JPH07179624A - Surfacing sheet and laminate prepared therefrom - Google Patents

Abstract

PURPOSE:To obtain a surfacing sheet having an improved scratch resistance by forming a noncross-linked thermoplastic elastomer compsn. contg. a specific crystalline poly-1-butene resin and an ethylene-alpha-olefin copolymer rubber in a specified wt. ratio. CONSTITUTION:A noncross-linked thermoplastic elastomer compsn. is prepd. by mixing 30-90 pts.wt. crystalline poly-1-butene resin having a crystallinity of 20-70% and a melt flow rate of 0.02-15g/10min, 10-70 pts.wt. ethylene-alpha-olefin copolymer rubber having an ethylene content of 55-85 mol % and a Mooney viscosity [ML1+4 (100 deg.C)] of 10-75, and if necessary 3-20 pts.wt. PP resin and 3-20 pts.wt. low-density PE resin. The compsn. is formed on a sheet-forming machine into a surfacing sheet with a thickness of 0.05-0.4mm and embossed to form a surface pattern. The sheet is then thermally bonded, through an adhesive olefin resin film, to a polyolefin foam produced from a polyolefin, a blowing agent, and an inorg. filler, thus giving a laminate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a skin sheet suitable for an automobile interior material and a carrying bag exterior material, and a laminate using the skin sheet.

[0002]

BACKGROUND OF THE INVENTION Conventionally, a soft polyvinyl chloride sheet has been mainly used as a skin sheet for an interior material for automobiles and an exterior material for carrying bags such as camera bags and attache cases. However, although a skin sheet made of soft polyvinyl chloride has excellent moldability and texture, it is difficult to incinerate because it generates hydrochloric acid during combustion, and difficult to recycle. An alternative to vinyl skin sheets is desired.

Therefore, as a substitute for the skin sheet made of soft polyvinyl chloride, the use of a polyolefin for the skin sheet used as an interior material for automobiles or an exterior material for a carrying bag has been studied. For example, as seen in Japanese Patent Laid-Open No. 62-257838, investigations are being made on olefinic thermoplastic elastomers. In this publication, a partially crosslinked thermoplastic elastomer consisting of a mixture of ethylene / α-olefin copolymer rubber, polypropylene resin, and polyethylene resin, a hindered amine type light stabilizer and a triazole type ultraviolet absorber are added. A skin sheet made of a blended thermoplastic elastomer composition is described.

However, the skin sheet made of the above-mentioned olefinic thermoplastic elastomer composition can effectively prevent the generation of cracks due to ultraviolet rays and the change in appearance such as discoloration, but the surface has scratch resistance. Also, there is a problem that the puncture resistance is not always sufficient. Further, it is difficult to form a thin skin sheet from the above olefin-based thermoplastic elastomer composition, and further, when a laminate using this skin sheet is subjected to further molding processing, wrinkles occur on the surface of the laminate. There is a problem that it is easy to do.

Therefore, the appearance of a thin skin sheet having excellent scratch resistance and puncture resistance on the surface and excellent cost performance, and further, having such a skin sheet, molding which does not cause wrinkles during molding. The appearance of a laminate having excellent properties has been conventionally desired.

[0006]

It is an object of the present invention to solve the problems associated with the prior art as described above, and to provide a thin skin sheet having excellent surface scratch resistance, puncture resistance and emboss transfer property. It is intended to be provided.

It is another object of the present invention to provide a laminate having excellent molding processability, which uses a skin sheet having the above effects as a skin layer.

[0008]

SUMMARY OF THE INVENTION A first skin sheet according to the present invention is
[I] Crystalline poly-1-butene resin: 30 to 90 parts by weight, and [II] Ethylene / α-olefin copolymer rubber: 10
~ 70 parts by weight (the total amount of components [I] and [II] is 100
(Part by weight) and a non-crosslinked thermoplastic elastomer composition.

The second skin sheet according to the present invention is
[I] Crystalline poly-1-butene resin: 30 to 90 parts by weight, and [II] Ethylene / α-olefin copolymer rubber: 10
To 70 parts by weight so that the total amount of the components [I] and [II] becomes 100 parts by weight, and further,
[III] Polypropylene resin: Characterized by being formed of a non-crosslinked thermoplastic elastomer composition containing 5 to 30 parts by weight.

Furthermore, the third skin sheet according to the present invention comprises [I] crystalline poly-1-butene resin: 30 to 90 parts by weight, and [II] ethylene / α-olefin copolymer rubber: 1
0 to 70 parts by weight so that the total amount of the components [I] and [II] is 100 parts by weight, and further, [III] polypropylene resin: 3 to 20 parts by weight,
[IV] Low-density polyethylene resin: It is characterized by being formed of a non-crosslinked thermoplastic elastomer composition containing 3 to 20 parts by weight.

The first laminate according to the present invention comprises [I] crystalline poly-1-butene resin: 30 to 90 parts by weight and [II] ethylene / α-olefin copolymer rubber: 10 to 70 parts by weight. (A total amount of components [I] and [II] is 100 parts by weight), and a skin sheet layer made of a non-crosslinked thermoplastic elastomer composition, and a polyolefin foam layer. It is characterized by becoming.

The second laminate according to the present invention is
[I] Crystalline poly-1-butene resin: 30 to 90 parts by weight, and [II] Ethylene / α-olefin copolymer rubber: 10
To 70 parts by weight so that the total amount of the components [I] and [II] becomes 100 parts by weight, and further,
[III] Polypropylene resin: It is characterized by being formed from a skin sheet layer made of a non-crosslinked thermoplastic elastomer composition containing 5 to 30 parts by weight, and a polyolefin foam layer.

Further, the third laminate according to the present invention is
[I] Crystalline poly-1-butene resin: 30 to 90 parts by weight, and [II] Ethylene / α-olefin copolymer rubber: 10
To 70 parts by weight so that the total amount of the components [I] and [II] becomes 100 parts by weight, and further,
[III] Polypropylene resin: 3 to 20 parts by weight, [I
V] Low-density polyethylene resin: characterized in that it is formed from a skin sheet layer made of a non-crosslinked thermoplastic elastomer composition containing 3 to 20 parts by weight and a polyolefin foam layer.

[0014]

DETAILED DESCRIPTION OF THE INVENTION The skin sheet having excellent moldability according to the present invention and the laminate using the skin sheet will be specifically described below.

The skin sheet according to the present invention comprises crystalline poly-1.
-A non-crosslinked thermoplastic elastomer composition containing butene resin [I] and ethylene / α-olefin copolymer rubber [II] in a specific ratio. The skin sheet according to the present invention is a crystalline poly-1-butene resin [I].
In addition to the ethylene / α-olefin copolymer rubber [II], a polypropylene resin [III] and a low-density polyethylene resin [IV] are contained in a specific amount to form a non-crosslinked thermoplastic elastomer composition. May be.

Crystalline poly-1-butene resin [I] Crystalline poly-1-butene resin [I] used in the present invention
Has a crystallinity of 20% or more, preferably 20 to 70%, particularly preferably 25 to 6 as measured by an X-ray diffraction method.
It is 0%. Specific examples of such crystalline poly-1-butene resin [I] include (1) melt flow rate (MFR; ASTM D 1238, 190 ° C., 2.1.
1-butene homopolymer having a 6 kg load) of 0.01 to 20 g / 10 min, preferably 0.02 to 15 g / 10 min, (2) melt flow rate (MFR; ASTM D
1238, 190 ℃, 2.16kg load) 0.01 ~
1-butene / ethylene copolymer having 20 g / 10 minutes, preferably 0.02 to 15 g / 10 minutes and an ethylene content of 0.5 to 15 mol%, preferably 1.0 to 13 mol%. , Or (3) Melt flow rate (MF
R; ASTM D 1238, 190 ° C., 2.16 kg load) is 0.01 to 20 g / 10 minutes, preferably 0.02
A 1-butene / α-olefin copolymer having an amount of ˜15 g / 10 minutes and an α-olefin content of 1.0 to 40 mol%, preferably 2.0 to 35 mol%, is preferred.

In the present invention, the crystalline poly-1-butene resin [I] is the total amount 1 of the crystalline poly-1-butene resin [I] and the ethylene / α-olefin copolymer rubber [II].
It is used in an amount of 30 to 90 parts by weight, preferably 35 to 85 parts by weight, more preferably 40 to 80 parts by weight, based on 00 parts by weight.

When the crystalline poly-1-butene resin [I] is used in the above proportion, it is possible to provide a skin sheet having excellent surface scratch resistance, puncture resistance and emboss transfer property. An elastomer composition is obtained.

Ethylene / α-olefin copolymer rubber [I
I] As the ethylene / α-olefin copolymer rubber [II] used in the present invention, specifically, ethylene / propylene copolymer rubber, ethylene / propylene / non-conjugated diene rubber, ethylene / 1-butene copolymer rubber, The ethylene / butadiene copolymer rubber has an ethylene content of 50 to 90 mol%, preferably 55 to 85 mol%, and a crystallinity measured by an X-ray diffraction method of less than 20%, preferably less than 10%. An elastic copolymer is mentioned.

Specific examples of the non-conjugated diene constituting the ethylene / propylene / non-conjugated diene rubber include dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene and ethylidene norbornene. The iodine value of the ethylene / propylene / non-conjugated diene rubber is 5 to 20, preferably 7 to
It is 15.

In addition, an oil-extended rubber prepared by blending 100 parts by weight of the above-mentioned ethylene / α-olefin copolymer rubber with a mineral oil-based softening agent in an amount of 50 parts by weight or less is used as an ethylene / α-olefin copolymer rubber [ II].

Mooney viscosity of ethylene / α-olefin copolymer rubber [II] when mixed with crystalline poly-1-butene resin [I] [Ethylene / α-olefin copolymer rubber with mineral oil softener blended II], the Mooney viscosity of the compound (oil extended rubber), JIS K 6300, ML _{1 + 4} (100 ° C)] is 8
It is 0 or less, preferably 10 to 75.

Among these, ethylene / propylene copolymer rubbers and ethylene / propylene / non-conjugated diene rubbers having the above Mooney viscosity are preferable, and particularly,
Ethylene / propylene / non-conjugated diene copolymer rubber is preferred. When the ethylene / propylene / non-conjugated diene copolymer rubber is used, a thermoplastic elastomer composition having excellent heat resistance, tensile properties and impact resilience can be obtained.

In the present invention, the ethylene / α-olefin copolymer rubber [II] is a crystalline poly-1-butene resin [I] and an ethylene / α-olefin copolymer rubber [I].
10 parts by weight, preferably 15 parts by weight to 65 parts by weight, more preferably 2 parts by weight, based on 100 parts by weight of the total amount of [I].
Used in an amount of 0 to 60 parts by weight.

Polypropylene Resin [III] The polypropylene resin [III] used in the present invention includes (1) melt flow rate (MFR:
(ASTM D 1238, 230 ° C, 2.16 kg load)
Is 0.1 to 20 g / 10 minutes, preferably 0.2 to 15 g
/ 10 min, melting point is 130 ° C. or higher, preferably 14
A homopolymer of propylene having a temperature of 0 ° C. or higher, particularly preferably 150 ° C. or higher, or (2) consisting of propylene and an α-olefin other than propylene, and having a content of the constitutional unit derived from the α-olefin of 30 mol. % Or less, preferably 25 mol% or less, particularly preferably 20 mol% or less, and the melt flow rate (MFR: ASTM
D 1238, 230 ℃, 2.16kg load) is 0.1
Propylene / α having a melting point of 130 ° C. or higher, preferably 140 ° C. or higher, particularly preferably 150 ° C. or higher.
-Examples include olefin copolymers.

Specific examples of the α-olefin include ethylene, 1-butene, 1-pentene, 1-hexene and 1-hexene.
Heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadodecene, 4-methyl-1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 3,3-dimethyl-1- Butene, diethyl-1-butene, trimethyl-1-butene, 3-methyl-1
Pentene, ethyl-1-pentene, propyl-1-pentene, dimethyl-1-pentene, methylethyl-1-pentene, diethyl-1-hexene, trimethyl-1-pentene,
3-methyl-1-hexene, dimethyl-1-hexene, 3,5,5-
Trimethyl-1-hexene, methylethyl-1-heptene,
Trimethyl-1-heptene, dimethyloctene, ethyl-1
-Octene, methyl-1-nonene, vinylcyclopentene, vinylcyclohexane, vinylnorbornane and the like.

The copolymer composed of propylene and these α-olefins may be a random copolymer or a block copolymer. Among these, propylene homopolymer or propylene
Ethylene copolymers are preferred.

The polypropylene resin [III] is the crystalline poly-1-butene resin [I] and ethylene / α-
It is used in an amount of 5 to 30 parts by weight, preferably 7 to 28 parts by weight, more preferably 10 to 25 parts by weight, based on 100 parts by weight of the total amount of the olefin copolymer rubber [II].

When the low-density polyethylene resin [IV] described below is used as one component of the thermoplastic elastomer composition for forming a skin sheet, the polypropylene resin [III] is the crystalline poly-1-butene resin. In an amount of 3 to 20 parts by weight, preferably 4 to 18 parts by weight, and more preferably 5 to 15 parts by weight, based on 100 parts by weight of the total amount of [I] and the ethylene / α-olefin copolymer rubber [II]. Used.

Low Density Polyethylene Resin [IV] The low density polyethylene resin [IV] used in the present invention is specifically ethylene and α having 3 to 20 carbon atoms.
-Olefin, and the content of the structural unit derived from this α-olefin is 30 mol% or less, preferably 2 to 25 mol%, particularly preferably 5 to 20 mol%
And the melt flow rate (MFR: ASTM D
1238, 190 ° C, 2.16kg load) is 0.1-1
5 g / 10 min, preferably 0.2 to 10 g / 10 min, and a density (D: ASTM D 1505) of 0.870 to.
0.920 g / cm ³ , preferably 0.880 to 0.9
Ethylene having a crystallinity of 15 g / cm ³ and a crystallinity of 25% or more, preferably 30% or more as measured by an X-ray diffraction method.
Examples include α-olefin copolymers.

Specific examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene,
1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadodecene, 4-methyl-1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 3,3-dimethyl- 1- butene,
Diethyl-1-butene, trimethyl-1-butene, 3-methyl
-1-pentene, ethyl-1-pentene, propyl-1-pentene, dimethyl-1-pentene, methylethyl-1-pentene, diethyl-1-hexene, trimethyl-1-pentene,
3-methyl-1-hexene, dimethyl-1-hexene, 3,5,5-
Trimethyl-1-hexene, methylethyl-1-heptene,
Trimethyl-1-heptene, dimethyloctene, ethyl-1
-Octene, methyl-1-nonene, vinylcyclopentene, vinylcyclohexane, vinylnorbornane and the like.

The low density polyethylene resin [IV], which is a copolymer of ethylene and these α-olefins, is
It may be a random copolymer or a block copolymer.

The low density polyethylene resin [IV] is the crystalline poly-1-butene resin [I] and ethylene / α.
-3 to 20 parts by weight, preferably 4 to 18 parts by weight, based on 100 parts by weight of the total amount of the olefin copolymer rubber [II],
More preferably, it is used in an amount of 5 to 15 parts by weight.

In the thermoplastic elastomer composition of the present invention, conventionally known additives such as a light resistance stabilizer, an ultraviolet absorber, a filler, a pigment, a colorant, an antioxidant, a processing aid and an antistatic agent are added. It can be appropriately blended within a range not impairing the object of the present invention.

The non-crosslinked thermoplastic elastomer composition used in the present invention is, for example, the above-mentioned crystalline poly-1-
Butene resin [I] and ethylene / α-olefin copolymer rubber [II], and further polypropylene resin [III],
It is obtained by melt-kneading the low-density polyethylene resin [IV] and the above-mentioned additives using a kneader such as an extruder or a Banbury mixer.

By molding the non-crosslinked thermoplastic elastomer composition obtained as described above into a sheet using a sheet molding machine, a skin sheet having a thickness of more than 0.4 mm can be obtained. And about 0.05 ~
A 0.4 mm thin skin sheet is obtained.

The skin sheet according to the present invention may have an embossed pattern formed on its surface. Since the skin sheet according to the present invention is formed of the above-mentioned non-crosslinked thermoplastic elastomer resin composition, it has excellent emboss transfer property and can provide a clear embossed pattern on the surface. The embossing method is not particularly limited, and a conventionally known embossing method can be adopted.

The surface of the skin sheet according to the present invention may be coated with a paint such as polyurethane resin paint, epoxy resin paint, acrylic resin paint or the like. Since the skin sheet according to the present invention is made of the above thermoplastic elastomer composition, it has excellent scratch resistance and puncture resistance.

Since the skin sheet according to the present invention has the above-mentioned excellent properties, it is suitable as a skin material used for automobile interior materials and carrying bag exterior materials. Laminated product The laminated product according to the present invention is composed of a layer (skin sheet layer) made of the above-mentioned skin sheet and a polyolefin foam layer.

Specific examples of the above-mentioned polyolefin include polyethylene, polypropylene and poly-1-butene. Specific examples of the foaming agent for forming the foam include azodicarbonamide (ADC).
A), N, N'-dinitrosopentamethylenetetramine, 4,
Organic blowing agents such as 4'-oxybis (benzenesulfonylhydrazide), diphenylsulfone-3,3'-disulfonylhydrazide, p-toluenesulfonylsemicarbazide, trihydrazinotriazine, sodium hydrogencarbonate, ammonium hydrogencarbonate, ammonium carbonate, etc. An inorganic foaming agent may be used. Among them, azodicarbonamide (ADCA), N, N'-dinitrosopentamethylenetetramine and trihydrazinotriazine are preferable as the organic foaming agent, and sodium hydrogen carbonate is preferable as the inorganic foaming agent.

The blowing agent as described above is a polyolefin,
It is usually used in an amount of 5 to 20 parts by weight, preferably 8 to 18 parts by weight, based on 100 parts by weight of the total amount of the foaming agent and the inorganic filler.

Further, an inorganic filler may be filled to the extent that the physical properties are not impaired. Specifically, glass fiber, calcium carbonate, calcium silicate, clay, kaolin, talc,
Silica, diatomaceous earth, mica powder, asbestos, alumina,
Examples thereof include barium sulfate, aluminum sulfate, calcium sulfate, basic magnesium carbonate, molybdenum disulfide, graphite, glass spheres and silas balloons. Of these, glass fiber and talc are preferable.

The above-mentioned inorganic filler is usually added in an amount of 1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the total amount of the polyolefin, the foaming agent and the inorganic filler. May be.

The polyolefin foam can be produced by heating and foaming a composition containing the above-mentioned polyolefin and a foaming agent by a conventionally known method. The laminate according to the present invention, for example, between the preformed skin sheet and the polyolefin foam, the olefin resin adhesive film is interposed, at a temperature equal to or higher than the melting temperature of the adhesive film, a skin sheet and It can be produced by heat-sealing a polyolefin foam, or can be directly attached at the time of forming a skin sheet.

[0045]

The skin sheet according to the present invention is made of crystalline poly
-1-A non-crosslinked thermoplastic elastomer composition containing a specific amount of butene resin [I] and ethylene / α-olefin copolymer rubber [II], or polypropylene resin [III] in addition to these components ] Furthermore, since it is formed from a non-crosslinked thermoplastic elastomer composition containing a specific amount of low-density polyethylene resin [IV], it is excellent in surface scratch resistance, puncture resistance and emboss transfer property, and has a thickness Can have a thickness of about 0.05 mm or more and 0.4 mm or less, and a thickness of more than 0.4 mm.

In addition, since the layered product of the above-mentioned skin sheet is formed on the polyolefin foam layer in the laminate according to the present invention, the surface is excellent in scratch resistance and puncture resistance, and further subjected to molding processing. Wrinkles do not occur on the surface even if it is performed, and it has excellent moldability.

The present invention will be described below with reference to examples.
The present invention is not limited to these examples. The crystalline poly-1-butene resin, ethylene / α-olefin copolymer rubber, polypropylene resin and low density polyethylene resin used in Examples and Comparative Examples are as follows.

[Crystalline poly-1-butene resin] 1) 1-butene homopolymer [hereinafter abbreviated as PB-1] MFR: 0.2 g / 10 minutes (ASTM D 1238, 1)
90 ° C, 2.16 kg load) Crystallinity: 55% (measured by X-ray diffraction method) 2) 1-butene / ethylene random copolymer [hereinafter, PB
Abbreviated as -2] ethylene content: 10 mol%, MFR: 0.5 g / 10 min (ASTM D 1238, 1
90 ° C., 2.16 kg load) Crystallinity: 27% (measured by X-ray diffraction method) 3) 1-butene / propylene random copolymer [hereinafter, P
Abbreviated as B-3] Propylene content: 25 mol% MFR: 1.0 g / 10 minutes (ASTM D 1238, 1
90 ° C, 2.16 kg load) Crystallinity: 30% (measured by X-ray diffraction method) [Ethylene / α-olefin copolymer rubber] 1) Ethylene / propylene / 5-ethylidene-2-norbornene terpolymer rubber [Oil-extended rubber, hereinafter abbreviated as EPT-1] Ethylene content: 78 mol% Iodine number: 13 Crystallinity: 0% (measured by X-ray diffraction method) Paraffin-based process oil content: Before blending with paraffin-based process oil 100 parts by weight of ethylene / propylene / 5-ethylidene-2-norbornene terpolymer rubber of 40 parts by weight Mooney viscosity [ML _{1 + 4} (100 ° C, JIS K 630
0)]: 75 2) Ethylene / propylene / 5-ethylidene-2-norbornene terpolymer rubber [hereinafter abbreviated as EPT-2] Ethylene content: 82 mol% Iodine value: 10 Crystallinity: 0% (X Mooney viscosity [ML _{1 + 4} (100 ° C, JIS K 630)
0)]: 15 3) Ethylene / propylene / 5-ethylidene-2-norbornene terpolymer rubber [hereinafter abbreviated as EPT-3] Ethylene content: 78 mol% Iodine value: 12 Crystallinity: 0% (X Mooney viscosity [ML _{1 + 4} (100 ° C, JIS K 630)
0)]: 90 [Polypropylene resin] 1) Propylene / ethylene random copolymer [hereinafter referred to as P
Abbreviated as P-1] Ethylene content: 4.0 mol% MFR: 1.0 g / 10 minutes (ASTM D 1238, 2
30 ° C., 2.16 kg load) Melting point: 139 ° C. 2) Propylene homocopolymer [hereinafter abbreviated as PP-2] MFR: 4.3 g / 10 minutes (ASTM D 1238, 2)
30 ° C., 2.16 kg load) Melting point: 164 ° C. 3) Propylene / ethylene block copolymer [hereinafter, P
Abbreviated as P-3] Ethylene content: 18 mol% MFR: 0.6 g / 10 minutes (ASTM D 1238, 2
30 ° C, 2.16 kg load) Melting point: 163 ° C [Low density polyethylene resin] 1) Ethylene / butene random copolymer [hereinafter referred to as LDP
Abbreviated as E] Ethylene content: 89 mol% MFR: 1.0 g / 10 minutes (ASTM D 1238, 1
90 ° C., 2.16 kg load) Density: 0.906 g / cm ³ (ASTM D 1505) Crystallinity: 33% (measured by X-ray diffraction method)

[0049]

Example 1 P as a crystalline poly-1-butene resin [I]
B-1, 20 parts by weight and PB-2, 40 parts by weight, and EPT as ethylene / α-olefin copolymer rubber [II]
-1, 40 parts by weight and furnace type carbon black [No. 30, manufactured by Mitsubishi Kasei Co., Ltd.] as a pigment.
3 parts by weight and Tinuvin 3 as a light stabilizer
26 [manufactured by Ciba Geigy] 0.5 parts by weight, 0.2 parts by weight of Irganox 1010 [manufactured by Ciba Geigy] as an antioxidant and Irganox 1076 [manufactured by Ciba Geigy] ] 0.2
The mixture containing 1 part by weight was melt-kneaded at 200 ° C. using a 65 mmφ uniaxial extruder to obtain a thermoplastic elastomer composition.

Then, the obtained thermoplastic elastomer composition was molded into a sheet having a thickness of 0.5 mm by a sheet molding machine, and the surface of the sheet was embossed by an embossing machine to obtain a skin sheet. The sheet molding machine is a 40 mmφ uniaxial extruder, and the sheet molding conditions are: die width 500 mm, lip opening 1.0 mm, cylinder temperature 220 ° C., die temperature 200 ° C., take-up speed 0.5 m / min. Met.

The obtained skin sheet was subjected to a tensile test,
A scratch resistance test and a puncture resistance test were conducted according to the following test methods. Further, the emboss transfer property was evaluated according to the following criteria. [Test Method] (a) The tensile test is performed according to ASTM D638, yield stress (YS), tensile breaking strength (TS), elongation at break (EL), tensile modulus (E), 50%. modulus (M _50), it was determined 100% modulus (M ₁₀₀₎ and modulus ratio [M ₁₀₀ / M _50]. (b) The scratch resistance test was conducted using a Tohoku Seiki Co., Ltd. academic vibration type abrasion tester with a load of 500 g (33 g / cm ² ), a friction count of 200 times, a stroke of 200 mm, and a speed of 30 times / min. The body was made as a cotton cloth (Kanakin No. 3).

The scratch resistance was evaluated according to the following 5 grades. 1 ・ ・ ・ ・ Clearly worn 2 ・ ・ ・ ・ ・ ・ ・ ・ Scratched greatly 3 ・ ・ ・ ・ Clearly scratched 4 ・ ・ ・ ・ Slightly scratched 5 ・ ・ ・・ ・ ・ Slightly changed in gloss (c) For the puncture resistance test, use a universal testing machine manufactured by Instron, fix the skin sheet to a jig with a diameter of 5 cm, and have a flat tip with a diameter of 0.7 mm. The maximum stress when the needle was pierced at a speed of 50 mm / min was determined and defined as the puncture strength. (d) The emboss transfer property was evaluated according to the following three grades.

5 ... ・ Transfers fine patterns clearly and is very good. 4 ・ ・ Good, but fine patterns are slightly unclear. 3 ... Fine The results are shown in Table 1 in which the pattern is unclear and the transferability is slightly inferior. Further, when producing the sheet under the above conditions, the take-up speed was gradually increased to make the sheet thin. The thickness of the sheet formed at the upper limit of the take-up speed at which the sheet can be stably produced was defined as the lower limit sheet thickness.

[0054]

Examples 2 and 3 and Comparative Examples 1 and 2 PB-1, P
B-2, PB-3, EPT-1, EPT-2, EPT-
A skin sheet was obtained in the same manner as in Example 1 except that 3 and PP-1 were mixed in the ratio shown in Table 1.

The obtained skin sheet was subjected to a tensile test,
The scratch resistance test and the puncture resistance test were conducted according to the above-mentioned test methods. In addition, the emboss transfer property and the lower limit sheet thickness were evaluated.

The results are shown in Table 1.

[0057]

Comparative Example 3 As a crystalline poly-1-butene resin [I],
PB-1, 20 parts by weight and PB-2, 40 parts by weight,
EP as ethylene / α-olefin copolymer rubber [II]
40 parts by weight of T-1 were melt-kneaded at 230 ° C. in the presence of 0.5 parts by weight of 1,3-bis (tert-butylperoxyisopropyl) benzene and 1 part by weight of divinylbenzene to partially crosslink. A thermoplastic elastomer composition was obtained.

Next, 0.3 part by weight of a furnace type carbon black [manufactured by Mitsubishi Kasei Kogyo KK, No. 30] was added to this thermoplastic elastomer composition as a pigment, and Tinuvin 326 [Ciba Geigy] as a light resistance stabilizer. Co., Ltd.] 0.5 part by weight, and Irganox 1010 [Ciba Geigy Co., Ltd.] as an antioxidant.
0.2 parts by weight and Irganox 1
076 [manufactured by Ciba-Geigy Co., Ltd.] was blended, and the resulting mixture was melt-kneaded at 200 ° C. using a 65 mmφ uniaxial extruder.

Next, a skin sheet was obtained from the thus obtained thermoplastic elastomer composition in the same manner as in Example 1. The obtained skin sheet was subjected to a tensile test, a scratch resistance test, and a puncture resistance test according to the above-mentioned test methods. In addition, the emboss transfer property and the lower limit sheet thickness were evaluated.

The results are shown in Table 1.

[0061]

[Table 1]

[0062]

[Example 4] An embossing sheet (skin sheet) having the same resin composition as in Example 1 and a thickness of 0.5 mm was formed by using a molding machine equipped with an embossing roll so that embossing can be performed simultaneously with sheet formation. At the time of molding, a polypropylene foam sheet having a foaming ratio of 15 times and a thickness of 3 mm was attached to obtain a laminate.

The molding machine is a 120 mmφ uniaxial extruder, and the sheet molding conditions are: die width 1400 mm, lip opening 1.0 mm, cylinder temperature 220 ° C., die temperature 20.
It was 0 ° C. and the take-up speed was 3 m / min.

The obtained laminate was subjected to a scratch resistance test, a puncture resistance test and a molding workability test. In addition, the emboss transfer property was evaluated. The molding workability test was performed by Ikegai Tekko KK's stamping mold system (65 mmφ vented twin-screw extruder, maximum injection amount in casting unit 3600 liters / shot, maximum pressing force 800 tons in forming press).
Was used under the following conditions.

The above twin-screw extruder was filled with 20% by weight of talc and had an MFR of 45 g / 10 minutes (ASTM D 12
Polypropylene block copolymer (aggregate) of 38,230 ° C. and 2.16 kg load) was melted at 210 ° C. and extruded by a predetermined amount onto a lower mold, and the laminated body obtained as described above was placed thereon. Then, the upper mold was lowered, and pressure of 50 kg / cm ² was applied for 20 seconds. The above mold had an automobile door trim shape, the lower mold was 50 ° C., and the upper mold was room temperature. After that, the upper and lower molds were opened and the surface of the laminate was visually observed to evaluate the moldability.

The moldability was evaluated according to the following three grades. ○ ・ ・ ・ ・ Wrinkle does not occur at the corner △ ・ ・ ・ ・ ・ ・ Slight wrinkle occurs at the corner × ・ ・ ・ ・ ・ ・ Clear wrinkle occurs at the corner Table 2 shows the results. .

[0067]

Example 5 Except that the same resin composition as in Example 2 was used,
A laminated body was obtained in the same manner as in Example 4.

The obtained laminate was subjected to a scratch resistance test, a puncture resistance test and a molding workability test. In addition, the emboss transfer property was evaluated. The results are shown in Table 2.

[0069]

Example 6 Except that the same resin composition as in Example 3 was used.
A laminated body was obtained in the same manner as in Example 4.

The obtained laminate was subjected to a scratch resistance test, a puncture resistance test and a molding workability test. In addition, the emboss transfer property was evaluated. The results are shown in Table 2.

[0071]

Comparative Example 4 A laminate was obtained with the same resin composition as in Comparative Example 1 and in the same manner as in Example 4. Regarding the obtained laminate,
A scratch resistance test, a puncture resistance test and a molding workability test were performed. In addition, the emboss transfer property was evaluated.

The results are shown in Table 2.

[0073]

[Comparative Example 5] A laminate was obtained with the same resin composition as in Comparative Example 2 and in the same manner as in Example 4. Regarding the obtained laminate,
A scratch resistance test, a puncture resistance test and a molding workability test were performed. In addition, the emboss transfer property was evaluated.

The results are shown in Table 2.

[0075]

Comparative Example 6 A laminate was obtained with the same resin composition as in Comparative Example 3 and in the same manner as in Example 4. Regarding the obtained laminate,
A scratch resistance test, a puncture resistance test and a molding workability test were performed. In addition, the emboss transfer property was evaluated.

The results are shown in Table 2.

[0077]

[Table 2]

[0078]

Examples 7, 8, 9 and Comparative Examples 7, 8 PB-
1, PB-2, EPT-1, EPT-3, PP-2, P
A thermoplastic elastomer composition was prepared in the same manner as in Example 1 except that P-3 and LDPE were mixed in the proportions shown in Table 3. Hereinafter, a laminate was obtained from this thermoplastic elastomer composition in the same manner as in Example 4.

When the sheet was produced under the above conditions, the take-up speed was gradually increased to make the skin sheet thin. The thickness of the skin sheet formed at the upper limit of the take-up speed at which the laminate can be stably produced was defined as the lower limit sheet thickness.

The obtained laminate was subjected to a scratch resistance test, a puncture resistance test and a molding workability test. In addition, the emboss transfer property was evaluated. The molding workability test was carried out by Fuse Vacuum Co., Ltd., vacuum pressure molding machine (molding area 1100 × 1500 mm, final mold clamping capacity 60 Ton,
Using a vacuum pump exhaust rate of 1.50 m ³ / min), the following conditions were used.

The laminate was set at a predetermined position, preheated until the surface of the skin sheet reached 130 ° C., and then the mold was pushed up to a predetermined position for vacuum forming. The mold has an automobile instrumental panel shape. After molding, the surface of the laminate was visually observed to evaluate the moldability.

Molding workability was evaluated according to the following three grades. A. Embossing Deformability ○ ・ ・ ・ ・ ・ ・ Embossing is hardly deformed △ ・ ・ ・ ・ ・ ・ Embossing is slightly deformed × ・ ・ ・ ・ ・ ・ Embossing is largely deformed and gloss is generated B ． Corner deformability ○ ・ ・ ・ ・ ・ ・ Corner deformation is uniform and no breakage occurs △ ・ ・ ・ ・ ・ ・ Corner is greatly stretched and a thin film is formed just before the breakage × ・ ・--- Table 3 shows the results of tearing at the corners.

[0083]

[Comparative Example 9] As a crystalline poly-1-butene resin [I],
PB-1, 20 parts by weight and PB-2, 30 parts by weight,
EP as ethylene / α-olefin copolymer rubber [II]
T-3, 35 parts by weight, polypropylene resin [III], PP-3, 15 parts by weight, 1,3-bis (tert-butylperoxyisopropyl) benzene 0.5 part by weight and divinylbenzene 1 part by weight In the presence thereof, melt kneading was carried out at 230 ° C. to obtain a partially crosslinked thermoplastic elastomer composition.

Next, 0.3 part by weight of a furnace type carbon black [manufactured by Mitsubishi Kasei Kogyo KK, No. 30] was added to the thermoplastic elastomer composition as a pigment, and Tinuvin 326 [Ciba Geigy] as a light resistance stabilizer. Co., Ltd.] 0.5 part by weight, and Irganox 1010 [Ciba Geigy Co., Ltd.] as an antioxidant.
0.2 parts by weight and Irganox 1
076 [manufactured by Ciba-Geigy Co., Ltd.] was blended, and the resulting mixture was melt-kneaded at 200 ° C. using a 65 mmφ uniaxial extruder.

Then, a laminate was prepared from the thus obtained thermoplastic elastomer composition in the same manner as in Example 4. The obtained laminate was evaluated in the same manner as in Example 7.

Further, 50 parts by weight of a mixture obtained by blending the above-mentioned partially crosslinked thermoplastic elastomer composition with a pigment, a light stabilizer and an antioxidant, and a crystalline poly-1-butene resin. As [I], 20 parts by weight of PB-1 and 30 parts by weight of PB-2 were melt-kneaded at 200 ° C. using a 65 mmφ uniaxial extruder.

Then, a laminate was vacuum-formed from the thus obtained thermoplastic elastomer composition in the same manner as in Example 7. The evaluation results are shown in Table 3.

[0088]

[Table 3]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C08L 23/12 LCF 23/16 LCY 23/20 LCZ

Claims (14)

[Claims] 1. A crystalline poly-1-butene resin [I]: 30-
Non-crosslinking containing 90 parts by weight and [II] ethylene / α-olefin copolymer rubber: 10 to 70 parts by weight (the total amount of the components [I] and [II] is 100 parts by weight) 1. A skin sheet formed of the thermoplastic elastomer composition of. 2. [I] crystalline poly-1-butene resin: 30-
Non-crosslinking containing 90 parts by weight and [II] ethylene / α-olefin copolymer rubber: 10 to 70 parts by weight (the total amount of the components [I] and [II] is 100 parts by weight) Of the thermoplastic elastomer composition, the crystalline poly-1-butene resin [I] has a crystallinity of 20.
~ 70%, melt flow rate 0.02-15g / 1
It is 0 minutes, and the ethylene / α-olefin copolymer rubber [II] has an ethylene content of 55 to 85 mol% and a Mooney viscosity [ML].
_{1 + 4} (100 ° C.)] is 10 to 75, The skin sheet according to claim 1, wherein 3. [I] Crystalline poly-1-butene resin: 30-
90 parts by weight and [II] ethylene / α-olefin copolymer rubber: 10 to 70 parts by weight are used as components [I] and [II].
And a total of 100 parts by weight of [III] polypropylene resin: 5 to 30 parts by weight of a non-crosslinked thermoplastic elastomer composition. A skin sheet to be used. 4. [I] crystalline poly-1-butene resin: 30-
90 parts by weight and [II] ethylene / α-olefin copolymer rubber: 10 to 70 parts by weight are used as components [I] and [II].
In an amount of 100 parts by weight, and further, [III] polypropylene resin: 5 to 30 parts by weight of a non-crosslinked thermoplastic elastomer composition. Poly-1-butene resin [I] has a crystallinity of 20.
~ 70%, melt flow rate 0.02-15g / 1
The ethylene / α-olefin copolymer rubber [II] has an ethylene content of 55 to 85 mol% and a Mooney viscosity [ML].
_{1 + 4} (100 ° C.)] is 10 to 75, and the polypropylene resin [III] has a melt flow rate of 0.2 to 15 g / 10 minutes and a melting point of 150 ° C. or higher. The skin sheet according to claim 3. 5. [I] Crystalline poly-1-butene resin: 30 to
90 parts by weight and [II] ethylene / α-olefin copolymer rubber: 10 to 70 parts by weight are used as components [I] and [II].
In a total amount of 100 parts by weight, and further contains [III] polypropylene resin: 3 to 20 parts by weight and [IV] low density polyethylene resin: 3 to 20 parts by weight. A skin sheet formed of a crosslinked thermoplastic elastomer composition. 6. [I] Crystalline poly-1-butene resin: 30 to
90 parts by weight and [II] ethylene / α-olefin copolymer rubber: 10 to 70 parts by weight are used as components [I] and [II].
In a total amount of 100 parts by weight, and further contains [III] polypropylene resin: 3 to 20 parts by weight and [IV] low density polyethylene resin: 3 to 20 parts by weight. The crystalline poly-1-butene resin [I] is made of a crosslinked thermoplastic elastomer composition and has a crystallinity of 20.
~ 70%, melt flow rate 0.02-15g / 1
The ethylene / α-olefin copolymer rubber [II] has an ethylene content of 55 to 85 mol% and a Mooney viscosity [ML].
_{1 + 4} (100 ° C.)] is 10 to 75, the polypropylene resin [III] has a melt flow rate of 0.2 to 15 g / 10 minutes, a melting point of 150 ° C. or higher, and the low density polyethylene. The resin [IV] is composed of ethylene and an α-olefin having 3 to 20 carbon atoms, the content of the constituent unit derived from this α-olefin is 5 to 20 mol%, and the melt flow rate is 0. 2-10g / 10min, density 0.880-0.91
Epidermal sheet according to claim 5, characterized in that a 5 g / cm ^3. 7. The skin sheet according to claim 1, wherein the surface is embossed. 8. [I] Crystalline poly-1-butene resin: 30-
Non-crosslinking containing 90 parts by weight and [II] ethylene / α-olefin copolymer rubber: 10 to 70 parts by weight (the total amount of the components [I] and [II] is 100 parts by weight) A laminate comprising a skin sheet layer made of the thermoplastic elastomer composition and a polyolefin foam layer. 9. [I] Crystalline poly-1-butene resin: 30-
Non-crosslinking containing 90 parts by weight and [II] ethylene / α-olefin copolymer rubber: 10 to 70 parts by weight (the total amount of the components [I] and [II] is 100 parts by weight) Of a thermoplastic elastomer composition and a polyolefin foam layer, and the crystalline poly-1-butene resin [I] has a crystallinity of 20.
~ 70%, melt flow rate 0.02-15g / 1
It is 0 minutes, and the ethylene / α-olefin copolymer rubber [II] has an ethylene content of 55 to 85 mol% and a Mooney viscosity [ML].
_{1 + 4} (100 ° C.)] is 10 to 75, The laminated body according to claim 8. 10. [I] crystalline poly-1-butene resin: 30
To 90 parts by weight and [II] ethylene / α-olefin copolymer rubber: 10 to 70 parts by weight, components [I] and [I
[I] is added so that the total amount is 100 parts by weight, and further, [III] polypropylene resin: 5 to 30
A laminate comprising a skin sheet layer made of a non-crosslinked thermoplastic elastomer composition containing 1 part by weight and a polyolefin foam layer. 11. [I] Crystalline poly-1-butene resin: 30
To 90 parts by weight and [II] ethylene / α-olefin copolymer rubber: 10 to 70 parts by weight, components [I] and [I
[I] is added so that the total amount is 100 parts by weight, and further, [III] polypropylene resin: 5 to 30
The crystalline poly-1-butene resin [I] is composed of a skin sheet layer made of a non-crosslinked thermoplastic elastomer composition containing 1 part by weight and a polyolefin foam layer. Is 20
~ 70%, melt flow rate 0.02-15g / 1
The ethylene / α-olefin copolymer rubber [II] has an ethylene content of 55 to 85 mol% and a Mooney viscosity [ML].
_{1 + 4} (100 ° C.)] is 10 to 75, and the polypropylene resin [III] has a melt flow rate of 0.2 to 15 g / 10 minutes and a melting point of 150 ° C. or higher. The laminated body according to claim 10. 12. [I] Crystalline poly-1-butene resin: 30
To 90 parts by weight and [II] ethylene / α-olefin copolymer rubber: 10 to 70 parts by weight, components [I] and [I
[I] is added so that the total amount is 100 parts by weight, and further, [III] polypropylene resin: 3 to 20
Parts of the non-crosslinked thermoplastic elastomer composition containing 3 parts by weight to [IV] low density polyethylene resin: 3 to 20 parts by weight, and a polyolefin foam layer. Characteristic laminate. 13. [I] Crystalline poly-1-butene resin: 30
To 90 parts by weight and [II] ethylene / α-olefin copolymer rubber: 10 to 70 parts by weight, components [I] and [I
[I] is added so that the total amount is 100 parts by weight, and further, [III] polypropylene resin: 3 to 20
1 part by weight and [IV] low-density polyethylene resin: 3 to 20 parts by weight, and a skin sheet layer made of a non-crosslinked thermoplastic elastomer composition, and a polyolefin foam layer. The crystalline poly-1-butene resin [I] has a crystallinity of 20.
~ 70%, melt flow rate 0.02-15g / 1
The ethylene / α-olefin copolymer rubber [II] has an ethylene content of 55 to 85 mol% and a Mooney viscosity [ML].
_{1 + 4} (100 ° C.)] is 10 to 75, the polypropylene resin [III] has a melt flow rate of 0.2 to 15 g / 10 minutes, a melting point of 150 ° C. or higher, and the low density polyethylene. The resin [IV] is composed of ethylene and an α-olefin having 3 to 20 carbon atoms, the content of the constituent unit derived from this α-olefin is 5 to 20 mol%, and the melt flow rate is 0. 2-10g / 10min, density 0.880-0.91
It is 5 g / cm < ³ >, The laminated body of Claim 12 characterized by the above-mentioned. 14. The laminate according to any one of claims 8 to 13, wherein the surface of the skin sheet layer is embossed.