JPH054307A - Laminate of thermoplastic elastomer - Google Patents

Abstract

PURPOSE:To import weather resistance and excellent heat resistance and dimensional stability to the above laminate, by a method wherein the laminate is constituted of a layer obtained by heat-treating dynamically a blended matter containing peroxide crosslinked olefin copolymeric rubber, olefin plastic and alpha,beta-unsaturated carboxylic acid and a superpolymeric polyolefin layer. CONSTITUTION:A thermoplastic elastomer laminate is constituted of a layer comprising a graft modified olefin elastomer which is crosslinked partly by being heat-treated dynamically in the presence of organic peroxide, a blended matter containing 95-10 pts.wt. peroxide crosslinked olefin copolymeric rubber, 5-90 pts.wt. olefin plastic (the total quantity of them are made 100 pts.wt.) and 0.01-10 pts.wt. alpha,beta-unsaturated carboxylic acid or its derivative or an unsaturated epoxy monomer and a layer comprised of superpolymeric polyolefin.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION The present invention relates to a thermoplastic elastomer laminate, and more particularly to a thermoplastic elastomer laminate effective for applications such as automobile interior materials and sealing materials.

[0002]

BACKGROUND OF THE INVENTION The glass run channel, which has been one of the important sealing materials used in automobiles, has been (1)
A composite material composed of a vulcanized rubber containing ethylene / propylene / diene copolymer rubber as a main component, which has excellent weather resistance and heat resistance, an adhesive, and nylon fiber. (2) This vulcanized rubber and abrasion resistance Composite material consisting of an adhesive with excellent properties,
(3) Soft polyvinyl chloride for profile extrusion is used.

Since the above composite materials (1) and (2) are based on a vulcanized product of an ethylene / propylene / diene copolymer rubber having excellent weather resistance and heat resistance,
Excellent heat resistance and dimensional stability. However,
The manufacturing process for these composite materials is ethylene / propylene /
It is very complicated and consists of a kneading step of a diene copolymer rubber and a filler, an extrusion molding step, a surface buffing step, an adhesive applying step, a drying step and a fiber flocking step. On the other hand, the above-mentioned composite material (3) is manufactured by the profile extrusion molding of soft polyvinyl chloride, so that the manufacturing process is simplified. However, this composite material has poor heat resistance and dimensional stability, and is inferior in practical performance as compared with the composite materials (1) and (2).

Therefore, it is excellent in weather resistance, heat resistance and dimensional stability and can be manufactured by a simplified manufacturing process.
It has been desired to develop a laminated body that can be effectively used for applications such as automobile interior materials and sealing materials.

[0005]

SUMMARY OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, and is excellent in weather resistance, heat resistance and dimensional stability, and has a simplified manufacturing process. It is an object of the present invention to provide a thermoplastic elastomer laminate which can be produced and is excellent in so-called economy.

[0006]

SUMMARY OF THE INVENTION The thermoplastic elastomer laminate according to the present invention comprises (a) 95 to 10 parts by weight of a peroxide-crosslinking olefin copolymer rubber and (b) 5 to 90 parts by weight of an olefin plastic [component (a ) And (b) is 100 parts by weight] and (c) 0.01 to 10 parts by weight of an α, β-unsaturated carboxylic acid or derivative thereof or an unsaturated epoxy monomer. The blended product
It is composed of a layer composed of a graft-modified polyolefin elastomer (A) that is dynamically heat-treated in the presence of an organic peroxide and partially crosslinked, and a layer composed of an ultrahigh molecular weight polyolefin (B). It has a feature.

The above graft-modified polyolefin elastomer (A) has the above-mentioned components (a) and (b).
(D) 5 to 100 parts by weight of a non-crosslinking peroxide type rubbery substance, and / or (e) 3 to 100 parts by weight of a mineral oil-based softening agent, based on 100 parts by weight of the total amount of the components. preferable.

The ultrahigh molecular weight polyolefin (B) preferably used in the present invention includes the following ultrahigh molecular weight polyolefins and ultrahigh molecular weight polyolefin compositions.

In particular, the ultrahigh molecular weight polyolefin compositions (2) and (3) which can be coextrusion laminated with the graft-modified polyolefin elastomer (A) are preferable for producing a laminate.

(1) The intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. is 10 to 40 dl / g, preferably 15
Ultra high molecular weight polyolefin in the range of ~ 35 dl / g. (2) Ultra-high molecular weight polyolefin having an intrinsic viscosity [η] measured in a 135 ° C decalin solvent of 10 to 40 dl / g and an intrinsic viscosity [η] measured in a 135 ° C decalin solvent are 0.1 A polyolefin composition consisting essentially of a low to high molecular weight polyolefin in the range of ~ 5 dl / g, wherein the ultra high molecular weight polyolefin is 100 total weight of ultra high molecular weight polyolefin and low to high molecular weight polyolefin. It exists in a ratio of 15 to 40% by weight with respect to the weight% and has an intrinsic viscosity [η] measured in a 135 ° C. decalin solvent of 3.5 to 8.
An ultra high molecular weight polyolefin composition in the range of 3 dl / g.

(3) An ultrahigh molecular weight polyolefin composition comprising the ultrahigh molecular weight polyolefin composition of the above (2) and 1 to 20% by weight of a liquid or solid lubricant based on the ultrahigh molecular weight polyolefin composition.

[0012]

DETAILED DESCRIPTION OF THE INVENTION The thermoplastic elastomer laminate according to the present invention will be specifically described below. The thermoplastic elastomer laminate according to the present invention comprises a layer made of a specific graft-modified polyolefin elastomer (A) and a layer made of an ultrahigh molecular weight polyolefin (B).

Graft-modified polyolefin elastomer
(A) The graft-modified polyolefin-based elastomer (A) used in the present invention includes (a) a peroxide-crosslinking olefin-based copolymer rubber, (b) an olefin-based plastic, and (c) α, β-unsaturation. A blend containing a carboxylic acid or a derivative thereof or an unsaturated epoxy monomer is a graft-modified polyolefin-based thermoplastic elastomer which is dynamically heat-treated and partially cross-linked in the presence of an organic peroxide.

Further, in the present invention, in the above blend, (d) a non-crosslinking peroxide type rubber-like substance,
(E) A mineral oil-based softening agent may be included. The peroxide-crosslinking olefin-based copolymer rubber (a) used in the present invention contains no olefin-based copolymer rubber such as ethylene / propylene / non-conjugated diene copolymer rubber and ethylene / butadiene copolymer rubber. A rubber which is an elastic copolymer of a fixed shape and which is crosslinked to reduce fluidity or become non-fluid when mixed with an organic peroxide and kneaded under heating.

Specific examples of the above-mentioned non-conjugated diene include dicyclopentadiene, 1,4-hexadiene, dicyclooctadiene, methylene-norbornene and ethylidene-.
Examples include norbornene.

In the present invention, among the above-mentioned peroxide-crosslinking type olefin-based copolymer rubbers, the molar ratio of ethylene component unit to propylene component unit (ethylene component unit / propylene component unit) is 50/50 to 50. 90/1
Ethylene / propylene copolymer rubbers and ethylene / propylene / non-conjugated diene copolymer rubbers, which are 0, particularly in the range of 55/45 to 85/15, are preferably used. Among them, ethylene / propylene / non-conjugated diene copolymer rubber, particularly ethylene / propylene / ethylidene norbornene copolymer rubber is preferable because it can provide a thermoplastic elastomer excellent in heat resistance, tensile strength characteristics and impact resilience.

The peroxide-crosslinking olefin copolymer rubber has a Mooney viscosity ML _{1 + 4} (100 ° C.) of 1
It is preferably in the range of 0 to 250, particularly 40 to 150. When a peroxide-crosslinking olefin copolymer rubber having a Mooney viscosity ML _{1 + 4} (100 ° C.) of less than 10 is used, the thermoplastic elastomer composition obtained tends to have reduced tensile strength properties. On the other hand, Mooney viscosity M
When a peroxide-crosslinking olefin-based copolymer rubber having L _{1 + 4} (100 ° C.) of more than 250 is used, the thermoplastic elastomer composition obtained tends to have low fluidity.

Further, the peroxide-crosslinking olefin copolymer rubber preferably has an iodine value of 25 or less. When the peroxide-crosslinking olefin copolymer rubber having an iodine value within the above range is used, a thermoplastic elastomer having a good balance of fluidity and rubber properties can be obtained.

In the present invention, the peroxide-crosslinking olefin copolymer rubber (a) is used in an amount of 100 parts by weight based on the total amount of the peroxide-crosslinking olefin copolymer rubber (a) and the olefin plastic (b). , 95
It is used in a proportion of 10 to 10 parts by weight, preferably 95 to 60 parts by weight.

When the peroxide-crosslinking olefin-based copolymer rubber (a) is used in the above proportion, the resulting graft-modified polyolefin-based elastomer (A) is excellent in moldability and has rubber-like properties such as rubber elasticity. It has excellent characteristics.

The olefinic plastic (b) used in the present invention can be produced by either the high pressure method or the low pressure method.
It consists of a crystalline, high molecular weight solid product obtained by polymerizing one or more mono-olefins. Examples of such resins include isotactic or syndiotactic monoolefin polymer resins. These representative resins are commercially available.

Specific examples of suitable raw material olefins include ethylene, propylene, 1-butene, 1-pentene, 1-
Hexene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, 1-
Examples include octene, 1-decene and mixed olefins of two or more of these. In the present invention, any polymerization method may be adopted, whether it is homopolymerization or copolymerization, as long as a resinous product is obtained.

In the present invention, a particularly preferable olefin-based plastic is a peroxide decomposition type olefin-based plastic. In the present invention, the peroxide-decomposable olefin-based plastic refers to an olefin-based plastic in which the fluidity of the resin is increased by reducing the molecular weight by thermally decomposing by mixing with peroxide and kneading with heating. Tactic polypropylene; a copolymer of propylene and a small amount of other α-olefin, such as propylene-ethylene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-4-methyl -1-Pentene copolymer and the like can be mentioned.

The olefinic plastic used in the present invention has a melt index (ASTM-D-1238).
-65T, 230 ° C) is preferably in the range of 0.1 to 50, particularly 5 to 20.

In the present invention, the olefinic plastic contributes to the improvement of the fluidity and the heat resistance of the elastomer composition. In the present invention, the olefin-based plastic (b) is 5 to 90 parts by weight, preferably 5 to 90 parts by weight, based on 100 parts by weight of the total amount of the peroxide-crosslinking olefin-based copolymer rubber (a) and the olefin-based plastic (b). It is used in a proportion of 5 to 40 parts by weight.

When the olefin-based plastic (b) is used in the above proportion, the resulting graft-modified polyolefin-based elastomer (A) has excellent rubber-like properties such as rubber elasticity and excellent fluidity. As a result, it has excellent moldability.

In the present invention, α, β-unsaturated carboxylic acid or its derivative, or unsaturated epoxy monomer (c)
Is used as a graft modifier. Above α, β-
Specific examples of the unsaturated carboxylic acid or its derivative include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, bicyclo [2,2,1] hept-2-ene. -5,6-Dicarboxylic acid and other unsaturated carboxylic acids; maleic anhydride, itaconic anhydride, citraconic anhydride,
Tetrahydrophthalic anhydride, bicyclo [2,2,1] hept
Anhydrides of unsaturated carboxylic acids such as 2-ene-5,6-dicarboxylic acid anhydride; methyl acrylate, methyl methacrylate, dimethyl maleate, monomethyl maleate, diethyl fumarate,
Dimethyl itaconic acid, diethyl citraconic acid, tetrahydrodimethyl phthalic anhydride, bicyclo [2,2,1] hept
Examples thereof include esters of unsaturated carboxylic acids such as dimethyl-2-ene-5,6-dicarboxylate. Among these, maleic acid, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid or their anhydrides are preferable.

Specific examples of the unsaturated epoxy monomer include glycidyl acrylate, glycidyl methacrylate, glycidyl ester of unsaturated monocarboxylic acid such as glycidyl p-styrylcarboxylate; maleic acid, itaconic acid, citraconic acid. , Butenetricarboxylic acid, endo-cis-bicyclo [2,2,1] hept-5-
Ene-2,3-dicarboxylic acid, endo-cis-bicyclo [2,
2,1] Hept-5-en-2-methyl-2,3-dicarboxylic acid and other unsaturated carboxylic acid monoglycidyl esters or polyglycidyl esters; allyl glycidyl ether, 2-methyl allyl glycidyl ether, O- Allylphenol glycidyl ether, m-Allylphenol glycidyl ether, p-
Unsaturated glycidyl ethers such as allylphenol glycidyl ether, isopropenylphenol glycidyl ether, m-vinylphenol glycidyl ether, p-vinylphenol glycidyl ether; 2- (o-vinylphenyl) ethylene oxide, 2- (p -Vinylphenyl) ethylene oxide, 2- (o-vinylphenyl) propylene oxide, 2- (p-vinylphenyl) propylene oxide, 2- (o-arylphenyl) ethylene oxide, 2- (p-arylphenyl) ethylene oxide,
2- (o-allylphenyl) propylene oxide, 2- (p-
Allylphenyl) propylene oxide, p-glycidyl styrene, 3,4-epoxy-1-butene, 3,4-epoxy-3-
Methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methyl-1-pentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide, allyl-
2,3-epoxycyclopentyl ether and the like are preferable.

In the present invention, the α, β-unsaturated carboxylic acid or its derivative, or the unsaturated epoxy monomer (c) is a peroxide-crosslinking olefin copolymer rubber (a) and an olefin plastic (b). 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight in total.

When the α, β-unsaturated carboxylic acid or its derivative or the unsaturated epoxy monomer (c) is used in the above proportion, the resulting graft-modified polyolefin elastomer (A) has a good moldability. Excellent and excellent in adhesive strength with the ultra high molecular weight polyolefin (B) layer.

The non-peroxide type rubber-like substance (d) used in the present invention is, for example, polyisobutylene, butyl rubber, propylene-containing 70% by mole or more of propylene.
It refers to a hydrocarbon rubber-like substance such as ethylene copolymer rubber and atactic polypropylene, which does not crosslink even when mixed with peroxide and heated and kneaded so as not to reduce fluidity. Of these, polyisobutylene is the most preferable in terms of performance and handling.

The above-mentioned peroxide non-crosslinking rubbery substance contributes to the improvement of the fluidity of the elastomer composition, and in particular, the peroxide noncrosslinking rubbery substance having a Mooney viscosity ML _{1 + 4} (100 ° C.) of 60 or less is preferable. .

In the present invention, the peroxide non-crosslinking rubber-like substance (d) is 5 parts by weight per 100 parts by weight of the total amount of the peroxide crosslinkable olefin copolymer rubber (a) and the olefin plastic (b). It is used in a proportion of -100 parts by weight, preferably 5-50 parts by weight.

Mineral oil softener (e) used in the present invention
Usually weakens the intermolecular force of rubber during roll processing, facilitates processing, and helps disperse carbon black, white carbon, etc., which are compounded as fillers, or the hardness of vulcanized rubber. It is a high boiling point petroleum fraction used for the purpose of decreasing the oil content and increasing the flexibility and elasticity, and is classified into paraffin type, naphthene type, aromatic type and the like.

In the present invention, a mineral oil softener (e)
Is used in a proportion of 3 to 100 parts by weight, preferably 5 to 80 parts by weight, based on 100 parts by weight of the total amount of the peroxide-crosslinking olefin-based copolymer rubber (a) and the olefin-based plastic (b).

The graft-modified polyolefin-based elastomer (A) used in the present invention is a peroxide-crosslinking olefin-based copolymer rubber (a), an olefin-based plastic (b) and an α, β-unsaturated carboxylic acid or its derivative, Alternatively, the unsaturated epoxy monomer (c), and if necessary, a peroxide non-crosslinking rubber-like substance (d) and a mineral oil-based softening agent (e) are blended in the above-mentioned proportions to prepare an organic peroxide. It is produced by a method of dynamically heat-treating in the presence to partially crosslink.

In the present invention, it is preferable to use the above-mentioned peroxide non-crosslinking rubbery substance (d) and mineral oil type softening agent (e). Further, in the present invention, the graft-modified polyolefin elastomer (A)
A filler and a coloring agent can be included therein within a range not impairing the object of the present invention.

Specific examples of the above-mentioned fillers include calcium carbonate, calcium silicate, clay, kaolin, talc, silica, diatomaceous earth, mica powder, asbestos, alumina, barium sulfate, aluminum sulfate, calcium sulfate and base. Examples thereof include soluble magnesium carbonate, molybdenum disulfide, graphite, glass fiber, glass sphere, shirasu balloon, and carbon fiber.

Specific examples of the colorant include carbon black, titanium oxide, zinc white, red iron oxide, ultramarine blue,
Examples include dark blue, azo pigments, nitroso pigments, lake pigments and phthalocyanine pigments.

Further, in the present invention, known heat-resistant stabilizers such as phenol-based, sulfite-based, phenylalkane-based, phosphite-based, and amine-based stabilizers in the graft-modified polyolefin elastomer (A); Additives such as agents, weather resistance stabilizers, antistatic agents, lubricants such as metal soaps, waxes, etc. can be contained in the proportions usually used in the production of olefin plastics or olefin copolymer rubbers.

In the present invention, the blend of the above components is dynamically heat treated in the presence of organic peroxide to produce a partially crosslinked graft-modified polyolefin elastomer (A).

The above-mentioned "dynamically heat-treating" means kneading each of the above components in a molten state. In the present invention, specific examples of the organic peroxide used in the production of the graft-modified polyolefin elastomer (A) include dicumyl peroxide and di-tert-.
Butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (t
ert-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-chloro Benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-
Examples include butyl perbenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butyl cumyl peroxide.

Among these, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane and 2,5-dimethyl-2,5-di-from the viewpoint of odor and scorch stability. (Tert-Butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4 1,4-Bis (tert-butylperoxy) valerate is preferred, and among them, 1,3-bis (tert-butylperoxyisopropyl) benzene is most preferred.

In the present invention, the organic peroxide is
Peroxide-crosslinking olefin copolymer rubber (a),
0.05 based on 100% by weight of the total amount of the olefin-based plastic (b) and the α, β-unsaturated carboxylic acid or its derivative, or the unsaturated epoxy monomer (c).
It is used in a proportion of ˜3% by weight, preferably 0.1 to 1% by weight.

When the organic peroxide is used in the above proportion, the resulting graft-modified polyolefin elastomer (A) has excellent rubber-like properties such as heat resistance, tensile properties, elastic recovery and impact resilience, and strength properties, and Excellent in moldability.

As the kneading device, a conventionally known kneading device,
For example, an open type mixing roll, a non-open type Banbury mixer, an extruder, a kneader, a continuous mixer and the like are used. Of these, a non-open type kneading device is preferable, and kneading is preferably performed in an atmosphere of an inert gas such as nitrogen gas or carbon dioxide gas.

The kneading is preferably carried out at a temperature at which the half-life of the organic peroxide used is less than 1 minute.
The kneading temperature is usually 150 to 280 ° C., preferably 17
The temperature is 0 to 240 ° C., and the kneading time is 1 to 20 minutes, preferably 3 to 10 minutes. The applied shearing force is usually 10 to 10 ⁴ sec ⁻¹ , preferably 10 ² to 10 ³ sec ⁻¹ , as the shearing force.

In the present invention, sulfur, p-quinonedioxime, p, p'-dibenzoylquinonedioxime and N-methyl-N are used in the partial crosslinking treatment with the above organic peroxide.
-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, peroxy crosslinking aids such as trimethylolpropane-N, N'-m-phenylenedimaleimide, or divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, A polyfunctional methacrylate monomer such as diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate or allyl methacrylate, or a polyfunctional vinyl monomer such as vinyl butyrate or vinyl stearate can be blended.

By using the above compound,
A uniform and mild crosslinking reaction can be expected. Particularly, divinylbenzene is most preferred in the present invention. Divinylbenzene is easy to handle, has good compatibility with the peroxide-crosslinking olefin-based copolymer rubber (a) and the olefin-based plastic (b), which are the main components of the material to be crosslinked, and is an organic peroxide. Since it has a solubilizing effect and acts as a dispersant for organic peroxides, a graft-modified polyolefin elastomer having a uniform cross-linking effect by heat treatment and a good balance of fluidity and physical properties can be obtained.

In the present invention, the above-mentioned crosslinking aid or polyfunctional vinyl monomer is contained in an amount of 0.1 to 2% by weight, particularly 0.3 to 1% by weight, based on the whole of the above-mentioned object to be crosslinked. It is preferable to use it in a ratio of. When the blending ratio of the cross-linking aid or the polyfunctional vinyl monomer exceeds 2% by weight, when the blending amount of the organic peroxide is large, the cross-linking reaction proceeds too fast. Inferiority, on the other hand, when the blending amount of the organic peroxide is small, the crosslinking aid and the polyfunctional vinyl monomer remain as an unreacted monomer in the graft-modified polyolefin-based elastomer, and the graft-modified polyolefin-based elastomer is Changes in physical properties may occur due to heat history during processing and molding.
Therefore, the cross-linking aid and the polyfunctional vinyl monomer should not be blended in excess.

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

The graft-modified polyolefin elastomer used in the present invention is partially crosslinked,
The term "partially crosslinked" means that the gel content measured by the following method is in the range of 20 to 98%,
In the present invention, the gel content is preferably within the range of 45 to 98%.

[Measurement method of gel content] As a sample, about 100 mg of a graft-modified polyolefin elastomer pellet was weighed, and 30 ml of cyclohexane, which was a sufficient amount for this pellet, was placed in a closed container at 23 ° C. for 48 hours. Soak.

Next, this sample is taken out on a filter paper and dried at room temperature for 72 hours or more until a constant weight is obtained. The gel content is represented by the following formula. Gel content [%] = (dry weight after immersion in cyclohexane)
÷ (Weight before immersion in cyclohexane) × 100 Graft-modified polyolefin elastomer (A) constituting one layer of the thermoplastic elastomer laminate according to the present invention
Has excellent fluidity because it comprises a partially cross-linked olefin-based copolymer rubber and an olefin-based plastic, preferably a peroxide-decomposable olefin-based plastic.

[0055] Specific examples of ultra high molecular weight polyolefin (B) preferably ultra high molecular weight polyolefin (B) used in the present invention, the ultra-high molecular weight polyolefin and the ultrahigh molecular weight polyolefin composition such as are exemplified below.

(1) Intrinsic viscosity [η] measured in decalin solvent at 135 ° C. is 10 to 40 dl / g, preferably 15
Ultra high molecular weight polyolefin in the range of ~ 35 dl / g. (2) Ultra-high molecular weight polyolefin having an intrinsic viscosity [η] measured in a 135 ° C decalin solvent of 10 to 40 dl / g and an intrinsic viscosity [η] measured in a 135 ° C decalin solvent are 0.1 A polyolefin composition consisting essentially of a low to high molecular weight polyolefin in the range of ~ 5 dl / g, wherein the ultra high molecular weight polyolefin is 100 total weight of ultra high molecular weight polyolefin and low to high molecular weight polyolefin. It exists in a ratio of 15 to 40% by weight with respect to the weight% and has an intrinsic viscosity [η] measured in a 135 ° C. decalin solvent of 3.5 to 8.
An ultra high molecular weight polyolefin composition in the range of 3 dl / g.

(3) An ultrahigh molecular weight polyolefin composition comprising the ultrahigh molecular weight polyolefin composition of (2) above and 1 to 20% by weight of a liquid or solid lubricant based on the ultrahigh molecular weight polyolefin composition.

In particular, the above-mentioned ultrahigh molecular weight polyolefin compositions (2) and (3) which can be coextrusion laminated with the graft-modified polyolefin elastomer are preferable for producing a laminate.

Examples of the ultrahigh molecular weight polyolefin and the low molecular weight to high molecular weight polyolefin as described above include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4 -Methyl
It is composed of a homopolymer or copolymer of α-olefin such as -1-pentene and 3-methyl-1-pentene. In the present invention, ethylene homopolymer, and ethylene and other α
-A copolymer containing ethylene as a main component and composed of an olefin is desirable.

As the liquid lubricating oil used in the composition (3), petroleum-based lubricating oil, synthetic lubricating oil and the like are used. Specific examples of the petroleum-based lubricating oil include liquid paraffin, spindle oil, refrigerating machine oil, dynamo oil, turbine oil, machine oil, and cylinder oil.

Specific examples of synthetic lubricating oils include synthetic hydrocarbon oils, polyglycol oils, polyphenyl ether oils, ester oils, phosphate ester oils, polychlorotrifluoroethylene oils, fluoroester oils, chlorinated biphenyls. Oil, silicone oil, etc. are used.

As the solid lubricating oil used in the composition (3), graphite and molybdenum disulfide are mainly used, but boron nitride, tungsten disulfide and lead oxide are also used. Glass powder, metallic soap, etc. can also be used. The solid lubricating oil can be used alone or in combination with the liquid lubricating oil, and can be blended with the ultra high molecular weight polyolefin in the form of, for example, powder, sol, gel, suspense.

Further, in the present invention, as in the case of the graft-modified polyolefin elastomer (A) described above, the above-mentioned filler and colorant are added to the ultra-high molecular weight polyolefin (B). It can be included as long as the purpose is not impaired.

Further, in the present invention, in the ultrahigh molecular weight polyolefin (B), as in the case of the graft-modified polyolefin elastomer (A) described above, a phenol type, a sulfite type, a phenylalkane type, and a phosphite type are used. , Known heat stabilizers such as amine stabilizers;
Anti-aging agent; Weather resistance stabilizer; Antistatic agent; Metal soap,
Additives such as lubricants such as wax can be included in the proportions usually used in the production of olefin-based plastics or olefin-based copolymer rubbers.

Thermoplastic Elastomer Laminate The thermoplastic elastomer laminate according to the present invention comprises the above graft-modified polyolefin elastomer (A).
And a layer composed of the ultra high molecular weight polyolefin (B). The thermoplastic elastomer laminate according to the present invention can be obtained by laminating both the above layers.

The method for laminating the graft-modified polyolefin elastomer (A) layer [hereinafter abbreviated as (A) layer] and the ultrahigh molecular weight polyolefin (B) layer [hereinafter abbreviated as (B) layer] is as follows: Depends on size and required physical properties,
Although not particularly limited, for example, the following laminating methods may be mentioned.

(1) A method of heat-sealing the preformed layers (A) and (B) by using a calender roll molding machine, a compression molding machine or the like at a temperature of at least one of the melting points. .

[0068] (2) advance either is sheet forming (A) layer or (B) layer extruded, a method of thermal fusion to the other layer that has a calendar molding. (3) A method in which the layer (A) and the layer (B) are simultaneously extrusion-molded by a multilayer extrusion molding machine and heat-sealed (coextrusion molding).

In the present invention, the above-mentioned lamination method (3) is preferable.

In the present invention, the thickness of the layer (A) is 0.
1 to 50 mm, and the thickness of the (B) layer is 5 μm to 10 m
m is generally preferred. In the thermoplastic elastomer laminate according to the present invention, the layer made of the graft-modified polyolefin elastomer (A) is a partially crosslinked olefin copolymer rubber, an olefin plastic, and preferably a peroxide-decomposable olefin plastic. Therefore, it has excellent heat resistance, heat aging resistance and rubber elasticity.

Further, in the thermoplastic elastomer laminate according to the present invention, the layer composed of the above-mentioned ultra-high molecular weight polyolefin (B) is excellent in abrasion resistance, scratch resistance, slidability and chemical resistance.

[0072]

INDUSTRIAL APPLICABILITY The thermoplastic elastomer laminate according to the present invention has remarkably excellent interlayer adhesion between the graft-modified polyolefin elastomer (A) layer and the ultrahigh molecular weight polyolefin (B) layer.

Further, the thermoplastic elastomer laminate according to the present invention is lighter in weight than the conventional composite material composed of vulcanized rubber and nylon fiber or soft polyvinyl chloride, and has a surface leached by a plasticizer or the like. It has no stickiness and is excellent in mechanical strength, heat resistance, heat aging resistance, weather resistance, abrasion resistance, scratch resistance, slidability and dimensional stability.

Further, the laminated body according to the present invention can be manufactured by simplifying the manufacturing process as compared with the conventional composite material as described above, and is therefore excellent in economic efficiency. In particular, a thermoplastic elastomer laminate using an ultrahigh molecular weight polyolefin composition that can be coextrusion laminated with the graft-modified polyolefin elastomer (A) as the ultrahigh molecular weight polyolefin (B) is economically excellent. .

Therefore, the thermoplastic elastomer laminate according to the present invention is not only used for automobile interior materials and sealing materials (in particular, glass run channels, belt line moldings, etc., which are required to have slidability with glass), Furniture, building materials,
Household appliances housing, bags, suitcases, sports equipment,
It can also be effectively used for applications such as office supplies and sundries.

The present invention will be described below with reference to examples.
The present invention is not limited to these examples.

[0077]

Example 1 Ethylene content 70 mol%, iodine value 1
2. 80 parts by weight of ethylene / propylene / ethylidene norbornene copolymer rubber [hereinafter, abbreviated as EPDM (1)] having a Mooney viscosity of ML _{1 + 4} (100 ° C.) of 120 and MFR
(ASTM D 1238-65T, 230 ° C) 13,
Polypropylene with a density of 0.91 g / cm ³ [hereinafter PP
20 parts by weight was kneaded using a Banbury mixer in a nitrogen atmosphere at 180 ° C. for 5 minutes, and the kneaded product was passed through a roll to form a sheet, which was then cut into square pellets.

Next, this square pellet and 1,3-bis (t
ert-butylperoxyisopropyl) benzene [hereinafter abbreviated as peroxide (A)] 0.3 part by weight, divinylbenzene [hereinafter abbreviated as DVB] 0.5 part by weight,
0.5 part by weight of maleic anhydride [hereinafter abbreviated as MAH] was mixed by stirring with a Henschel mixer.

Then, this mixture was extruded at 220 ° C. in a nitrogen atmosphere using a uniaxial extruder having L / D = 30 and a screw diameter of 50 mm to obtain a graft-modified polyolefin elastomer (a).

Then, the gel content of the copolymer rubber in the obtained graft-modified polyolefin elastomer (a) was measured by the above method. The results are shown in Table 1. Further, the graft resulting modified polyolefin elastomer (a) was compression molded at 190 ° C., to prepare a sheet for measuring physical properties, tensile stress at break (T _B), flexibility and test moldability according to the following method did. The results are shown in Table 1.

[Test Method] (1) Tensile Breaking Point Stress (T _B ) According to JIS K 6301, 200 mm / min
Tensile strength at break (T _B : unit kgf /
cm ² ) was measured.

(2) Flexibility The torsional rigidity (unit: kgf / cm ² ) was determined according to ASTM D 1043, and the flexibility was evaluated by the torsional rigidity.

(3) Formability According to ASTM D 1238, melt flow rate (MFR: unit g / 10 min, 230 ° C., 2.16).
(kg) and the melt flow rate was used to evaluate the moldability.

Next, the obtained graft-modified polyolefin elastomer (a) was manufactured by Toshiba Machine Co., Ltd.
Using a diameter T-die extruder, screw is full flight, L / D = 28, extrusion temperature 240 ° C, T die is coat hanger die, and extrusion speed is 2.5m / min. Then, the extruded sheet-like graft-modified polyolefin elastomer (a) in a melted state was converted into an ultra high molecular weight polyethylene film [135 ° C.
Intrinsic viscosity [η] measured in decalin solvent is 15 dl /
g of ultra-high molecular weight polyethylene having a thickness of 0.1 mm] and being passed through a pair of rolls in a state of being laminated, the thickness of the graft-modified polyethylene elastomer (a) layer is 1.0 mm, the ultra-high molecular weight polyethylene layer A laminate having a thickness of 0.1 mm was obtained. However, the graft-modified polyolefin-based elastomer (a) has a roll temperature of 60 ° C.
Was passed through the roll side so that the ultra high molecular weight polyethylene film was in contact with the roll side at room temperature.

The interlayer adhesion strength of the obtained laminate was measured according to the following method. The results are shown in Table 1. [Interlayer adhesion strength test] Test method: 180 degree peeling test piece: width 25 mm, length 100 mm Tensile speed: 25 mm / min Interlayer adhesion strength: value obtained by dividing peeling load by width of test piece (unit: kgf / cm) When the dynamic friction coefficient of the ultra high molecular weight polyolefin layer surface constituting the laminate was determined by the following test method,
It was 0.15.

[Dynamic Friction Coefficient Measurement Test] Dynamic friction coefficient is measured using a Matsubara friction and wear tester.
It was measured by the Wise method. Test condition Counterpart material: SUS304 (Roughness: around 6s) Peripheral speed: 12m / min Load: 10kg Contact area: 2 cm²

[0087]

Example 2 In Example 1, the amount of peroxide (A) was 0.6 part by weight, and the amount of maleic anhydride was 2.
The same procedure as in Example 1 was carried out except that the amount was 0 part by weight.

The results are shown in Table 1.

[0089]

Example 3 In Example 1, when the graft-modified polyolefin-based elastomer was manufactured, EPDM (1) was used.
In addition to PP and PP, butyl rubber [manufactured by Esso, IIR
-065, unsaturation 0.8 mol%, hereinafter abbreviated as IIR] 10 parts by weight and paraffin-based process oil [manufactured by Idemitsu Kosan, trade name Diana Process Oil] 30 parts by weight, and Example 1 The same was done.

The results are shown in Table 1.

[0091]

Example 4 Example 3 was repeated except that 0.5 part by weight of glycidyl methacrylate was used instead of 0.5 part by weight of MAH.

The results are shown in Table 1.

[0093]

Fifth Embodiment In the third embodiment, EPDM (1), P
The amounts of P, IIR and paraffinic process oil are 60 parts by weight, 40 parts by weight, 20 parts by weight and 40 parts by weight, respectively.
The same procedure as in Example 3 was carried out except that the parts by weight were used.

The results are shown in Table 1.

[0095]

Sixth Embodiment In the third embodiment, EPDM (1), PDM
The amounts of P, IIR and paraffinic process oil are 90 parts by weight, 10 parts by weight, 20 parts by weight and 40 parts by weight, respectively.
Parts by weight, and instead of 0.5 parts by weight of MAH,
Example 3 was repeated except that 3 parts by weight of glycidyl methacrylate was used.

The results are shown in Table 1.

[0097]

Seventh Embodiment In the third embodiment, EPDM (1), P
P, IIR, paraffinic process oil and MAH
Example 3 was repeated, except that the blending amounts of 70 parts by weight, 30 parts by weight, 40 parts by weight, 60 parts by weight, and 6 parts by weight, respectively.

The results are shown in Table 1.

[0099]

[Embodiment 8] In place of T-die molding in Embodiment 1.
In addition, the obtained graft-modified polyolefin elastomer
-Extruded at a temperature of 230 ° C and its surface
Intrinsic viscosity [η] measured in decalin solvent at 135 ℃
Contains 23 wt% of ultra high molecular weight polyethylene of 30 dl / g
Ultra high molecular weight polyethylene composition [Dissolve decalin at 135 ° C
Intrinsic viscosity [η] measured in medium is 5.5 dl / g, density
Is 0.955 g / cm ³The ultra-high molecular weight poly of (2) above
Corresponds to olefin composition] at 250 ° C
Delaminated and graft-modified polyolefin elastomer
(A) Layer thickness is 1.0 mm, ultra high molecular weight polyethylene
Except that a laminate having a thickness of 0.1 mm was obtained.
The procedure was as in Example 1.

The results are shown in Table 1. The dynamic friction coefficient of the ultra high molecular weight polyethylene layer constituting the laminate is 0.15
Met.

[0101]

[Comparative Example 1] In Example 1, instead of the ultra high molecular weight polyethylene film, a polyamide sheet [Toray Industries, Inc.
Made nylon 6, 0.1 mm thick], the thickness of the graft-modified polyolefin elastomer (a) layer is 1.0 m
m and the thickness of the polyamide layer was 0.1 mm, except that a laminated body was obtained.

The results are shown in Table 1. The coefficient of dynamic friction of the surface of the polyamide layer constituting the laminate was 0.8.

[0103]

[Table 1]

Claims (6)

[Claims] (1) 95 to 10 parts by weight of a peroxide-crosslinking olefin-based copolymer rubber (a) and 5 to 90 parts by weight of (b) an olefin-based plastic [the total amount of components (a) and (b) is 100). Parts by weight] and (c) 0.01 to 10 parts by weight of an α, β-unsaturated carboxylic acid or derivative thereof, or an unsaturated epoxy monomer in the presence of an organic peroxide. A thermoplastic elastomer comprising a layer composed of a graft-modified polyolefin elastomer (A) which is dynamically heat-treated and partially crosslinked, and a layer composed of an ultrahigh molecular weight polyolefin (B). Laminate. 2. The graft-modified polyolefin elastomer (A) comprises 5 to 100 parts by weight of (d) a non-crosslinking peroxide type rubber-like substance based on 100 parts by weight of the total of the components (a) and (b). Part and / or (e)
The thermoplastic elastomer laminate according to claim 1, which contains 3 to 100 parts by weight of a mineral oil-based softening agent. 3. The (a) peroxide cross-linking olefin-based copolymer rubber is 95-60 parts by weight, and the (b) olefin-based plastic is 5-40 parts by weight [components (a) and (b). The total amount of) is 100 parts by weight]. 3. The thermoplastic elastomer laminate according to claim 1, wherein 4. The ultra high molecular weight polyolefin (B) comprises:
Intrinsic viscosity [η] measured in decalin solvent at 135 ℃ is 1
The thermoplastic elastomer laminate according to any one of claims 1 to 3, which is an ultrahigh molecular weight polyolefin in the range of 0 to 40 dl / g. 5. The ultra high molecular weight polyolefin (B) comprises:
Intrinsic viscosity [η] measured in decalin solvent at 135 ℃ is 1
From an ultra-high molecular weight polyolefin in the range of 0 to 40 dl / g and a low molecular weight or high molecular weight polyolefin having an intrinsic viscosity [η] measured in a decalin solvent of 135 ° C. in the range of 0.1 to 5 dl / g A polyolefin composition consisting essentially of an ultra high molecular weight polyolefin, wherein the ultra high molecular weight polyolefin is 15% based on 100% by weight of the total weight of the ultra high molecular weight polyolefin and the low to high molecular weight polyolefin.
-40 wt% and has an intrinsic viscosity [η] measured in a 135 ° C decalin solvent of 3.5 to 8.3 dl.
The thermoplastic elastomer laminate according to any one of claims 1 to 3, which is an ultrahigh molecular weight polyolefin composition in the range of / g. 6. The ultra high molecular weight polyolefin is 135
The intrinsic viscosity [η] measured in a decalin solvent at 10 ° C is 10 to 4
Ultra-high molecular weight polyolefin in the range of 0 dl / g and intrinsic viscosity [η] measured in 135 ° C decalin solvent
Is a polyolefin composition consisting essentially of a low molecular weight or high molecular weight polyolefin in the range of 0.1 to 5 dl / g, wherein the ultra high molecular weight polyolefin comprises an ultra high molecular weight polyolefin and a low molecular weight or high molecular weight polyolefin. In an amount of 15 to 40% by weight based on the total weight of 100% by weight, and the intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. is in the range of 3.5 to 8.3 dl / g. An ultrahigh molecular weight polyolefin composition and an ultrahigh molecular weight polyolefin composition comprising 1 to 20% by weight of the liquid or solid lubricating oil based on the ultrahigh molecular weight polyolefin composition. The thermoplastic elastomer laminate according to any one of items 1 to 3.