JPH06287377A - Thermoplastic poly-1-butene elastomer composition, skinning sheet and laminate skinned therewith - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in scratch resistance, sticking resistance and emboss transfer by mixing a poly-1-butene resin with a specified thermoplastic poly-1-butene elastomer. CONSTITUTION:100 pts.wt. mixture of 30-90 pts.wt. ethylene/alpha-olefin copolymer rubber of an ethylene content of 50-90mol% with 70-10 pts.wt. poly-1-butene resin of an alpha-olefin content of 40mol% is dynamically heat-treated at 150-280 deg.C for 1-20min at a shear rate of 10-10sec<-1> in the presence of 0.05-3wt.% organic peroxide to obtain a partially crosslinked thermoplastic poly-1-butene elastomer. 100 pts.wt. total of 30-90 pts.wt. poly-1-butene resin having a melt flow rate of 0.01-20g/10min (ASTM D-1238, at 190 deg.C under a load of 2.16kg) and 70-10 pts.wt. above obtained elastomer is melt-kneaded to obtain the composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a composition capable of providing a skin sheet suitable for interior materials for automobiles and exterior materials for carrying bags, the skin sheet 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. And puncture resistance is not always sufficient, and
When a laminate using this skin sheet is subjected to further forming processing, there is a problem that wrinkles easily occur on the surface of the laminate.

Therefore, the advent of a composition and a skin sheet capable of providing a skin sheet excellent in scratch resistance and puncture resistance of the surface, and further, having such a skin sheet, wrinkles are generated during the molding process. The emergence of a laminate excellent in moldability that does not occur has been conventionally desired.

[0006]

An object of the present invention is to solve the problems associated with the prior art as described above, and to provide a skin sheet having excellent surface scratch resistance, puncture resistance and emboss transfer property. It is an object to provide a composition that can be used and this skin sheet.

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 The first poly-1-butene thermoplastic elastomer composition according to the present invention comprises [I] poly-1-butene resin: 30 to 90 parts by weight, and [II] poly-1-butene. -Based thermoplastic elastomer: 10 to 70 parts by weight (component [I]
And the total amount of [II] is 100 parts by weight),
The poly-1-butene thermoplastic elastomer [II] is an ethylene / α-olefin copolymer rubber (a): 30 to 90.
And a poly-1-butene resin (b): 10 to 70 parts by weight (the total amount of components (a) and (b) is 100 parts by weight) in the presence of an organic peroxide. It is characterized in that it is a partially crosslinked thermoplastic elastomer obtained by dynamically heat treating.

The second poly-1-butene-based thermoplastic elastomer composition according to the present invention is [I] poly-1-butene resin: 30 to 90 parts by weight, and [II] poly-1-butene. Thermoplastic elastomer: 10 to 70 parts by weight (the total amount of the components [I] and [II] is 100 parts by weight), and the poly-1-butene thermoplastic elastomer [II]
Is an ethylene / α-olefin copolymer rubber (a): 30
To 90 parts by weight and poly-1-butene resin (b): 5 to 50
Parts by weight and polyethylene resin (c): 5 to 25 parts by weight (the total amount of components (a), (b) and (c) is 100
(Parts by weight) and is a partially crosslinked thermoplastic elastomer obtained by dynamic heat treatment in the presence of an organic peroxide.

The first skin sheet according to the present invention is [I]
Poly-1-butene resin: 30 to 90 parts by weight, and [II]
Poly-1-butene thermoplastic elastomer: 10 to 70 parts by weight (the total amount of components [I] and [II] is 100 parts by weight), and the poly-1-butene thermoplastic elastomer [II ], Ethylene-α-olefin copolymer rubber (a): 30 to 90 parts by weight, poly-1-butene resin (b): 10 to 70 parts by weight (the total amount of components (a) and (b) is , 100 parts by weight), and is a partially crosslinked thermoplastic elastomer obtained by a dynamic heat treatment in the presence of an organic peroxide.

The second skin sheet according to the present invention is
[I] poly-1-butene resin: 30 to 90 parts by weight, and [II] poly-1-butene thermoplastic elastomer: 10
70 parts by weight (the total amount of the components [I] and [II] is 100 parts by weight), and the poly-1-butene thermoplastic elastomer [II] is an ethylene / α-olefin copolymer rubber ( a): 30 to 90 parts by weight, poly-1-butene resin (b): 5 to 50 parts by weight, polyethylene resin (c):
5 to 25 parts by weight (the total amount of components (a), (b) and (c) is 100 parts by weight) was obtained by dynamically heat treating in the presence of an organic peroxide. It is characterized by being a partially crosslinked thermoplastic elastomer.

The first laminate according to the present invention is [I] poly.
-1-Butene resin: 30 to 90 parts by weight, and [II] poly
-1-Butene thermoplastic elastomer: formed from a skin sheet layer comprising 10 to 70 parts by weight (the total amount of components [I] and [II] is 100 parts by weight) and a polyolefin foam layer The poly-1-butene thermoplastic elastomer [II] comprises ethylene / α-olefin copolymer rubber (a): 30 to 90 parts by weight and poly-1-butene resin (b): 10 to 70 parts by weight. Partly crosslinked thermoplastic elastomer obtained by dynamically heat treating a mixture consisting of parts (the total amount of components (a) and (b) is 100 parts by weight) in the presence of an organic peroxide. It is characterized by being.

The second laminate according to the present invention is
[I] poly-1-butene resin: 30 to 90 parts by weight, and [II] poly-1-butene thermoplastic elastomer: 10
70 parts by weight (the total amount of components [I] and [II] is 100 parts by weight) and a polyolefin foam layer, and the poly-1-butene thermoplastic resin The elastomer [II] comprises ethylene / α-olefin copolymer rubber (a): 30 to 90 parts by weight, poly-1-butene resin (b): 5 to 50 parts by weight, and polyethylene resin (c): 5 to 25 parts by weight (the total amount of components (a), (b) and (c) is 100 parts by weight), and a partial heat treatment was carried out in the presence of an organic peroxide. It is characterized by being a cross-linked thermoplastic elastomer.

[0014]

DETAILED DESCRIPTION OF THE INVENTION The poly-1-butene-based thermoplastic elastomer composition according to the present invention, a skin sheet, and a laminate using the skin sheet will be specifically described below.

The poly-1-butene thermoplastic elastomer composition according to the present invention comprises a poly-1-butene resin [I] and a specific poly-1-butene thermoplastic elastomer [II] in a specific ratio. It contains. The skin sheet according to the present invention is formed from this poly-1-butene thermoplastic elastomer composition.

Poly-1-butene Resin [I] The poly-1-butene resin [I] used in the present invention is specifically (1) a melt flow rate (MFR;
(ASTM D 1238, 190 ° C, 2.16 kg load)
Is 0.01 to 20 g / 10 minutes, preferably 0.02 to 1
5 g / 10 min 1-butene homopolymer, (2) melt flow rate (MFR; ASTM D 1238, 19
0.01 to 20 g / 10 at 0 ° C and 2.16 kg load)
Min, preferably 0.02 to 15 g / 10 min and an ethylene content of 0.5 to 15 mol%, preferably 1.0 to 13 mol%, or ( 3) Melt flow rate (MFR; AS
TM D 1238, 190 ° C., 2.16 kg load) is 0.01 to 20 g / 10 minutes, preferably 0.02 to 15
g / 10 min and α-olefin content of 1.0
~ 40 mol%, preferably 2.0-35 mol% 1-
Butene / α-olefin copolymer is preferred.

In the present invention, the poly-1-butene resin [I] is based on 100 parts by weight of the total amount of the poly-1-butene resin [I] and the poly-1-butene thermoplastic elastomer [II]. , 30 to 90 parts by weight, preferably 35 to 85
It is used in an amount of parts by weight, more preferably 40 to 80 parts by weight.

A poly-1-butene thermoplastic elastomer [I] containing the poly-1-butene resin [I] in the above-mentioned amount.
The composition with I] can provide a skin sheet having excellent surface scratch resistance, puncture resistance, and emboss transfer resistance.

Poly-1-butene thermoplastic elastomer
[II] The poly-1-butene thermoplastic elastomer [II] used in the present invention comprises (1) an ethylene / α-olefin copolymer rubber (a) and a poly-1-butene resin (b). A partially crosslinked thermoplastic elastomer obtained by dynamically heat treating the mixture containing the above in a proportion of (2) ethylene / α-olefin copolymer rubber (a) , A poly-1-butene resin (b) and a polyethylene resin (c) in a specific ratio were subjected to a dynamic heat treatment in the presence of an organic peroxide and partially crosslinked. It is a thermoplastic elastomer.

In the present invention, the polyethylene resin (c) is contained in order to improve the puncture resistance.
The thermoplastic elastomer (2) is preferably used. As the ethylene / α-olefin copolymer rubber (a) used in the present invention, specifically, ethylene / propylene copolymer rubber, ethylene / propylene / non-conjugated diene rubber,
The ethylene content of ethylene / 1-butene copolymer rubber, ethylene / butadiene copolymer rubber, etc. is 50 to 90 mol%,
It is preferably 55 to 85 mol% of an amorphous random elastic copolymer. Among these, ethylene / propylene copolymer rubber and ethylene / propylene / non-conjugated diene rubber are preferable, and ethylene / propylene / non-conjugated diene copolymer rubber is particularly preferable. Ethylene propylene
When the non-conjugated diene copolymer rubber is used, an olefinic thermoplastic elastomer excellent in heat resistance, tensile properties and impact resilience can be obtained. Specific examples of the non-conjugated diene include dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene and ethylidene norbornene.

The poly-1-butene resin (b) used in the present invention is specifically a homopolymer of 1-butene,
Or a 1-butene / α-olefin copolymer comprising 1-butene and an α-olefin other than 1-butene and containing a constituent unit derived from the α-olefin in an amount of 40 mol% or less Is mentioned.

Specific examples of such α-olefins include ethylene, propylene, 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, etc. .

The copolymer of 1-butene and these olefins may be a random copolymer or a block copolymer. Among these, 1-butene homopolymer, 1-butene / ethylene copolymer or 1-butene / propylene copolymer is preferable.

The polyethylene resin (c) used in the present invention is specifically a homopolymer of ethylene,
Alternatively, the crystallinity measured by X-ray analysis is 20% or more, which is composed of ethylene and an α-olefin other than ethylene, and contains a structural unit derived from the α-olefin in an amount of 15 mol% or less, Preferably, 30% or more of ethylene / α-olefin copolymer and the like are mentioned.

Specific examples of such α-olefins 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, etc. To be

The copolymer of ethylene and these α-olefins may be a random copolymer or a block copolymer. The thermoplastic elastomer used in the present invention is an ethylene / α-olefin copolymer rubber (a).
And the poly-1-butene resin (b), the ethylene / α-olefin copolymer rubber (a) includes the ethylene / α-olefin copolymer rubber (a) and the poly-1-butene resin (a). It is used in an amount of 30 to 90 parts by weight, preferably 35 to 85 parts by weight, based on 100 parts by weight of the total amount of b), and the poly-1-butene resin (b) is an ethylene / α-olefin copolymer rubber. It is used in an amount of 10 to 70 parts by weight, preferably 15 to 65 parts by weight, based on 100 parts by weight of the total amount of (a) and the poly-1-butene resin (b).

The thermoplastic elastomer used in the present invention is ethylene / α-olefin copolymer rubber (a).
And a poly-1-butene resin (b) and a polyethylene resin (c), the ethylene / α-olefin copolymer rubber (a) is an ethylene / α-olefin copolymer rubber (a), 30 to 30 parts by weight based on 100 parts by weight of the total amount of the poly-1-butene resin (b) and the polyethylene resin (c).
It is used in an amount of 90 parts by weight, preferably 35 to 85 parts by weight, and the poly-1-butene resin (b) is an ethylene / α-olefin copolymer rubber (a), a poly-1-butene resin (b) and It is used in an amount of 5 to 50 parts by weight, preferably 8 to 45 parts by weight, based on 100 parts by weight of the total amount of the polyethylene resin (c). The polyethylene resin (c) is the total amount of the ethylene / α-olefin copolymer rubber (a), the poly-1-butene resin (b) and the polyethylene resin (c) 1
5 to 25 parts by weight, preferably 7 to 100 parts by weight
Used in an amount of 20 parts by weight.

In the present invention, the poly-1-butene thermoplastic elastomer [II] is the above ethylene / α-olefin copolymer rubber (a) and poly-1-butene resin (b), or the above ethylene. In addition to the α-olefin copolymer rubber (a), the poly-1-butene resin (b) and the polyethylene resin (c), a conventionally known mineral oil softener,
A light resistance stabilizer, an ultraviolet absorber, a filler, a pigment, a colorant, an antioxidant, a processing aid, and an antistatic agent can be appropriately added within a range that does not impair the object of the present invention.

The poly-1-butene-based thermoplastic elastomer as described above can be obtained, for example, by dynamically heat-treating a blend of the above-mentioned components in the presence of an organic peroxide to partially cross-link it. it can.

Dynamic heat treatment means kneading in a molten state. The organic peroxide used in producing the thermoplastic elastomer in the present invention, specifically, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butyl Peroxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert
-Butyl peroxybenzoate, tert-butyl perbenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butyl cumyl peroxide and the like can be mentioned.

Above all, in terms of odor and scorch stability 2,
5-Dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-Dimethyl-2,5-di (tert-butylperoxy)
Hexine-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane and n-butyl
-4,4-Bis (tert-butylperoxy) valerate is preferred, with 1,3-bis (tert-butylperoxyisopropyl) benzene being most preferred.

The amount of the organic peroxide compounded is from 0.05 to 5 per the total amount of the above components (a) and (b) or per the total amount of the above components (a), (b) and (c).
3% by weight, preferably 0.1 to 1% by weight, more preferably 0.1 to 0.5% by weight. By setting the blending amount within the above range, the resulting thermoplastic elastomer has sufficient rubber-like properties such as heat resistance, tensile properties, elastic recovery and impact resilience and strength, and also has excellent fluidity.

In the present invention, an extruder is used as the kneading device. Among them, it is preferable to use a non-open type device,
The kneading is preferably performed in an atmosphere of an inert gas such as nitrogen or carbon dioxide. The kneading is performed at a temperature at which the half-life of the organic peroxide used is less than 1 minute, usually 150 to 28.
It may be carried out at 0 ° C., preferably 170 to 240 ° C. for 1 to 20 minutes, preferably 1 to 10 minutes. The shearing force applied is usually 10 to 10 ⁴ sec ^-1 and preferably 10 ² to 10 ³ sec ^{-1 in} terms of shear rate.

In the present invention, sulfur, p-quinonedioxime, p, p'-dibenzoylquinonedioxime, N-methyl-in the partial cross-linking treatment with the organic peroxide is carried out.
Crosslinking aids such as N, 4-dinitrosoaniline, nitrobenzene, diphenylguanidine, trimethylolpropane-N, N'-m-phenylenedimaleimide, or divinylbenzene, triallyl cyanurate, eletin glycol dimethacrylate, diethylene glycol diethylene It is possible to incorporate polyfunctional methacrylate monomers such as methacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate, polyfunctional vinyl monomers such as vinyl butyrate or vinyl stearate. With such a compound, a uniform and mild crosslinking reaction can be expected. Particularly, divinylbenzene is preferable from the viewpoint of easy handling. In the present invention, the blending amount of such a crosslinking aid or a polyfunctional vinyl monomer is preferably 0.1 to 2% by weight, particularly preferably 0.3 to 1% by weight, based on the whole object to be treated, By blending within this range, a composition having excellent fluidity and having no change in physical properties due to heat history during molding of the composition can be obtained.

In order to accelerate the decomposition of organic peroxide, triethylamine, tributylamine, 2,4,6-
It is also possible to use tertiary amines such as tris (dimethylamino) phenol and decomposition accelerators such as naphthenates such as aluminum, cobalt, vanadium, copper, calcium, zirconium, manganese, magnesium, lead and mercury.

Partial crosslinking is carried out by the dynamic heat treatment in the presence of organic peroxide as described above. In the present invention, the term "partially crosslinked thermoplastic elastomer" means that the gel content measured by the following method is 20% or more, preferably 20 to 99.5%, and particularly preferably 45 to 98%. In the case of. Measurement of gel content 100 mg of a thermoplastic elastomer sample was weighed and cut into 0.5 mm × 0.5 mm × 0.5 mm strips, which were then placed in 30 ml of cyclohexane in a closed container at 23 ° C.
After soaking for 48 hours, the sample is taken out on a filter paper and dried at room temperature for 72 hours or more until a constant weight is obtained.

From the weight of the dry residue, the weight of all cyclohexane-insoluble components (fibrous filler, filler, pigment, etc.) other than the polymer component and the weight of the olefin resin component in the sample before immersion in cyclohexane were subtracted. , "Corrected final weight (Y)".

On the other hand, the weight of the ethylene / α-olefin copolymer rubber in the sample, [that is, from the weight of the sample to (1)
Cyclohexane soluble components other than ethylene / α-olefin copolymer rubber (for example, mineral oil and plasticizer) and (2) olefin resin component and (3) cyclohexane insoluble component other than polymer component (fibrous filler, filler, pigment, etc.) ) Is the “corrected initial weight (X)”.

Here, the gel content is calculated by the following formula. Gel content (% by weight) = [corrected final weight (Y)] ÷
[Corrected initial weight (X)] × 100 In the present invention, the poly-1-butene thermoplastic elastomer [II] is a poly-1-butene resin [I] and a poly-1.
-Total amount of butene-based thermoplastic elastomer [II] 100
10 to 70 parts by weight, preferably 15 to 70 parts by weight
It is used in an amount of 65 parts by weight, more preferably 20 to 60 parts by weight.

The poly-1-butene thermoplastic elastomer composition according to the present invention comprises the above poly-1-butene resin [I].
And poly-1-butene thermoplastic elastomer [II],
It can be obtained by melt-kneading using a kneader such as an extruder or a Banbury mixer.

Skin Sheet The skin sheet according to the present invention is obtained by molding the poly-1-butene thermoplastic elastomer composition obtained as described above into a sheet using a sheet molding machine.

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 poly-1-butene resin composition containing the above-mentioned specific thermoplastic elastomer, it is excellent in emboss transfer property and can have 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 a polyurethane resin paint, an epoxy resin paint, an acrylic resin paint or the like. The thickness of the skin sheet is usually 0.1 to 1.5 mm, preferably 0.2 to 1.2 mm, although it depends on the application.

The skin sheet according to the present invention is the above-mentioned poly-1.
-Since it is composed of a butene-based thermoplastic elastomer composition,
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 an automobile interior material and a carrying bag exterior material.

Laminated Body The laminated body according to the present invention comprises the layer made of the above-mentioned skin sheet (skin sheet layer) and the 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 foaming 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.

Inorganic fillers 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.

[0051]

The poly-1-butene thermoplastic elastomer composition according to the present invention comprises a poly-1-butene resin and a specific poly-1-butene thermoplastic elastomer.
It is possible to provide a skin sheet having excellent surface scratch resistance, puncture resistance and emboss transfer resistance. The skin sheet according to the present invention is the poly-1-
Since it is formed from a butene-based thermoplastic elastomer composition, it has excellent properties as described above.

Further, since the laminate according to the present invention uses the above-mentioned skin sheet, it has excellent scratch resistance and puncture resistance on the surface, and does not cause wrinkles on the surface even if molding is further performed. Excellent moldability.

The present invention will be described below with reference to examples.
The present invention is not limited to these examples. The poly-1-butene resin used in Examples and Comparative Examples,
The poly-1-butene thermoplastic elastomer and the propylene / ethylene random copolymer are as follows.

[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) 2) 1-butene / ethylene random copolymer (hereinafter PB
-2) Ethylene content: 1.5 mol%, MFR: 2.0 g / 10
Min (ASTM D 1238, 190 ° C, 2.16 kg load) 3) 1-butene / propylene random copolymer (hereinafter, P
B-3) Propylene content: 15 mol%, MFR: 1.0 g / 10
Min (ASTM D 1238, 190 ° C, 2.16 kg load) [Poly-1-butene thermoplastic elastomer] 1) Ethylene / propylene / 5-ethylidene-2-norbornene terpolymer rubber (EPT) [Ethylene content: 80 mol%, iodine value: 13, Mooney viscosity ML _{1 + 4} (100
℃, JIS K 6300): 75] 70 parts by weight, poly
-1-Butene resin [ethylene content: 1.5 mol%, density:
0.91 g / cm ³ MFR: 7.0 g / 10 minutes (ASTM D
1238, 190 ° C., 2.16 kg load)] and 20 parts by weight of polyethylene resin [density: 0.92 g / cm ³ , MF
R: 18 g / 10 minutes (ASTM D 1238, 190
C., 2.16 kg load)] 10 parts by weight of 1,3-bis (tert-butylperoxyiropropyl)
Partially crosslinked thermoplastic elastomer (hereinafter abbreviated as TPE-1) obtained by adding 0.5 part by weight of benzene and 1 part by weight of divinylbenzene and performing a dynamic heat treatment 2) EPT [ethylene content: 75 Mol%, iodine value: 1
0, Mooney viscosity ML _{1 + 4} (100 ° C, JIS K 63
00): 120] 55 parts by weight, poly-1-butene resin [1-butene homopolymer, density: 0.92 g / cm ³ , MF
R: 15 g / 10 minutes (ASTM D 1238, 190
C., 2.16 kg load)] and 20 parts by weight of polyethylene resin [density: 0.92 g / cm ³ , MFR: 18 g / 10 min (ASTM D 1238, 190 ° C., 2.16 kg load)] 5 parts by weight, 20 parts by weight of paraffinic process oil and Irg manufactured by Ciba-Geigy Co., Ltd. as an antioxidant
A mixture of 0.3 parts by weight of anox1010 and 2,5-
Dimethyl-2,5-di (tert-butylperoxy) hexyne
-3 Partially crosslinked thermoplastic elastomer (hereinafter abbreviated as TPE-2) obtained by adding 0.5 parts by weight and 1 part by weight of divinylbenzene and performing a dynamic heat treatment [propylene / ethylene random copolymer Coalescence] 1) Propylene / ethylene random copolymer [ethylene content: 4.0 mol%, MFR: 1.0 g / 10 min (AS
TM D 1238, 230 ° C., 2.16 kg load), hereinafter abbreviated as PP-1]

[0055]

Example 1 PB-1,60 as poly-1-butene resin
Parts by weight, TPE-1, 40 parts by weight as a poly-1-butene thermoplastic elastomer, and furnace type carbon black as a pigment [manufactured by Mitsubishi Kasei Co., Ltd., No. 30]
0.3 parts by weight, 0.5 parts by weight of Tinuvin 326 [manufactured by Ciba Geigy Co., Ltd.] as a light resistance stabilizer, and 0.2 parts by weight of Irganox 1010 and Irganox 1076 [manufactured by Ciba Geigy Co., Ltd.] as antioxidants, respectively. The mixture was melt-kneaded using a 65 mmφ uniaxial extruder to obtain a composition.

Then, the obtained composition was molded into a sheet having a thickness of 0.5 mm by a sheet molding machine and then 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. there were. The obtained skin sheet was subjected to a tensile test, a scratch resistance test and a puncture resistance test 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.

[0059]

Examples 2 and 3 and Comparative Examples 1 and 2 PB-1, P
B-2, PB-3, TPE-1 and TPE-2 first
A skin sheet was obtained in the same manner as in Example 1 except that the mixing ratios shown in the table were used.

A tensile test was conducted on the obtained skin sheet,
The scratch resistance test and the puncture resistance test were conducted according to the above-mentioned test methods. In addition, the emboss transfer property was 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 3 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 4 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]

[Table 2]

Claims (7)

[Claims] 1. [I] poly-1-butene resin: 30 to 90 parts by weight, and [II] poly-1-butene thermoplastic elastomer: 10 to 70 parts by weight (of components [I] and [II]). The total amount is 100 parts by weight), and the poly-1-butene thermoplastic elastomer [II] is an ethylene / α-olefin copolymer rubber (a): 30 to 90.
And a poly-1-butene resin (b): 10 to 70 parts by weight (the total amount of components (a) and (b) is 100 parts by weight) in the presence of an organic peroxide. A poly-1-butene-based thermoplastic elastomer composition, which is a partially crosslinked thermoplastic elastomer obtained by dynamically heat-treating. 2. [I] poly-1-butene resin: 30 to 90 parts by weight, and [II] poly-1-butene thermoplastic elastomer: 10 to 70 parts by weight (of components [I] and [II]). The total amount is 100 parts by weight), and the poly-1-butene thermoplastic elastomer [II] is an ethylene / α-olefin copolymer rubber (a): 30 to 90.
Parts by weight, poly-1-butene resin (b): 5 to 50 parts by weight, polyethylene resin (c): 5 to 25 parts by weight (the total amount of components (a), (b) and (c) is 100 parts by weight), which is a partially crosslinked thermoplastic elastomer obtained by a dynamic heat treatment in the presence of an organic peroxide. Elastomer composition. 3. [I] poly-1-butene resin: 30 to 90 parts by weight, and [II] poly-1-butene thermoplastic elastomer: 10 to 70 parts by weight (of components [I] and [II]). The total amount is 100 parts by weight), and the poly-1-butene thermoplastic elastomer [II] is an ethylene / α-olefin copolymer rubber (a): 30 to 90.
And a poly-1-butene resin (b): 10 to 70 parts by weight (the total amount of components (a) and (b) is 100 parts by weight) in the presence of an organic peroxide. A skin sheet, which is a partially crosslinked thermoplastic elastomer obtained by dynamically heat-treating. 4. [I] poly-1-butene resin: 30 to 90 parts by weight, and [II] poly-1-butene thermoplastic elastomer: 10 to 70 parts by weight (of components [I] and [II]). The total amount is 100 parts by weight), and the poly-1-butene thermoplastic elastomer [II] is an ethylene / α-olefin copolymer rubber (a): 30 to 90.
Parts by weight, poly-1-butene resin (b): 5 to 50 parts by weight, polyethylene resin (c): 5 to 25 parts by weight (the total amount of components (a), (b) and (c) is 100 parts by weight) and a partially cross-linked thermoplastic elastomer obtained by dynamically heat-treating a mixture thereof in the presence of an organic peroxide. 5. The skin sheet according to claim 3 or 4, wherein the surface is embossed. 6. [I] poly-1-butene resin: 30 to 90 parts by weight, and [II] poly-1-butene thermoplastic elastomer: 10 to 70 parts by weight (of components [I] and [II]). The total amount is 100 parts by weight) and a polyolefin foam layer, and the poly-1-butene thermoplastic elastomer [II] is an ethylene / α-olefin copolymerized Rubber (a): 30 to 90
And a poly-1-butene resin (b): 10 to 70 parts by weight (the total amount of components (a) and (b) is 100 parts by weight) in the presence of an organic peroxide. A laminate, which is a partially cross-linked thermoplastic elastomer obtained by dynamically heat-treating. 7. [I] poly-1-butene resin: 30 to 90 parts by weight, and [II] poly-1-butene thermoplastic elastomer: 10 to 70 parts by weight (of components [I] and [II]). The total amount is 100 parts by weight) and a polyolefin foam layer, and the poly-1-butene thermoplastic elastomer [II] is an ethylene / α-olefin copolymerized Rubber (a): 30 to 90
Parts by weight, poly-1-butene resin (b): 5 to 50 parts by weight, polyethylene resin (c): 5 to 25 parts by weight (the total amount of components (a), (b) and (c) is 100 parts by weight) and a partially cross-linked thermoplastic elastomer obtained by dynamically heat-treating the mixture in the presence of an organic peroxide.