JPH0796574A - Laminate of vinyl chloride resin - Google Patents

Abstract

PURPOSE:To obtain a laminate of vinyl chloride resin superior in moisture- absorbing and moisture-releasing properties and suitable in the application to insole and vamp of a shoe or a bottom member of a scuff. CONSTITUTION:A vinyl chloride resin sheet is formed by laminating a vinyl chloride resin layer on at least one surface of a base cloth. The vinyl chloride resin layer is made of a vinyl chloride composition having an open-cell structure, which 3-50 contains 100 pts.wt. of vinyl chloride resin and 3-50 pts.wt. water absorptive resin. As the water absorptive resin, a starch-acrylic acid copolymer is preferably used. As the base cloth, a hydrophobic base cloth is desirably used.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin laminated sheet in which a vinyl chloride resin layer and a base cloth are laminated,
Specifically, it relates to a vinyl chloride resin laminated sheet having excellent moisture absorption and desorption.

[0002]

2. Description of the Related Art A sheet in which a vinyl chloride resin such as vinyl chloride resin leather and a base cloth are laminated and integrated (hereinafter sometimes abbreviated as "vinyl chloride resin laminated sheet") is used for furniture and bags. It is widely used as a surface material for office supplies and exercise equipment, an interior material such as a mat, a wall material, a floor material, an interior material for a car, a shoe covering material, an insole material, and a bottom member for slippers. A vinyl chloride resin laminated sheet such as the above is prepared by kneading a mixture of a vinyl chloride resin and an additive such as a plasticizer and a stabilizer, and then rolling with a calendar or the like and laminating a base fabric ( (Hereinafter, it may be referred to as the "calendar method.")
And a method in which a vinyl chloride resin blended with a plasticizer, a stabilizer, etc. is made into a paste state, which is coated on a release paper by various means, and further laminated with a base cloth (hereinafter referred to as “paste method”). Are manufactured).

[0003]

However, the vinyl chloride resin laminated sheet as described above has poor moisture absorption and release properties, and when it is used as a shoe covering material, an insole, a bottom part of a slipper, etc. The part in contact with the feet was sticky and uncomfortable. Therefore, a hydrophilic cloth is usually used as the base cloth, but its water absorption is extremely small and it is not sufficient to solve the above problems.

As a result of earnest studies to solve the above-mentioned problems, the present inventor has made a vinyl chloride resin contain a water-absorbing resin and has a vinyl chloride resin layer having an open cell foam cell. Due to the structure, even if it is used as a covering material for shoes, an insole, the bottom of slippers, etc., it does not stick to the parts that come into contact with feet due to moisture such as sweat, and it has excellent moisture absorption and desorption properties. The inventors have found that a resin-based laminated sheet can be obtained, and completed the present invention.

[0005]

The vinyl chloride resin laminated sheet of the present invention comprises a vinyl chloride resin composition containing 3 to 50 parts by weight of a water-absorbent resin to 100 parts by weight of the vinyl chloride resin. It is characterized by being formed by laminating an open cell foam layer and a base cloth. As the water absorbent resin, a starch-acrylic acid type copolymer can be preferably used.

As the vinyl chloride resin used in the present invention, any vinyl chloride resin used in ordinary vinyl chloride resin sheets can be used. Specifically, the average degree of polymerization is about 800 to 2000, preferably 800 to 1
500 polyvinyl chloride or a copolymer mainly composed of vinyl chloride (for example, ethylene-vinyl chloride copolymer, vinyl acetate-vinyl chloride copolymer, vinyl chloride-methacrylic acid ester copolymer, etc.), or other Resin (for example, polyester resin, epoxy resin, acrylic resin,
Blends with vinyl acetate resin, urethane resin, acrylonitrile-styrene-butadiene copolymer, partially saponified polyvinyl alcohol, etc.) can be mentioned.

As the water-absorbent resin added to the above vinyl chloride resin, starch-acrylic acid copolymer, cross-linked polyethylene oxide, cross-linked polyvinyl alcohol, starch-acrylonitrile graft copolymer and the like can be used. A starch-acrylic acid-based copolymer is particularly preferable in terms of properties and economical efficiency. As the starch-acrylic acid-based copolymer, gelled starch is copolymerized with acrylic acid, methacrylic acid, an acrylic acid salt, a methacrylic acid salt, etc., and polyols such as ethylene glycol,
It was made water-insoluble by crosslinking with acrylic acid esters such as diacrylic acid ester, triacrylic acid ester, dimethacrylic acid ester, and trimethacrylic acid ester, and bisacrylamide such as N, N-methylenebisacrylamide. It is a thing.

The amount of the water-absorbent resin blended with the vinyl chloride resin is 3 to 50 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If the amount of the water-absorbent resin is small, sufficient moisture absorption and desorption cannot be obtained. Conversely, if the amount is too large, a molten state suitable for foaming cannot be obtained, abnormal foaming will occur, and an appropriate open-cell foam layer will be obtained. In addition to the possibility of disappearing, there arises a problem that the obtained vinyl chloride resin layer becomes brittle.

In addition to the water absorbent resin, a plasticizer and a foaming agent are added to the vinyl chloride resin. Examples of the plasticizer include phthalate ester plasticizers such as di-2-ethylhexyl phthalate, phosphate ester plasticizers such as tricresyl phosphate, adipic ester plasticizers such as di-2-ethylhexyl adipate, and diester Sebacate ester plasticizers such as 2-ethylhexyl sebacate, polyester plasticizers such as polypropylene adipate, epoxy plasticizers such as epoxidized soybean oil, chlorinated fatty acid ester plasticizers such as chlorinated paraffin, and vinyl chloride It is not particularly limited as long as it is a usual plasticizer used for the resin sheet. The content of the plasticizer is 10 to 120 parts by weight, preferably 30 to 90 parts by weight, based on 100 parts by weight of the vinyl chloride resin.

As the foaming agent to be added to the vinyl chloride resin, a conventional foaming agent used for a vinyl chloride resin sheet such as a thermally decomposable chemical foaming agent such as azodicarbamide or oxybisbenzenesulfonhydrazide. Can be used. The content of the foaming agent is 0.5 to 8.0 parts by weight, preferably 1.0 to 4.0 parts by weight, based on 100 parts by weight of the vinyl chloride resin.

The vinyl chloride resin layer of the present invention can be used as an open-cell foam layer by appropriately setting the type of vinyl chloride resin, the type and amount of the foaming agent, and the foaming processing conditions. However, the vinyl chloride resin layer can also be made into an open-cell foam layer by adding a thermoplastic resin powder such as powdered polyethylene or powdered vinyl chloride as a filler. The blending amount of the thermoplastic resin powder at this time is, relative to the vinyl chloride resin part by weight,
The amount is 0.5 to 10 parts by weight, preferably 1 to 7 parts by weight.

A composition containing 100 parts by weight of a vinyl chloride resin and 1 to 10 parts by weight, preferably 1 to 5 parts by weight of a hydrocarbon compound or a halogenated hydrocarbon compound having a boiling point of 130 to 200 ° C. The vinyl chloride resin layer can also be used as an open-cell foam layer by using a material. Specific examples of the hydrocarbon compound having a boiling point of 130 to 200 ° C. include cyclohexanol, propylene glycol, ethylene glycol, n-hexanol, furfuryl alcohol, and 2-ethylbutanol. Specific examples of the halogenated hydrocarbon compound having a boiling point of 130 to 200 ° C. include dichlorobenzene and the like.

The vinyl chloride resin layer of the present invention may contain Ba-Z, if necessary, in addition to the above-mentioned additives such as a plasticizer and a foaming agent.
n-based composite stabilizer, Na-Zn-based composite stabilizer, Ca-Na
It is also possible to add various additives such as a system composite stabilizer, a stabilizer such as a Cd—Zn composite stabilizer, a filler such as talc, calcium carbonate, calcined kaolin, and a colorant such as a pigment and a dye. Any of these various additives may be used as long as they are additives used in the conventional vinyl chloride resin sheet, and the compounding amount may be the same as in the conventional vinyl chloride resin sheet.

As the base fabric used in the present invention, any fabric composed of natural fibers, synthetic resins and the like can be used, and the fiber form can be either long fibers or short fibers. In particular, it is preferable to use a hydrophobic base cloth made of a low water absorption fiber such as vinylidene, nylon, vinylon, polyester, acrylic, aurone, carbon, glass fiber, polyurethane. These fibers may be used alone or in combination as the base fabric, and may be in the form of any of woven fabric, knitted fabric and non-woven fabric.

The vinyl chloride resin laminated sheet of the present invention can be produced by a known method such as a calendering method or a paste method as in the case of producing a conventional vinyl chloride resin laminated sheet.

When the vinyl chloride resin laminated sheet of the present invention is produced by the calendar method, the vinyl chloride resin mainly obtained by suspension polymerization (suspension polymerization), the above water-absorbent resin, plasticizer, Additives such as stabilizers are mixed in a desired ratio and sufficiently kneaded with a mixer such as a Henschel mixer or a Banbury mixer, and the obtained mixture is formed into a sheet with a calendar or the like. After this is attached to a base cloth, foaming is performed or the previously foamed vinyl chloride resin sheet and the base cloth are laminated.

When laminating the base cloth and the vinyl chloride resin layer, various adhesives may be used, but the air permeability between the vinyl chloride resin layer containing the water-absorbent resin and the base cloth. It is necessary to select the type of adhesive, the coating amount, the coating method, etc., so that the loss is not lost. Moreover, the vinyl chloride resin layer may be a single layer or a multilayer. When using multiple layers,
You may mix different vinyl chloride resin for each layer,
At least the position where the vinyl chloride resin layer containing the water absorbent resin is required to absorb and release moisture (for example, the vinyl chloride resin laminate sheet of the present invention is used as a shoe lining material and the base fabric is applied to the user's foot. (If it is in contact with the base cloth, it is adjacent to the base cloth, or if the vinyl chloride resin layer is in contact with the user as the skin material of the chair, it is the surface of the vinyl chloride resin laminated sheet) Need to be laminated to come to. Further, the vinyl chloride resin layer may be laminated only on the front surface side of the base cloth, or may be laminated on both surfaces of the base cloth. In this case, the vinyl chloride resin layer may be laminated on the front side of the base fabric first, and then the vinyl chloride resin laminated sheet obtained may be used as the base fabric to laminate the vinyl chloride resin layer on the back side. .

When the vinyl chloride resin laminated sheet of the present invention is manufactured by the paste method, the above water absorbent resin, plasticizer, and plasticizer are added to the vinyl chloride resin mainly obtained by emulsion polymerization (emulsion polymerization). Additives such as stabilizers in desired proportions, dissolver, paste sol obtained by sufficiently mixing with a homogenizer or other disperser doctor knife on release paper, comma doctor, roll coater,
Coating is performed by various means such as a reverse roll coater and a rotary screen coater, and then a base cloth is laminated, or the base cloth is directly coated by the above means.
At this time, the coating may be performed only once, or may be performed a plurality of times to form the coating layer as a multilayer. Further, when the coating layer is a multi-layer, different vinyl chloride-based resin may be mixed for each layer, but at least the vinyl chloride-based resin layer containing the above water-absorbent resin is required to have a moisture absorption / release property. Need to be laminated to come.

The coated layers are heat-gelled and then heat-cured and foamed. The gelling conditions at this time, and the curing conditions are appropriately set depending on the composition of the vinyl chloride resin paste, the solid content concentration, the coating amount, etc., but the same conditions as in the case of the conventional vinyl chloride resin sheet may be used, There is no need to change the conditions.

When the release paper or the like is coated, the release paper or the like is peeled off after heating and foaming. At this time, similar to the conventional vinyl chloride resin laminated sheet, if a release paper having an uneven pattern formed on the surface (the side coated with the vinyl chloride resin paste) is used, the vinyl chloride resin laminated sheet produced An uneven pattern can be transferred to the surface of the sheet. Further, the layering with the base fabric may be performed after heating and foaming, or immediately after coating with the vinyl chloride resin paste. Various adhesives may be used when pasting with the base cloth after heating and foaming, but the air permeability between the vinyl chloride resin layer containing the water absorbent resin and the base cloth. Is not lost,
It is necessary to select the type of adhesive, coating amount, coating method, etc.

Also when the vinyl chloride resin laminated sheet of the present invention is manufactured by the paste method, the vinyl chloride resin layer may be laminated only on the front surface side of the base fabric, as in the case of the calender method. However, they may be laminated on both sides of the base fabric.
In this case, the vinyl chloride resin layer may be formed on the front surface side of the base fabric first, and then the vinyl chloride resin laminated sheet obtained may be used as the base fabric to form the vinyl chloride resin layer on the back surface side. .

The vinyl chloride resin laminated sheet of the present invention is
Any of the above-mentioned calendar method, a method other than the paste method, for example, a method in which a conventional vinyl chloride-based resin sheet is produced, such as a laminate of a vinyl chloride-based resin sheet and a base fabric obtained by an extrusion method, Although it can be used in the manufacturing method, it has advantages such as a product with excellent design and functionality and a soft texture, easy control of the expansion ratio and the state of foam cells, and further heat shrinkage. It is also possible to use a large base cloth, and the fact that the base cloth that can be used is rich in variety, etc. makes it possible to use a wide range of products manufactured by the paste method.

The vinyl chloride resin laminated sheet of the present invention is
If necessary, a drawing pattern can be imparted by an embossing roll, or secondary processing such as vacuum forming, thermoforming, high-frequency welder or the like can be performed. The conditions at this time are
The same conditions as in the case of the conventional vinyl chloride resin sheet may be used, and there is no particular need to change the conditions. Further, the vinyl chloride resin laminated sheet of the present invention may be provided with an overcoat layer containing various synthetic resins such as polyurethane resin and acrylic resin as a main component on the surface side, if necessary. It is also possible to perform surface treatment with a treating agent for the purpose of color tone adjustment, surface protection and the like. Also at this time, it is necessary to select the overcoat layer and the surface treatment layer so that the performance of the vinyl chloride resin laminated sheet of the present invention is not impaired.

The vinyl chloride resin laminated sheet of the present invention obtained as described above is the same as the conventional vinyl chloride resin laminated sheet, and is used as a skin material for furniture, bags, office supplies, sports equipment, etc. It can be used as an interior material such as mat, wall material, floor material, vehicle interior material, shoe covering material or insole material, slipper bottom material, etc., but especially for shoes that require moisture absorption and release. It can be suitably used as a base material, an insole material, or a bottom member of a slipper. At this time, if the surface contacting the user's foot is used as the hydrophobic base cloth, the user will not feel sticky even after absorbing moisture.

[0025]

The vinyl chloride resin laminated sheet of the present invention has a moisture absorbing / releasing property by containing a specific amount of a water absorbing resin in the vinyl chloride resin and forming the vinyl chloride resin layer as an open-cell foam layer. Excel.

[0026]

The present invention will be described in more detail with reference to specific examples, but the present invention is not limited thereto.

Example 1 A vinyl chloride resin paste having the composition shown in Table 1 was placed on a paper (release paper) having a surface coated with a special release agent with a knife coater at 250 g / m ^2.
And a heat treatment for gelation at 140 ° C. for 1 minute, and then a heat treatment for curing and foaming at 200 ° C. for 3 minutes to obtain a vinyl chloride resin foam sheet.

[Table 1] Vinyl chloride resin ^{* 1} 100 parts by weight Di-2-ethylhexyl phthalate 70 parts by weight Ba-Zn composite stabilizer 3 parts by weight Foaming agent (azodicarbamide type) ^{* 2} 1.5 parts by weight Powdered polyethylene 3.5 parts by weight Water absorbent resin ^{* 3} 5 parts by weight * 1 Sumitomo Chemical PX-QHP (Average degree of polymerization 140
0) * 2 Otsuka Chemical AZ-S * 3 Starch-sodium acrylate copolymer Sanyo Chemical Industries AD-81

A polyurethane adhesive is applied to the surface of the above vinyl chloride resin foamed sheet with a doctor knife to make 50
It is coated so that it will be g / m ^2, and it is pressed against a hydrophobic polyester base cloth before the adhesive is completely dried.
It was dried at 0 ° C. for 2 minutes to obtain a vinyl chloride resin laminated sheet. The obtained vinyl chloride-based resin laminated sheet had a foaming ratio of 3 times, and the cross section of the foamed layer was observed by a scanning electron microscope to find that it had a vertically long open-celled cell structure. Further, the moisture absorption and desorption properties of the obtained vinyl chloride resin laminated sheet were tested by the following method.

Test method The obtained vinyl chloride resin laminated sheet was 10 cm × 10
It was cut into a size of cm and left for 24 hours in a desiccator containing dry silica gel to remove moisture absorbed during processing, and then weighed. Then 90% relative humidity,
The sample was placed in a humidified oven at a temperature of 40 ° C., weighed at regular intervals, and the change was recorded. After 7 hours from the start of measurement, the weight-measured sample was transferred to the desiccator and weighed at regular intervals. The above measurement results are shown as a graph shown in FIG.

Example 2 A vinyl chloride resin laminated sheet was obtained in the same manner as in Example 1 except that the blending amount of the water absorbent resin was changed to 20 parts by weight. The obtained vinyl chloride-based resin laminated sheet had a foaming ratio of 3 times, and the cross section of the foamed layer was observed by a scanning electron microscope to find that it had a vertically long open-celled cell structure. Further, the moisture absorption and desorption properties of the obtained vinyl chloride resin laminated sheet were tested in the same manner as in Example 1.

Example 3 A vinyl chloride resin laminated sheet was obtained in the same manner as in Example 1 except that the blending amount of the water absorbent resin was changed to 45 parts by weight. The obtained vinyl chloride-based resin laminated sheet had a foaming ratio of 3 times, and the cross-section of the foamed layer was observed by a scanning electron microscope to find that the cells were slightly non-uniform, but had a vertically long open-celled cell structure. Met. Further, the moisture absorption and desorption properties of the obtained vinyl chloride resin laminated sheet were tested in the same manner as in Example 1.

Example 4 A vinyl chloride resin laminated sheet was obtained in the same manner as in Example 1 except that ethylene glycol was added instead of powdered polyethylene. The obtained vinyl chloride resin laminated sheet has an expansion ratio of 3 times,
When observing the cross section of the foam layer with a scanning electron microscope,
It had a vertically long open-celled cell structure. Also,
The moisture absorption and desorption properties of the obtained vinyl chloride resin laminated sheet were tested in the same manner as in Example 1.

Comparative Example 1 A vinyl chloride resin laminated sheet was obtained in the same manner as in Example 1 except that the water absorbent resin was not added. The obtained vinyl chloride-based resin laminated sheet had a foaming ratio of 3 times, and the cross-section of the foamed layer was observed by a scanning electron microscope to find that the cells were slightly non-uniform, but had a vertically long open-celled cell structure. Met. Further, the moisture absorption and desorption properties of the obtained vinyl chloride resin laminated sheet were tested in the same manner as in Example 1.

Comparative Example 2 A vinyl chloride resin laminated sheet was obtained in the same manner as in Example 1 except that the composition of the vinyl chloride resin was changed to that shown in Table 2. The obtained vinyl chloride-based resin laminated sheet had a foaming ratio of 3 times, and the cross-section of the foamed layer was observed by a scanning electron microscope to find that it had a closed cell structure. Further, the moisture absorption and desorption properties of the obtained vinyl chloride resin laminated sheet were tested in the same manner as in Example 1.

[Table 2] Vinyl chloride resin ^{* 4} 100 parts by weight Di-2-ethylhexyl phthalate 70 parts by weight Ba-Zn composite stabilizer 3 parts by weight Foaming agent (azodicarbamide-based) ^{* 5} 1.5 parts by weight Powdered polyethylene 3.5 parts by weight Water-absorbent resin ^{* 3} 5 parts by weight * 4 Mitsubishi Kasei Vinyl P-510 * 5 Otsuka Chemical AZ-S * 3 Starch-sodium acrylate copolymer Sanyo Kasei Kogyo AD-81

Comparative Example 3 A vinyl chloride resin laminated sheet was obtained in the same manner as in Example 1 except that the blending amount of the water absorbent resin was changed to 55 parts by weight. The vinyl chloride resin laminated sheet thus obtained had a foaming ratio of 2 times, and the cross section of the foamed layer was observed by a scanning electron microscope. As a result, it had an extremely nonuniform cell structure and was fragile in strength. Was not suitable. Further, the moisture absorption and desorption properties of the obtained vinyl chloride resin laminated sheet were tested in the same manner as in Example 1.

[0036]

INDUSTRIAL APPLICABILITY The vinyl chloride resin laminated sheet of the present invention is obtained by the same method as the conventional vinyl chloride resin laminated sheet and has excellent hygroscopicity. Widely used as materials for skins, bags, office supplies, sports equipment, etc., interior materials such as mats, wall materials, floor materials, interior materials for vehicles, shoe coverings and insoles, slipper soles, etc. Not only can it be used, but even when it is used as a shoe cover material or insole material that requires hygroscopicity, or as a bottom member of slippers, the parts that come into contact with feet due to moisture such as sweat can become sticky. Since it does not occur, the user does not feel uncomfortable, and it can be used particularly suitably.
Moreover, since the vinyl chloride resin laminated sheet of the present invention has excellent moisture releasing property, even if the vinyl chloride resin layer absorbs moisture, the vinyl chloride resin laminated sheet is released moisture just by leaving it still, and it is always comfortable. The tactile sensation can be given to the user.

[Brief description of drawings]

FIG. 1 is a graph showing test results (relationship between water absorption rate and time) of moisture absorption amount and moisture release amount in Examples of the present invention.

Claims (6)

[Claims] 1. A vinyl chloride resin laminated sheet in which a base cloth and a vinyl chloride resin layer are laminated, wherein the vinyl chloride resin layer contains 3 to 50 parts by weight of a water-absorbent resin with respect to 100 parts by weight of the vinyl chloride resin. A vinyl chloride resin laminated sheet, which is an open-cell foam layer. 2. The vinyl chloride resin laminated sheet according to claim 1, wherein the water absorbent resin is a starch-acrylic acid copolymer. 3. The vinyl chloride resin laminated sheet according to claim 1, wherein the base cloth is a hydrophobic base cloth. 4. The vinyl chloride resin laminated sheet according to claim 1, wherein the vinyl chloride resin layer is formed by coating a vinyl chloride resin paste. 5. The vinyl chloride resin layer contains 0.5 to 10 parts of thermoplastic resin powder based on 100 parts by weight of the vinyl chloride resin.
The vinyl chloride resin laminated sheet according to claim 1, wherein the vinyl chloride resin laminated sheet contains a part by weight. 6. The vinyl chloride resin layer contains 1 to 10 parts by weight of a hydrocarbon compound having a boiling point of 130 to 200 ° C. and / or a halogenated hydrocarbon compound with respect to 100 parts by weight of the vinyl chloride resin. The vinyl chloride resin laminated sheet according to claim 1, which is formed from a vinyl chloride resin composition.