JP2011062950A - Sheet material for molding and leather-like molded article obtained by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sheet material for machining a mold which keeps a difference in elongation and in stress with respect to the meridian direction and the latitude direction of a synthetic leather or an artificial leather with woven fabric, textile fabric and nonwoven fabric as a relieved base material and moldability is improved. <P>SOLUTION: The sheet material for molding is obtained by piling a porous membrane obtained by mixing a polyvinyl chloride resin with a polyurethane resin and a non-porous membrane obtained by mixing a polyvinyl chloride resin with a polyurethane resin. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a sheet material mainly composed of a polyurethane resin having excellent moldability in vacuum forming. In more detail, automotive interior materials (center panels, door panels, etc.), mobile phone / notebook computer cases, cases for home appliances, jewelry display mannequins, display panels, partition panels, housing equipment, etc. It is related with the sheet material from which the leather-like molded product which can be used for is obtained.

  Luxury, texture, unique surface and touch of genuine leather are attracting attention as decorations for automobile interiors and mobile phones. However, since it is natural, the uniformity of quality is not desired and is only used as an option.

  On the other hand, when synthetic leather or artificial leather is subjected to vacuum forming, the warp and weft directions and constant elongation are determined depending on the woven structure, knitted structure, structure, etc. of the woven fabric, knitted fabric, and nonwoven fabric used as the base material. There was a problem that the stress at the time was different and the finish of the corner part of the molded product lacked elegance (Patent Document 1).

  In addition, when synthetic leather or artificial leather is stretched to 50 to 200% at the time of molding, the texture of the base substrate, such as texture, stitch, unevenness, etc., is conspicuous on the surface, and there is no commercial value. Also have.

  In addition, polyurethane resin, which is often used as a raw material for synthetic leather, etc., has too much elastic recovery force, and even after molding, the residual elastic recovery force may cause the substrate to warp or have a high development rate (150 to 200%). There is also a problem that peeling from the substrate occurs at the molding part.

  Furthermore, non-porous membranes such as polyvinyl chloride resin sheets and polyolefin resin sheets are also used in this application, but they all lack cushioning properties, and the polyvinyl chloride resin sheet is heavy. is there.

JP-A-11-117181

  The present invention has been made in view of the above-mentioned problems, and could not be solved by conventional synthetic leather or artificial leather, problems of uniformizing tensile strength and elongation in all directions, and high temperature range during molding The problem of proper molding due to the stress behavior in the vicinity of the stress of the resin substrate at the same temperature range as well as various problems such as substrate warping and floating from the substrate due to the residual elastic recovery force of the sheet after molding It is an object of the present invention to provide a molding sheet material that is light and can provide a leather-like molded product.

  As a result of intensive studies, the present inventors have laminated a porous film in which a polyurethane resin is blended with a thermoplastic resin such as polyvinyl chloride resin and a nonporous film in which a polyurethane resin is blended with a thermoplastic resin such as polyvinyl chloride resin. As a result, it was found that the above problems could be solved, and the present invention was completed.

  That is, the sheet material of the present invention is a sheet material that is subjected to a molding process, and in order to solve the above problems, a porous film formed by blending a polyurethane resin with a polyvinyl chloride resin, and a polyurethane resin It is assumed that a nonporous membrane formed by blending a vinyl chloride resin is laminated.

  In the porous material and the nonporous membrane, the compounding ratio of the polyvinyl chloride resin is preferably 5 to 30% by weight in the mixture with the polyurethane resin.

  The sheet material is suitable for use in vacuum forming.

  The molded product of the present invention is formed of the sheet material of the present invention.

  According to the present invention, since base materials such as woven fabrics and knitted fabrics that have been used in conventional synthetic leather and artificial leather are not used, tensile strength and tensile strength are also obtained in the length direction, the width direction, and other directions. It is possible to obtain a leather-like sheet having high dimensional stability and exhibiting substantially the same elongation.

  In addition, problems such as substrate warping and peeling from the substrate at the molding part with a high development rate (150 to 200%) when the polyurethane sheet is subjected to vacuum molding, etc. are eliminated, and conventional synthetic leather is applied It can also be used for molding applications that were not possible.

  Furthermore, the adhesion between the polyurethane sheet and the ABS resin as the base material has conventionally required the intervention of a vinyl chloride-based adhesive or a special polyurethane-based or polyester-based hot-melt type film. Use of thermoplastic resin such as vinyl resin enables direct bonding to an ABS resin substrate near 200 ° C. immediately after extrusion molding, and provides sufficient adhesion strength. It is.

  In this specification, “leather-like” refers to all sheet-like materials having the appearance (surface feel) and tactile feel (elasticity) reminiscent of leather, and the color and pattern of the surface, texture (butterfly and other irregularities), The gloss and the like are not limited.

  As described above, the sheet material of the present invention is a laminate of a porous film formed by blending a polyvinyl chloride resin with a polyurethane resin and a nonporous film formed by blending a polyvinyl chloride resin with a polyurethane resin. is there.

  The polyurethane resin that forms the porous film and the nonporous film may be any one using polycarbonate polyol, polyester polyol, polyether polyol, silicon-based diol, fluorine-based polyol, or polyamide-based polyol as the polyol component. Moreover, what uses a castor oil-type polyol as a plant-derived component may be used.

  In this invention, the polyvinyl chloride resin mix | blended with a polyurethane resin is mix | blended, However In addition to a polyvinyl chloride resin, another thermoplastic resin can also be mix | blended. As other thermoplastic resins, those that are soluble in dimethylformamide (DMF) or dimethyl sulfoxide (DMSO), which are solvents for polyurethane resins, can be used as appropriate. Examples thereof include polyvinylidene chloride and polyvinyl acetate. And acrylic resin. When the polyvinyl chloride resin and other thermoplastic resins are used in combination, the proportion of the polyvinyl chloride resin in the total amount of these thermoplastic resins is preferably 50% by weight or more in terms of resin solids. Polyvinyl chloride resin and other thermoplastic resins may be selected from commercially available grades that can be dissolved in DMF or DMSO.

  In both the porous membrane and the nonporous membrane, the compounding ratio of the polyvinyl chloride resin (the total amount of the thermoplastic resin including the polyvinyl chloride resin when other thermoplastic resins are used together) is in the mixture with the polyurethane resin. It is preferably 5 to 30% by weight (however, the resin solid content, the same applies hereinafter), and more preferably 10 to 30% by weight. By setting the compounding ratio of the polyvinyl chloride resin within this range, the elasticity which is a characteristic of the polyurethane resin as the main component resin is obtained in the temperature range assumed at the time of use (ordinary temperature range: −10 ° C. to 80 ° C.). While holding, the effects of the present invention such as improvement in adhesion to the substrate and prevention of warping of the substrate can be obtained. When the blending ratio is less than 5% by weight, the effect expected by blending cannot be sufficiently obtained, and when it exceeds 30% by weight, the elastic recovery force of the porous film is lowered.

  As a method for producing the porous film, a resin in which a polyvinyl chloride resin is blended with a polyurethane resin is used on one side of a fabric (release cloth) or film (release film) as a base material (release material), for example, directly. A method of applying by coating and forming by wet coagulation is used. The woven fabric or film as the substrate is peeled off before or after the formation of the nonporous film described later.

  The base material is preferably dimensionally stable with respect to wetness, heat, tension, etc. during production. For example, a polyester fiber woven fabric or film can be used, and a polyester fiber woven fabric is preferable in terms of productivity. .

  To give a more specific example of the production method, the porous membrane is a polyurethane resin solution obtained by dissolving a polyurethane resin in a water-soluble polar solvent (dimethylformamide (DMF), dimethylsulfoxide (DMSO), etc.). In addition, a solution in which polyvinyl chloride resin is dissolved in DMF is blended, mixed, and this mixed solution is coated on a base material, which is immersed in water or an aqueous solution containing the polar solvent as described above, and wet. It can be formed by solidification.

  The polyurethane resin is prepared by dissolving the above divalent polyol in a polar solvent such as DMF or DMSO or a solvent such as methyl ethyl ketone (MEK), toluene or xylene, and divalent isocyanate (hexamethylene diisocyanate, isophorone diisocyanate, After adding diphenylmethane diisocyanate (MDI, hydrogenated MDI, etc.) and reacting sufficiently to make a prepolymer having isocyanate or hydroxyl group at the terminal, diols (ethylene glycol, propylene glycol, butylene glycol, etc. only from petroleum) Plant-derived 1,3-propanediol, 1,2-hexanediol, etc.) or divalent isocyanate (hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane) Isocyanate (MDI), were added hydrogenated MDI, etc.), increasing the degree of polymerization chain lengths reaction may be a polyurethane resin.

  When reacting with a prepolymer having an isocyanate group at the terminal, a divalent polyol (polycarbonate diol, polyethylene adipate, polybutylene adipate, polycaprolactone diol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc.) It is also possible to copolymerize certain castor oil-based polyols.

  On the other hand, the non-porous membrane, which is the surface layer, is prepared by blending the above polyurethane resin with a solution obtained by dissolving a thermoplastic resin such as polyvinyl chloride resin in a polar solvent such as DMF, and coating the mixed solution on release paper or the like. Then, it can be formed by drying the solvent.

  In order to laminate the porous film and the nonporous film, the entire surface is bonded with a two-component polyurethane resin adhesive, or when the one-component polyurethane resin is thermally laminated near the flow start temperature, or when the nonporous film is formed. A method of peeling the release paper after laminating on the porous film by a method such as adhesion by re-dissolution of the surface of the porous film with a residual solvent in a semi-dried state is used, but is not limited thereto.

  In the above, as a coating method, various coating methods such as knife coating, knife over roll coating, and reverse roll coating can be used.

  For the surface of the sheet material of the present invention, in order to obtain a design effect as required, for example, a release paper having a leather pattern, a geometric pattern pattern, a woven pattern, a grain pattern, or the like is used. Thus, irregularities of these patterns can be imparted. Moreover, the desired color and pattern by dyes and pigments can also be provided by a conventional method.

  The thickness of the porous membrane is not particularly limited, and the thicker one can maintain the cushioning property even after molding. However, in the molding of a complicated shape, wrinkles are generated and the quality is easily lowered. Therefore, it is preferable to set the thickness at which the cushioning property can be touched while preventing wrinkles to be about 250 to 700 μm, and more preferably 400 to 600 μm.

  Further, the thickness of the nonporous film is not particularly limited, but is preferably about 10 to 80 μm, and more preferably 40 to 60 μm. When the concave / convex pattern is imparted to the surface as described above, the thickness of the concave portion and the convex portion is different, so there is a possibility that a hue difference between the concave portion and the convex portion may occur when the sheet is unfolded during molding. If so, it is possible to prevent such problems, and it is also possible to prevent the degradation of valley cracks.

  Furthermore, the thickness of the sheet material of the present invention obtained by laminating both is about 260 to 750 μm, preferably 450 to 650 μm, in view of the balance between the finished quality of the molded product and the cushioning property.

  When the sheet material of the present invention obtained as described above is superposed on a resin plate as a substrate and pressed to form a composite plate, and this composite plate is subjected to vacuum forming (vacuum foam) or heat press, In addition, a molded product that does not peel off from the substrate at a molded portion having a high development rate (150 to 200%) can be obtained. A polyolefin resin such as ABS resin or polypropylene is used as the substrate.

  In order to bond the sheet material of the present invention to the substrate, an adhesive may be used as appropriate. However, when an ABS resin is used as a constituent resin of the substrate, conventionally used vinyl chloride adhesives and hot melts are used. Without intervening the film, it is possible to obtain high adhesion by directly bonding to an ABS resin plate near 200 ° C. immediately after extrusion molding, which is advantageous in terms of process and economy.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by a following example.

[Example 1]
A plain woven fabric of polyester fibers (250 denier Oxford) was refined by a continuous refining machine such as paste removal using caustic soda 2.5% and acetic acid 0.5% as chemicals.

  After that, it was immersed in 0.8% aqueous solution of fluorine water repellent AG-710 manufactured by Asahi Chemical Co., Ltd., squeezed with mangle, dried with hot air at 120 ° C, heat-treated at 160 ° C, and with a calendar roll at 190 ° C. A linear release pressure of 90 kg / cm was applied and pressed to obtain a smooth release cloth.

  Polycarbonate urethane resin CU-590H manufactured by Toray Cortex Co., Ltd .: 120 parts by weight (hereinafter referred to as “parts”), DMF dissolved (12.0% concentration) product of polyvinyl chloride resin PR410 manufactured by Vitec Co., Ltd. To 40 parts, DMF: 72 parts, Dainichi Seika Kogyo Co., Ltd. foam control agent CUT-101: 2 parts, DIC Corporation Pigment L-7560: 5 parts are added and sufficiently stirred, and the resin content concentration A 15% polyurethane / polyvinyl chloride resin formulation was obtained.

Apply the polyurethane / polyvinyl chloride resin mixture at 1000 g / m ² by direct coating on the smoothed surface of the release cloth and immerse it in a coagulation bath containing 10% by weight of DMF. It was precipitated and solidified, washed in an 80 ° C. water bath for 30 minutes, DMF was completely removed, and then dried by hot air drying at 120 ° C. to obtain a polyurethane / polyvinyl chloride porous membrane having a thickness of 550 μm.

  On the other hand, polycarbonate resin-based polyurethane resin CU-590H manufactured by Toray Cortex Co., Ltd. CU-590H: 100 parts of DMF-dissolved (12.0% concentration) product of polyvinyl chloride resin PR410 manufactured by Vitec Co., Ltd., 100 parts: 100 parts of methyl ethyl ketone , Shin-Etsu Chemical Co., Ltd. Silicone Oil KP-366: 3 parts, Dainichi Seika Kogyo Co., Ltd. pigment masterbatch BS-780: 30 parts were mixed and stirred to obtain a polyurethane / polyvinyl chloride resin blending solution 1 .

Applying 180 g / m ^{2 of} polyurethane / polyvinyl chloride resin formulation solution 1 to Dai Nippon Printing Co., Ltd. release paper DE-126 by direct coating, drying with hot air at 140 ° C. 180 g / m ^{2 of the} vinyl resin preparation solution 1 was applied and dried with hot air at 140 ° C. to obtain a polyurethane / polyvinyl chloride resin nonporous film having a thickness of 50 μm.

  Next, 70 parts of methyl ethyl ketone: 70 parts of Coronate HL manufactured by Nippon Polyurethane Industry Co., Ltd. was added to 100 parts of the polycarbonate-based polyurethane resin Crisbon S-123 manufactured by DIC Corporation, and a polyurethane preparation solution 2 was obtained.

The polyurethane / polyvinyl chloride resin porous film formed on the release cloth by applying 180 g / m ² of the polyurethane preparation solution 2 to the polyurethane / polyvinyl chloride resin nonporous film formed on the release paper and drying with hot air. A 180 ° C. heat roll was applied to the film from the release paper side, and after pressure laminating, the release paper was peeled off, and then the release cloth was peeled off to obtain a leather-like sheet.

[Example 2]
A plain woven fabric of polyester fibers (250 denier Oxford) was refined by a continuous refining machine such as paste removal using caustic soda 2.5% and acetic acid 0.5% as chemicals.

  After that, it was immersed in 0.8% aqueous solution of fluorine water repellent AG-710 manufactured by Asahi Chemical Co., Ltd., squeezed with mangle, dried with hot air at 120 ° C, heat-treated at 160 ° C, and with a calendar roll at 190 ° C. A linear release pressure of 90 kg / cm was applied and pressed to obtain a smooth release cloth.

  Polycarbonate urethane resin CU-590H manufactured by Toray Cortex Co., Ltd .: 120 parts by weight (hereinafter referred to as “parts”), DMF dissolved (12.0% concentration) product of polyvinyl chloride resin PR410 manufactured by Vitec Co., Ltd. To 60 parts, DMF: 68 parts, Dainichi Seika Kogyo Co., Ltd. foam control agent CUT-101 2 parts, DIC Co., Ltd. Pigment L-7560: 5 parts were added and stirred sufficiently to give a resin concentration of 15 % Polyurethane / polyvinyl chloride resin formulation liquid was obtained.

Apply the polyurethane / polyvinyl chloride resin mixture at 1000 g / m ² by direct coating on the smoothed surface of the release cloth and immerse it in a coagulation bath containing 10% by weight of DMF. It was precipitated and solidified, washed in an 80 ° C. water bath for 30 minutes, DMF was completely removed, and then dried by hot air drying at 120 ° C. to obtain a polyurethane / polyvinyl chloride porous membrane having a thickness of 550 μm.

  On the other hand, polycarbonate-based polyurethane resin CU-590H manufactured by Toray Cortex Co., Ltd. CU-590H: 100 parts of DMF-dissolved (12.0% concentration) polyvinyl chloride resin PR410 manufactured by Vitec Co., Ltd. 20 parts of methyl ethyl ketone: 100 parts, Shin-Etsu Chemical Industry Co., Ltd. Silicone Oil KP-366: 3 parts and Dainichi Seika Kogyo Co., Ltd. Pigment Master Batch BS-780: 30 parts were mixed and stirred to obtain a polyurethane / polyvinyl chloride resin preparation solution 1.

Applying 180 g / m ^{2 of} polyurethane / polyvinyl chloride resin formulation solution 1 to Dai Nippon Printing Co., Ltd. release paper DE-126 by direct coating, drying with hot air at 140 ° C. 180 g / m ^{2 of the} vinyl resin preparation solution 1 was applied and dried with hot air at 140 ° C. to obtain a polyurethane / polyvinyl chloride resin nonporous film having a thickness of 50 μm.

  Next, 70 parts of methyl ethyl ketone, and 3 parts of Coronate HL manufactured by Nippon Polyurethane Industry Co., Ltd. are added to 100 parts of polycarbonate-based polyurethane resin Chrisbon S-123 manufactured by DIC Corporation, and a polyurethane preparation solution 2 is obtained. It was.

The polyurethane / polyvinyl chloride resin nonporous film formed on the release paper is coated with 180 g / m ² of polyurethane preparation solution and dried with hot air, and the polyurethane porous film formed on the release cloth is heated to 180 ° C. A heat roll was applied from the release paper side, and after pressure laminating, the release paper was peeled off, and then the release cloth was peeled off to obtain a leather-like sheet.

[Example 3]
A plain woven fabric of polyester fibers (250 denier Oxford) was refined by a continuous refining machine such as paste removal using caustic soda 2.5% and acetic acid 0.5% as chemicals.

  After that, it was immersed in 0.8% aqueous solution of fluorine water repellent AG-710 manufactured by Asahi Chemical Co., Ltd., squeezed with mangle, dried with hot air at 120 ° C, heat-treated at 160 ° C, and with a calendar roll at 190 ° C. A linear release pressure of 90 kg / cm was applied and pressed to obtain a smooth release cloth.

  On the other hand, polycarbonate urethane resin CU-590H manufactured by Toray Cortex Co., Ltd. CU-590H: 120 parts by weight (hereinafter referred to as “part”), DMF dissolution (12.0% concentration) of polyvinyl chloride resin PR410 manufactured by Vitec Co., Ltd. ) 80 parts of DMF: 64 parts of DMF, 2 parts of foam regulator CUT-101 manufactured by Dainichi Seika Kogyo Co., Ltd. and 5 parts of pigment L-7560 manufactured by DIC Co., Ltd. A polyurethane / polyvinyl chloride resin blend solution having a concentration of 15% was obtained.

Applying 1000g / m ² of polyurethane / polyvinyl chloride resin formulation liquid to the smoothened surface of the release cloth by direct coating and immersing it in a coagulation bath containing 10% by weight of DMF, polyurethane / polyvinyl chloride resin The precipitate was solidified, washed in an 80 ° C. water bath for 30 minutes, and after DMF was completely removed, it was dried by hot air drying at 120 ° C. to obtain a 550 μm polyurethane / polyvinyl chloride porous membrane.

  Toray Reco-Tex Co., Ltd. Polycarbonate-based polyurethane resin CU-590H: 100 parts DMF-dissolved (12.0% concentration) polyvinyl chloride resin PR410 made by Vitec Co., Ltd. 20 parts methyl ethyl ketone: 100 parts, Shin-Etsu Chemical Industrial / silicone oil KP-366: 3 parts and Dainichi Seika Kogyo's pigment master batch BS-780: 30 parts were mixed and stirred to obtain a polyurethane / polyvinyl chloride resin blend solution 1.

180 g / m ^{2 of} polyurethane / polyvinyl chloride resin formulation solution 1 is applied by direct coating onto release paper DE-126 manufactured by Dai Nippon Printing Co., Ltd., dried with hot air at 140 ° C. 180 g / m ^{2 of the} vinyl chloride resin formulation solution 1 was applied and dried with hot air at 140 ° C. to obtain a polyurethane / polyvinyl chloride resin nonporous film having a thickness of 50 μm.

  Next, 70 parts of methyl ethyl ketone, and 3 parts of Coronate HL manufactured by Nippon Polyurethane Industry Co., Ltd. are added to 100 parts of polycarbonate-based polyurethane resin Chrisbon S-123 manufactured by DIC Corporation, and a polyurethane preparation solution 2 is obtained. It was.

The polyurethane / polyvinyl chloride resin nonporous film formed on the release paper is coated with 180 g / m ² of polyurethane preparation solution and dried with hot air, and the polyurethane porous film formed on the release cloth is heated to 180 ° C. A heat roll was applied from the release paper side, and after pressure laminating, the release paper was peeled off, and then the release cloth was peeled off to obtain a leather-like sheet.

[Example 4]
A plain woven fabric of polyester fibers (250 denier Oxford) was refined by a continuous refining machine such as paste removal using caustic soda 2.5% and acetic acid 0.5% as chemicals.

After that, it was immersed in 0.8% aqueous solution of fluorine water repellent AG-710 manufactured by Asahi Chemical Co., Ltd., squeezed with mangle, dried with hot air at 120 ° C, heat-treated at 160 ° C, and with a calendar roll at 190 ° C. A linear release pressure of 90 kg / cm was applied and pressed to obtain a smooth release cloth.

  Polycarbonate urethane resin CU-590H manufactured by Toray Cortex Co., Ltd .: 120 parts by weight (hereinafter referred to as “parts”), DMF dissolved (12.0% concentration) product of polyvinyl chloride resin PR410 manufactured by Vitec Co., Ltd. To 100 parts, DMF: 60 parts, Dainichi Seika Kogyo Co., Ltd. foam control agent CUT-101: 2 parts, DIC Corporation pigment L-7560: 5 parts, and sufficiently stirred, resin concentration A 15% polyurethane / polyvinyl chloride resin formulation was obtained.

Apply the polyurethane / polyvinyl chloride resin mixture at 1000 g / m ² by direct coating on the smoothed surface of the release cloth and immerse it in a coagulation bath containing 10% by weight of DMF. Precipitated and solidified, washed in an 80 ° C. water bath for 30 minutes, completely removed DMF, and then dried by hot air drying at 120 ° C. to obtain a 550 μm polyurethane / polyvinyl chloride porous membrane.

  On the other hand, polycarbonate-based polyurethane resin CU-590H manufactured by Toray Cortex Co., Ltd. CU-590H: 100 parts of DMF-dissolved (12.0% concentration) polyvinyl chloride resin PR410 manufactured by Vitec Co., Ltd. 20 parts of methyl ethyl ketone: 100 parts, Shin-Etsu Chemical Industry Co., Ltd. Silicone Oil KP-366: 3 parts and Dainichi Seika Kogyo Co., Ltd. pigment master batch BS-780: 30 parts were mixed and stirred to obtain a polyurethane / polyvinyl chloride resin preparation solution 1.

Applying 180 g / m ^{2 of} polyurethane / polyvinyl chloride resin formulation solution 1 to Dai Nippon Printing Co., Ltd. release paper DE-126 by direct coating, drying with hot air at 140 ° C. 180 g / m ^{2 of the} vinyl resin preparation solution 1 was applied and dried with hot air at 140 ° C. to obtain a polyurethane / polyvinyl chloride resin nonporous film having a thickness of 50 μm.

  Next, 70 parts of methyl ethyl ketone, and 3 parts of Coronate HL manufactured by Nippon Polyurethane Industry Co., Ltd. are added to 100 parts of polycarbonate-based polyurethane resin Chrisbon S-123 manufactured by DIC Corporation, and a polyurethane preparation solution 2 is obtained. It was.

The polyurethane / polyvinyl chloride resin nonporous film formed on the release paper is coated with 180 g / m ² of polyurethane preparation solution and dried with hot air, and the polyurethane porous film formed on the release cloth is heated to 180 ° C. A heat roll was applied from the release paper side, and after pressure laminating, the release paper was peeled off, and then the release cloth was peeled off to obtain a leather-like sheet.

[Comparative Example 1]
A plain woven fabric of polyester fibers (250 denier Oxford) was refined by a continuous refining machine such as paste removal using caustic soda 2.5% and acetic acid 0.5% as chemicals.

  After that, it was immersed in 0.8% aqueous solution of fluorine water repellent AG-710 manufactured by Asahi Chemical Co., Ltd., squeezed with mangle, dried with hot air at 120 ° C, heat-treated at 160 ° C, and with a calendar roll at 190 ° C. A linear release pressure of 90 kg / cm was applied and pressed to obtain a smooth release cloth.

  To Recoatx Co., Ltd. Polycarbonate urethane resin CU-590H: 120 parts by weight (hereinafter referred to as “parts”), DMF: 80 parts, DIC Corporation pigment L-7560: 5 parts are added. The mixture was sufficiently stirred to obtain a polyurethane resin preparation liquid having a resin concentration of 15%.

By direct coating on the smoothened surface of the release cloth, 1000 g / m ² of the polyurethane resin preparation liquid is applied, immersed in a coagulation bath containing 10% by weight of DMF, and the polyurethane resin is precipitated and solidified. Washing was performed in a water bath for 30 minutes, and DMF was completely removed, followed by drying with hot air drying at 120 ° C. to obtain a 550 μm polyurethane resin porous membrane.

  On the other hand, polycarbonate-based polyurethane resin CU-590H manufactured by Toray Cortex Co., Ltd .: 100 parts, methyl ethyl ketone: 100 parts, Shin-Etsu Chemical Co., Ltd. silicone oil KP-366: 3 parts, pigment master manufactured by Dainichi Seika Kogyo Co., Ltd. 30 parts of batch BS-780 was mixed and stirred to obtain polyurethane resin preparation solution 1.

Apply 180 g / m ^{2 of} polyurethane resin formulation solution 1 by direct coating on release paper DE-126 of Dai Nippon Printing Co., Ltd. and dry with hot air at 140 ° C. Further, the above polyurethane / polyvinyl chloride resin formulation solution 1 was applied at 180 g / m ² , and hot air drying at 140 ° C. was performed to obtain a polyurethane resin nonporous film having a thickness of 50 μm.

  Next, 70 parts of methyl ethyl ketone, and 3 parts of Coronate HL manufactured by Nippon Polyurethane Industry Co., Ltd. are added to 100 parts of polycarbonate-based polyurethane resin Chrisbon S-123 manufactured by DIC Corporation, and a polyurethane preparation solution 2 is obtained. It was.

The polyurethane compound solution 2 is applied to the polyurethane resin nonporous film formed on the release paper at 180 g / m ² and dried with hot air, and the polyurethane resin porous film formed on the release cloth is heated with a 180 ° C. hot roll. After applying and laminating by pressure from the release paper side, the release paper was peeled, and then the release cloth was peeled to obtain a leather-like sheet.

  The blending ratio of the thermoplastic resin (vinyl chloride resin) of each leather-like sheet obtained in Examples 1 to 4 and Comparative Example 1 to the polyurethane resin, and the tensile strength at room temperature (20 ° C.) (stress at break, elongation) Table 1 shows the results of tensile strength (stress at break, elongation) in a constant temperature bath at 160 ° C.

  In addition, the tensile strength measurement was performed at a speed of 100 mm / min with an orientec tensile tester STA-1225.

  The leather-like sheet obtained in Examples 1 to 4 and Comparative Example 1 was pressure-bonded to a general-purpose grade ABS resin extruded plate when the temperature dropped to 190 to 200 ° C., and the composite of the leather-like sheet and the resin plate A plate was formed. Since the leather-like sheet obtained in Comparative Example 1 cannot be adhered by this method, a polyester-based hot melt film (melt point 150 ° C.) is laminated on the back side of the leather-like sheet, and the resin plate is pressed at a temperature of 160 ° C. A composite plate was formed.

  Each composite plate of Example and Comparative Example is vacuum-molded in the same mold and under the same molding conditions (no upper heater heating, lower heater temperature 450 ° C., heating time 120 seconds, vacuum time 30 seconds, cooling time 30 seconds) The molded product obtained was evaluated. That is, a rectangular cut with a width of 2 cm and a length of 5 cm is made with a razor blade in the same part of the skin sheet of each molded product, and toluene is soaked from the cut portion with a width of 2 cm at one end to dissolve the ABS resin as a substrate. The skin sheet was peeled off by 2 cm. After leaving at room temperature for 24 hours and evaporating toluene during that time, the peeled skin sheet was picked with a finger and pulled in the direction of the unpeeled portion, and the remaining 3 cm portion was peeled off. The peeled state of the skin sheet was observed, and the adhesion with the ABS resin was examined. As a judgment criterion, the destruction of the porous film was regarded as material destruction, and peeling at the interface with the substrate was judged as insufficient adhesion. Further, the appearance of the molded product was visually confirmed, and the adhesion was also examined by a cross-cut test. The results are shown in Table 2.

  As shown in Table 2, the composite plates of Examples 1 to 4 have excellent adhesion to the ABS resin, and are hardly molded due to the floating from the substrate and the warpage of the substrate that occurred in the comparative example. It was confirmed to have sex. As shown in Table 1, under the temperature condition of about 160 ° C., which is the temperature condition at the time of molding, the sheet of the example has a large increase in elongation while the tensile strength is lower than that of the comparative example. It is thought to be due to.

  The sheet material of the present invention is used for automobile interior materials (center panels, door panels, etc.), mobile phone / notebook PC cases, home appliances and other cases, jewelery display mannequins, display panels, partition panels, and housing equipment. It is suitably used for manufacturing related molded articles.

Claims (4)

A sheet material used for molding processing,
A sheet material characterized by laminating a porous film formed by blending a polyvinyl chloride resin with a polyurethane resin and a nonporous film formed by blending a polyvinyl chloride resin with a polyurethane resin.   2. The sheet material according to claim 1, wherein a blending ratio of the polyvinyl chloride resin in the porous film and the nonporous film is 5 to 30 wt% in the mixture with the polyurethane resin.   The sheet material according to claim 1, wherein the sheet material is subjected to vacuum forming.   The molded product formed with the sheet | seat material of any one of Claims 1-3.