70 ° C. for 4 weeks.

(Example 2) The polycarbonate-based polyurethane and the polytetraethylene glycol-based polyurethane used in Example 1 were mixed at 50: 5.
A vinyl chloride resin sheet was obtained in the same manner as in Example 1 except that the polyurethane resin mixed at 0 was used.

The same measurement as in Example 1 was performed for the obtained vinyl chloride resin sheet, and the results are shown in Table 1.

Comparative Example 1 The polycarbonate polyurethane and the polypropylene ether glycol polyurethane used in Example 1 were used.
A vinyl chloride resin sheet was obtained in the same manner as in Example 1 except that the polyurethane resin mixed at 40:60 was used.

The same measurement as in Example 1 was performed for the obtained vinyl chloride resin sheet, 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 a polypropylene ether glycol-based polyurethane was used instead of the polycarbonate-based polyurethane used in Example 1.

The same measurement as in Example 1 was performed for the obtained vinyl chloride resin sheet, and the results are shown in Table 1.

(Comparative Example 3) The same polyvinyl chloride paste sol as that used in Example 1 was applied to the surface of silicon paper in the same order, and a cloth 79 (base cloth) was attached with an adhesive. After heating and foaming hardening for a minute, the silicone paper was peeled off to obtain a polyvinyl chloride resin foam sheet.

On the other hand, a solvent solution of polypropylene ether glycol polyurethane
μm, and dried by heating to form a polyurethane resin layer. A two-component polyurethane adhesive was applied on the polyurethane resin layer, and the polyvinyl chloride resin foam sheet obtained above was used. The paste resin layer was bonded so as to be in contact with the adhesive to obtain a vinyl chloride resin sheet.

The same measurement as in Example 1 was performed for the obtained vinyl chloride resin sheet, and the results are shown in Table 1.

(Comparative Example 4) The same polyvinyl chloride paste sol as used in Example 1 was applied to the surface of silicon paper in the same order, and a staple 79 (base cloth) was attached with an adhesive. After heating and foaming hardening for a minute, the silicone paper was peeled off to obtain a polyvinyl chloride resin foam sheet.

On the other hand, a solvent solution of polyester polyurethane obtained by reacting polyester obtained by reacting ethylene glycol and adipic acid with another silicon paper with diphenylmethane diisocyanate and 1,4-butanediol has a dry thickness of 15 μm. And apply
This is heated and dried to form a polyurethane resin layer, a two-component polyurethane adhesive is applied on the polyurethane resin layer, and the polyvinyl chloride paste resin layer of the previously obtained polyvinyl chloride resin foam sheet comes into contact with the adhesive. To obtain a vinyl chloride resin sheet.

The same measurement as in Example 1 was performed for the obtained vinyl chloride resin sheet, and the results are shown in Table 1.

As is clear from Table 1, only the vinyl chloride resin sheets of Examples 1 and 2 which are excellent in the adhesiveness, feeling and hydrolysis resistance of the polyurethane resin layer and the vinyl chloride paste resin layer are excellent. In Comparative Examples 1 and 2, in which a polyurethane resin mainly composed of polycarbonate-based polyurethane was not used and an adhesive was not used for bonding to a vinyl chloride paste resin layer, adhesion between the polyurethane resin layer and the paste resin layer was poor, and Also in this case, the polyurethane resin layer has an unpleasant tactile sensation of lifting.

Comparative Examples 3 and 4, in which an adhesive was used for bonding to the vinyl chloride paste resin layer without using a polyurethane resin mainly composed of polycarbonate-based polyurethane, had good adhesiveness, but had a hard feel and a rough touch. It is extremely bad. In particular, Comparative Example 4 uses a polyester-based polyurethane having a polyol obtained by reacting a hydroxyl compound having 2 carbon atoms with a dibasic acid as a polyurethane resin, so that an adhesive must be used. Therefore, the feeling is poor and the hydrolysis resistance is extremely poor.

〔The invention's effect〕

Since the present invention is configured as described above, even if an adhesive is not used, the adhesiveness between the polyurethane resin layer and the polyvinyl chloride paste resin layer is excellent, and therefore, the feeling due to the adhesive is not deteriorated. In addition, since it has excellent hydrolysis resistance, it can be used as a material for shoes, bags, clothing, and the like, and is extremely effective particularly for long-term applications such as furniture and vehicle seats.

Further, the method for producing a vinyl chloride resin sheet of the present invention,
By using no adhesive, one or two steps can be omitted as compared with the conventional production method, so that a vinyl chloride resin sheet having excellent adhesion between the polyurethane resin layer and the polyvinyl chloride resin paste can be obtained extremely efficiently. Can be done.

Claims (2)

(57) [Claims] 1. A polyurethane resin layer mainly composed of a polycarbonate-based polyurethane resin is formed on a release carrier,
A polyvinyl chloride resin sheet formed by forming a polyvinyl chloride paste resin layer on the polyurethane resin layer without interposing an adhesive layer and peeling off a release carrier. 2. A polyurethane resin solution mainly comprising a polycarbonate-based polyurethane resin is applied to a release carrier,
A method for producing a vinyl chloride resin sheet, comprising drying and then applying a polyvinyl chloride paste sol, peeling the releasable carrier after heating and gelling.