JP5069736B2 - Thermoplastic polyolefin resin skin material - Google Patents

Description

  The present invention relates to a thermoplastic polyolefin resin skin material used for automobile interior materials, home appliance parts, and the like, and is particularly excellent in scratch resistance, abrasion resistance, chemical resistance, and forms a uniform matte film. The present invention relates to a thermoplastic polyolefin resin skin material.

  Conventionally, vehicle interior materials (instrument panels, door trims, etc.) and household electrical appliance parts have been strongly desired to recycle these members in order to reduce waste materials after use as much as possible in view of recent dust problems and environmental problems. In view of this, thermoplastic polyolefins that can be recycled, such as polypropylene (PP), ABS resin, AS resin, and polyolefin-based thermoplastic elastomer (TPO), are used. However, these thermoplastic polyolefins are inferior to conventional vinyl chloride resins in terms of surface adhesion, scratch resistance, abrasion resistance, and chemical resistance, and are designed to give a sense of quality and automobiles. In the case of the interior material, various coatings are applied to the thermoplastic polyolefin base material in consideration of anti-glare properties for the driver.

  Therefore, the paint used is a chlorinated polypropylene-modified acrylic resin that has good adhesion to polyolefin resins such as PP resin and TPO resin as a binder resin, and this includes inorganic extender pigments (silica, talc), acrylic There has been proposed a method in which a paint containing a matting agent such as resin particles or a chlorinated polypropylene primer is applied and a polyester resin or polyurethane resin is applied thereon.

  Furthermore, recently, a growing number of manufacturers are actively working on this countermeasure due to the growing environmental problems, and there is a movement to construct products using materials with excellent environmental conservation. For example, there are studies that do not select specific solvents (such as toluene) from the organic solvents used in the paint, and studies that use water-based resins instead of organic solvents to minimize VOC (volatile organic compound) emissions. Although it is actively performed, it is still insufficient for the current global environmental conservation (Patent Documents 1 to 3).

JP 2006-307015 A JP 2004-051901 A JP 2006-176615 A

  Under such circumstances, regarding the thermoplastic polyolefin resin skin material used for vehicle interior materials and home appliance parts, it has excellent surface scratch resistance, abrasion resistance, chemical resistance and uniform matte effect. There is a demand for the development of environmentally friendly products with environmental conservation on a global scale.

  Therefore, the object of the present invention is excellent in scratch resistance, abrasion resistance, chemical resistance and uniform matting effect, and contributes to the reduction of greenhouse gases by incorporating carbon dioxide from the viewpoint of the global environment. It is to provide a thermoplastic polyolefin resin skin material as an environmentally friendly product.

The above object is achieved by the present invention described below. That is, the present invention includes a thermoplastic polyolefin resin sheet, and a said thermoplastic polyolefin resin sheet on a directly or topcoat layer applied over the primer layer, the topcoat layer, 5-membered cyclic carbonate include polyhydroxy polyurethane resin derived from the reaction of a compound with an amine compound, wherein 5-membered cyclic carbonate compound, wherein the compound der Rukoto obtained by reacting an epoxy compound and carbon dioxide heat A plastic polyolefin resin skin material is provided.

In the said invention, it is preferable that the hydroxyl value of the said polyhydroxy polyurethane resin is 25-300 mgKOH / g ; The said polyhydroxy polyurethane resin contains 1-25 mass% of carbon dioxide content.

Moreover, in the said invention, the said topcoat layer is 1-150 mass parts of at least 1 sort (s) of fine powder chosen from an organic fine powder and an inorganic fine powder with respect to 100 mass parts of said polyhydroxy polyurethane resins. the polyhydroxy polyurethane resin in the topcoat layer, the cross-linking agent which reacts with hydroxyl groups of the polyhydroxy polyurethane resin; that a composition prepared by blending in a ratio; the top coat layer further comprise other resins it is preferred but a crosslinked coating formed is crosslinked.

  According to the present invention, by using a polyhydroxypolyurethane resin for the topcoat layer of the thermoplastic polyolefin resin skin material, it is excellent in scratch resistance, abrasion resistance, chemical resistance and uniform matte effect, Incorporating carbon dioxide also from an environmental point of view provides a thermoplastic polyolefin resin skin material as an environmentally friendly product by contributing to the reduction of greenhouse gases.

The infrared absorption spectrum of an epoxy compound (Epicoat 828). The infrared absorption spectrum of a 5-membered cyclic carbonate compound. GPC elution curve of a 5-membered cyclic carbonate compound. Mobile phase: THF, column: TSK-Gel GMHXL + G2000HXL + G3000HXL, detector: IR

Next, the present invention will be described in more detail with reference to preferred embodiments.
The thermoplastic polyolefin resin skin material of the present invention has a topcoat layer applied directly or via a primer layer on a resin sheet, and the topcoat layer reacts with a 5-membered cyclic carbonate compound and an amine compound. It is characterized by comprising a polyhydroxy polyurethane resin derived from

  The 5-membered cyclic carbonate compound used in the present invention can be produced by reacting an epoxy compound and carbon dioxide as shown in the following formula -A. More specifically, the epoxy compound is reacted with carbon dioxide in the presence or absence of an organic solvent and in the presence of a catalyst at a temperature of 40 ° C. to 150 ° C. under normal pressure or slightly increased pressure for 10 to 20 hours. Can be obtained.

［参考文献］
N.Kihara,T.Endo,J.Org.Chem.,1993,58,6198
N.Kihara,T.Endo,J.Polymer Sci.,PartA Polmer Chem.,1993,31(12),2765

[References]
N. Kihara, T. Endo, J. Org. Chem., 1993, 58, 6198
N. Kihara, T. Endo, J. Polymer Sci., Part A Polmer Chem., 1993, 31 (12), 2765

  Examples of the epoxy compound used in the present invention include the following compounds.

  The epoxy compounds listed above are preferable compounds used in the present invention, and the present invention is not limited to these exemplified compounds. Accordingly, not only the above-exemplified compounds but also any other compounds that are currently commercially available and can be easily obtained from the market can be used in the present invention.

  Examples of the catalyst used in the reaction between the epoxy compound and carbon dioxide include a base catalyst and a Lewis acid catalyst. Examples of the base catalyst include tertiary amines such as triethylamine, tributylamine, diazabicycloundecene, diazabicyclooctane, and pyridine, alkali metal salts such as lithium chloride, lithium bromide, lithium fluoride, and sodium chloride, and chloride. Alkaline earth metal salts such as calcium, quaternary ammonium salts such as tetrabutylammonium chloride, tetraethylammonium bromide, benzyltrimethylammonium chloride, carbonates such as potassium carbonate and sodium carbonate, zinc acetate, lead acetate, copper acetate, iron acetate Metal oxides such as calcium oxide, magnesium oxide, metal oxides such as zinc oxide, and phosphonium salts such as tetrabutylphosphonium chloride.

  Examples of the Lewis acid catalyst include tin compounds such as tetrabutyltin, dibutyltin dilaurate, dibutyltin diacetate, and dibutyltin octoate.

  The amount of the catalyst is 0.1 to 100 parts by mass, preferably 0.3 to 20 parts by mass, per 50 parts by mass of the epoxy compound. When the amount used is less than 0.1 parts by mass, the effect as a catalyst is small, and when it exceeds 50 parts by mass, various performances of the final resin are lowered.

  Examples of the organic solvent that can be used in the reaction between the epoxy compound and carbon dioxide include dimethylformamide, dimethylsulfoxide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, and tetrahydrofuran. These organic solvents may be used in a mixed system with other poor solvents such as methyl ethyl ketone, xylene, toluene, tetrahydrofuran, diethyl ether, cyclohexanone and the like.

  Next, the obtained 5-membered cyclic carbonate compound and amine compound are reacted in the presence of an organic solvent at a temperature of 20 ° C. to 150 ° C. as shown in the following [Formula-B] to be used in the present invention. A hydroxy polyurethane resin is obtained.

  As the amine compound used in the present invention, any of those conventionally used for producing a polyurethane resin can be used and is not particularly limited. For example, aliphatic diamines such as methylenediamine, ethylenediamine, trimethylenediamine, 1,3-diaminopropane, hexamethylenediamine, octamethylenediamine; phenylenediamine, 3,3′-dichloro-4,4′-diaminodiphenylmethane, 4 , 4′-methylenebis (phenylamine), 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylsulfone, metaxylylenediamine, paraxylylenediamine, and the like; 1,4-cyclohexanediamine, 4 , 4'-diaminocyclohexylmethane, 1,4'-diaminomethylcyclohexane, isophoronediamine and other alicyclic diamines; monoethanoldiamine, ethylaminoethanolamine, hydroxyethylaminopropylamine Such as alkanol diamine and the like.

  The amine compounds listed above are preferable compounds used in the present invention, and the present invention is not limited to these exemplified compounds. Accordingly, not only the above-exemplified compounds but also any other compounds that are currently commercially available and can be easily obtained from the market can be used in the present invention.

  Moreover, the number average molecular weight (measured by GPC and converted to standard polystyrene) of the polyhydroxy polyurethane resin of the present invention is preferably 2,000 to 100,000, more preferably 5,000 to 70,000.

The hydroxyl group content of the polyhydroxy polyurethane resin used in the present invention is preferably about 3 to 30% by mass (hydroxyl value 25 to 300 mg KOH / g ). When the hydroxyl group content is less than the above range, the effect of reducing carbon dioxide is insufficient. On the other hand, when the hydroxyl group content exceeds the above range, various physical properties as a polymer are insufficient.

  As the matting agent to be blended with the polyhydroxy polyurethane resin, at least one selected from organic fine powders and inorganic fine powders is used. The organic fine powder is not particularly limited. For example, acrylic resin particles, styrene resin particles, styrene-acrylic resin particles, phenol resin particles, melamine resin particles, acrylic-polyurethane resin particles, polyurethane resin particles, polyester Examples thereof include resin particles, nylon resin particles, silicone resin particles, and polyethylene resin particles. The average particle size of these powders is in the range of 0.1 to 10 μm, and the shape is preferably spherical or substantially spherical because the matteness of the formed coating film is particularly excellent.

  In addition, inorganic fine powders include talc, mica, calcium carbonate, barium sulfate, magnesium carbonate, clay, alumina, silica, carbon fiber, glass fiber, metal fiber, carbon black, titanium oxide, molybdenum, magnesium hydroxide, bentonite. And graphite. The average particle size of these powders is 10 μm or less in accordance with the object of the present invention, but is preferably as small as possible.

  The amount of the matting agent used is 1 to 150 parts by mass, preferably 3 to 60 parts by mass with respect to 100 parts by mass of the polyhydroxy polyurethane resin. When the amount of the matting agent used is less than 1 part by mass, the matting effect is not sufficient, and when the amount of the matting agent used exceeds 150 parts by mass, the mechanical properties of the coating film are greatly deteriorated. .

  In the polyhydroxypolyurethane resin used in the present invention, the hydroxyl group produced by the reaction of the 5-membered cyclic carbonate compound with the amine compound brings about further improvement in the performance of the thermoplastic polyolefin resin skin material of the present invention. Since the hydroxyl group has hydrophilicity, the adhesion to the thermoplastic polyolefin resin sheet can be improved, and an antistatic effect that cannot be achieved by conventional products can be obtained. Further, it is possible to further improve the scratch resistance, abrasion resistance, and chemical resistance of the surface by utilizing the reaction between the hydroxyl group and the crosslinking agent.

  In the present invention, a film of a composition comprising a polyhydroxy polyurethane resin and a matting agent can be used as it is, but it can also be used as a crosslinked film using a crosslinking agent. As the crosslinking agent, any crosslinking agent that reacts with a hydroxyl group can be used. For example, an alkyl titanate compound or a polyisocyanate compound may be mentioned, but a known crosslinking agent conventionally used for crosslinking polyurethane resins is preferred, but is not particularly limited. Examples include adducts of polyisocyanates having the following structural formula and other compounds.

  In addition, in the composition comprising the polyhydroxypolyurethane resin and matting agent of the present invention, various conventionally known binder resins are mixed in order to improve sprayability, coating suitability and film formability for thermoplastic polyolefin resin. Can be used. The binder resin is preferably one that can chemically react with a crosslinking agent such as the above-mentioned polyisocyanate adduct, but those that are not reactive can also be used in the present invention.

  As these binder resins, binder resins conventionally used for the surface of thermoplastic polyolefin resins can be used, and are not particularly limited. For example, acrylic resin, polyurethane resin, polyester resin, polybutadiene resin, silicone resin, melamine resin, phenol resin, polyvinyl chloride resin, cellulose resin, alkyd resin, modified cellulose resin, fluorine resin, polyvinyl butyral resin, epoxy resin, polyamide resin Etc. can be used. Moreover, when using these binder resin together, the usage-amount is 5-90 mass% with respect to the polyhydroxy polyurethane resin of this invention.

  In addition, the composition comprising the polyhydroxy polyurethane resin of the present invention and a matting agent may be applied to various coating materials such as a coating surface adjusting agent, a fluidity adjusting agent, an ultraviolet absorber, a dispersing agent, and an anti-settling agent as necessary. Additives may be blended.

  In the present invention, the thermoplastic polyolefin resin constituting the sheet is low density to high density polyethylene (LDPE, LLDPE, HDPE, etc.), polypropylene, polypropylene such as propylene-ethylene copolymer, and ethylene-propylene rubber (EPR), It consists of at least one resin selected from the group consisting of thermoplastic polyolefin resins such as ethylene-butene rubber (EBR) and ethylene-propylene-diene terpolymer (EDPM). In order to have good flexibility and elasticity as well as excellent mechanical strength, a polypropylene resin and a polyolefin-based thermoplastic elastomer are preferable.

  The thermoplastic polyolefin resin that constitutes the above sheet is inactive on the surface and often has poor adhesion to the coating on the surface. Therefore, the surface is physically or chemically activated by corona discharge treatment, etc. After coating, the composition comprising the polyhydroxy polyurethane resin and matting agent of the present invention is directly applied, or a chlorinated polyolefin resin, polyester resin and polyisocyanate compound or polyurethane resin and polyisocyanate compound is applied as a primer layer. After that, a composition comprising the polyhydroxy polyurethane resin of the present invention and a matting agent is applied.

  The composition comprising the polyhydroxy polyurethane resin of the present invention and the matting agent can be applied directly to the thermoplastic polyolefin resin sheet or on the primer layer by a known coating method such as brush coating, spraying, roll coating, gravure, or dipping. It coats so that the thickness after drying may be set to about 3-20 micrometers, and it heat-processes at the temperature of about 50-120 degreeC after drying, and a film is formed. In this way, the thermoplastic polyolefin resin skin sheet of the present invention is processed into a predetermined shape by vacuum forming.

  By using a polyhydroxypolyurethane resin for the topcoat layer of the thermoplastic polyolefin resin skin material of the present invention, the polyhydroxypolyurethane resin is excellent in scratch resistance, abrasion resistance, chemical resistance and uniform matting effect. By virtue of the strong interaction between the hydroxyl group and the base sheet at the interface, excellent adhesion and flexibility to the base material and an antistatic effect can be obtained.

  Also, from the viewpoint of reducing greenhouse gases, by incorporating carbon dioxide into the resin, an environment-friendly thermoplastic polyolefin resin skin material that could not be achieved with conventional products is provided.

  Next, the present invention will be described in more detail with reference to reference examples, specific polymerization examples, examples and comparative examples, but the present invention is not limited to these examples. In the following examples, “part” and “%” are based on mass unless otherwise specified.

Reference Example 1 (Production of 5-membered cyclic carbonate compound)
In a reaction vessel equipped with a stirrer, a thermometer, a gas introduction tube and a reflux condenser, a divalent epoxy compound represented by the following formula A (Japan Epoxy Resin Co., Ltd., Epicoat 828; epoxy equivalent 187 g / mol [Figure] 1]) After 100 parts, 100 parts of N-methylpyrrolidone and 1.5 parts of sodium iodide were added and dissolved uniformly, carbon dioxide gas was added at 0.5 liter / min. The mixture was heated and stirred at 80 ° C. for 30 hours while bubbling at a speed of 5 ° C.

  After completion of the reaction, the obtained solution was gradually added to 300 parts of n-hexane with high-speed stirring at 300 rpm, and the resulting powdered product was filtered with a filter, further washed with methanol, and N-methylpyrrolidone and Sodium iodide was removed. The powder was dried in a drier to obtain 118 parts (yield 95%) of a white powder 5-membered cyclic carbonate compound (1-A).

In the infrared absorption spectrum (Horiba FT-720) of the obtained product, the peak derived from the epoxy group in the vicinity of 910 cm ⁻¹ almost disappears in the product, and the cyclic that does not exist in the raw material in the vicinity of 1,800 cm ^−1. Absorption of the carbonyl group of the carbonate group was confirmed ([FIG. 2]). Moreover, the number average molecular weight of the product was 414 (polystyrene conversion, Tosoh; GPC-8220) ([FIG. 3]).
In the obtained 5-membered cyclic carbonate compound (1-A), 19% of carbon dioxide is immobilized.

Reference Example 2 (Production of 5-membered cyclic carbonate compound)
In place of the divalent epoxy compound A used in Reference Example 1, the reaction was carried out in the same manner as in Reference Example 1 except that the following formula B (manufactured by Toto Kasei Co., Ltd., YDF-170; epoxy equivalent 172 g / mol) was used. 121 parts (yield 96%) of powdered 5-membered cyclic carbonate compound (1-B) were obtained. The product was confirmed by infrared absorption spectrum, GPC and NMR. In the obtained 5-membered cyclic carbonate compound (1-B), 20.3% of carbon dioxide is immobilized.

Reference Example 3 (Production of 5-membered cyclic carbonate group compound)
Instead of the divalent epoxy compound A used in Reference Example 1, the reaction was carried out in the same manner as in Reference Example 1 except that the following formula C (manufactured by Nagase ChemteX Corporation, EX-212; epoxy equivalent 151 g / mol) was used. A colorless and transparent liquid 5-membered cyclic carbonate compound (1-C) (111 parts, yield 86%) was obtained. The product was confirmed by infrared absorption spectrum, GPC and NMR. In the obtained 5-membered cyclic carbonate compound (1-C), 22.5% of carbon dioxide is immobilized.

Polymerization Examples 1 to 3 (Production of polyhydroxy polyurethane resin)
A reaction vessel equipped with a stirrer, a thermometer, a gas introduction tube and a reflux condenser was replaced with nitrogen so that the 5-membered cyclic carbonate compound obtained in Reference Examples 1 to 3 and a solid content of 35% were obtained. N-methylpyrrolidone was added and dissolved uniformly. Next, a predetermined equivalent of the amine compound shown in Table 1 was added, and the mixture was stirred for 10 hours at a temperature of 90 ° C. until the amine compound could not be confirmed. Table 3 shows the properties of the obtained three types of polyhydroxypolyurethane resins and films made of the resins.

Comparative polymerization example 1 (polyester urethane resin)
A reaction vessel equipped with a stirrer, thermometer, gas inlet tube and reflux condenser was replaced with nitrogen, and 150 parts of polybutylene adipate having an average molecular weight of about 2,000 and 15 parts of 1,4-butanediol were mixed with 200 parts of methyl ethyl ketone. Dissolve in a mixed organic solvent consisting of 50 parts of dimethylformamide, slowly drop in 62 parts of hydrogenated MDI dissolved in 171 parts of dimethylformamide while stirring well at 60 ° C. The reaction was performed for 6 hours.
This solution had a viscosity of 3.2 MPa · s (25 ° C.) at a solid content of 35%. The film obtained from this solution had a breaking strength of 45 MPa, a breaking elongation of 480%, and a thermal softening temperature of 110 ° C.

Comparative polymerization example 2 (polycarbonate polyurethane resin)
As in Comparative Polymerization Example 1, 150 parts of polycarbonate diol (Ube Industries, Ltd.) having an average molecular weight of about 2,000 and 15 parts of 1,4-butanediol are composed of 200 parts of methyl ethyl ketone and 50 parts of dimethylformamide. It melt | dissolved in the mixed organic solvent, what melt | dissolved 62 parts hydrogenated MDI in 171 parts dimethylformamide was dripped gradually, stirring at 60 degreeC, and it was made to react at 80 degreeC after completion | finish of dripping. This solution has a solid content of 35% and a viscosity of 1.6 MPa · s (25 ° C.). The film obtained from this solution has a breaking strength of 21 MPa and a breaking elongation of 250%, and the thermal softening temperature is 135 ° C. Met.

Examples 1-6, Comparative Examples 1-4
Using the resins of Polymerization Examples 1 to 3 and Comparative Polymerization Examples 1 and 2, blended skin coating compositions shown in Table 2 were prepared and evaluated by the following methods.

  Corona discharge treatment, thermoplastic polyolefin base material sheet activated with a wetting index of 45 dyn / cm, and chlorinated polypropylene (Super Clone; manufactured by Nippon Paper Industries Co., Ltd.) as a primer layer on a 120 mesh gravure roll The coating was dried so that the thickness after drying was 3 μm and dried at 100 ° C. for 2 minutes. On this coating film, the coating material for the skin shown in Table 2 was applied with a 120 mesh gravure roll so that the thickness after drying was 5 μm, dried at 100 ° C. for 2 minutes, and aged at 80 ° C. for 24 hours. Molded by a convex vacuum forming machine having a surface temperature of 160 ° C.

(Formability)
The sheet surface after vacuum forming was visually observed and evaluated.
○: Good (no molding cracking or whitening phenomenon)
×: Defect (either molding cracking or whitening phenomenon is recognized)

(Gross value)
It is measured with a gloss meter according to JIS K5600, and a gloss value of 1.2 or less (standard value required by the industry) is accepted.

(Adhesiveness)
Evaluation was performed by performing a cellophane tape peeling test on the surface of the skin coating.
○: Good (no peeling part on the coated surface)
X: Defect (There is a peeling part on the coated surface)

(Abrasion resistance)
The surface of the skin coating was rubbed with nails, and whether or not scars or whitening occurred was evaluated by visual judgment.
○: Good (difficult to determine claw scratches / whitening on the coated surface)
×: Defect (Nail scratches and whitening marks on the coated surface can be clearly identified)

(Oil resistance)
Beef oil (Nacalai Tech Co., Ltd.) was applied in a circle with a radius of 2 cm on the surface of the epidermis, and was allowed to stand for 5 days in an 80 ° C atmosphere. did.
○: Good (no peeling part on the coated surface)
×: Defect (there is a peeled part on the coated surface)

(chemical resistance)
Ethanol was dropped on the surface of the skin coating film, and a solvent was added dropwise to keep the surface always wet, and wiped off after 1 hour.
○: No dripping traces are observed on the coated surface. Δ: Slight dropping traces are observed but not noticeable.

(Surface wear resistance)
Using a flat abrasion tester, No. 6 canvas was rubbed with a load of 1 kgf, and the number of times until a scratch was generated was measured.
○: 5,000 times or more Δ; 2,000 to less than 5,000 ×; less than 2,000 times

(Environmental compatibility)
A judgment was made as to whether or not carbon dioxide was immobilized.

  According to the present invention as described above, the top coat layer of the thermoplastic polyolefin resin sheet is molded using the composition comprising the polyhydroxy polyurethane resin, so that the scratch resistance, the wear resistance, the chemical resistance and the uniform are uniform. In addition to excellent matting effect, it has excellent performance such as excellent adhesion and flexibility due to strong interaction between the hydroxyl group of polyhydroxy polyurethane resin and the base sheet at the interface, and antistatic effect. Can do. Also, from the viewpoint of reducing greenhouse gases, by incorporating carbon dioxide into the resin, an environment-friendly thermoplastic polyolefin resin skin material that could not be achieved with conventional products is provided.

Claims (6)

A thermoplastic polyolefin resin sheet, and a top coat layer applied directly or through a primer layer to the thermoplastic polyolefin resin sheet,
The topcoat layer comprises a polyhydroxypolyurethane resin derived from the reaction of a 5-membered cyclic carbonate compound and an amine compound ;
The 5-membered cyclic carbonate compound, a thermoplastic polyolefin resin skin material and said compound der Rukoto obtained by reacting an epoxy compound and carbon dioxide. The thermoplastic polyolefin resin skin material according to claim 1, wherein the polyhydroxy polyurethane resin has a hydroxyl value of 25 to 300 mgKOH / g. The thermoplastic polyolefin resin skin material according to claim 1 or 2 , wherein the polyhydroxypolyurethane resin contains 1 to 25% by mass of carbon dioxide. The top coat layer, from the relative polyhydroxy polyurethane resin 100 parts by weight, a composition in which at least one fine powder selected from organic fine powder and inorganic fine powder were blended at a ratio of 1 to 150 parts by weight The thermoplastic polyolefin resin skin material according to any one of claims 1 to 3 . The thermoplastic polyolefin resin skin material according to any one of claims 1 to 4 , wherein the topcoat layer further contains another resin. The top coat layer, heat according to any one of the polyhydroxy polyurethane claim hydroxyl and the polyhydroxy polyurethane resin with a crosslinking agent which reacts in the resin is a crosslinked coating formed is crosslinked 1-5 Plastic polyolefin resin skin material.

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