JP3110141B2 - Thermoplastic elastomer laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. 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 automotive interior materials and sealing materials.

[0002]

BACKGROUND OF THE INVENTION Conventionally, glass run channels, which are one of the important sealing materials used in automobiles, include (1)
A composite material comprising a vulcanized rubber mainly composed of an ethylene-propylene-diene copolymer rubber excellent in weather resistance and heat resistance, an adhesive and a nylon fiber, (2) the vulcanized rubber and abrasion resistance Composite material consisting of an adhesive with excellent properties,
(3) Soft polyvinyl chloride for profile extrusion molding is used.

The above-mentioned composite materials (1) and (2) are based on a vulcanized ethylene / propylene / diene copolymer rubber having excellent weather resistance and heat resistance.
Excellent heat resistance and dimensional stability. However,
The manufacturing process of these composite materials is ethylene, propylene,
It consists of a kneading process of a diene copolymer rubber and a filler, an extrusion molding process, a surface buffing process, an adhesive application process, a drying process and a fiber flocking process, and is very complicated. On the other hand, since the above-mentioned composite material (3) is manufactured by extrusion molding of soft polyvinyl chloride, 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 above-mentioned 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.
There has been a demand for a laminate that can be used effectively for applications such as automotive interior materials and sealing materials.

[0005]

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

[0006]

SUMMARY OF THE INVENTION A thermoplastic elastomer laminate according to the present invention comprises a thermoplastic elastomer (A) layer composed of a crystalline polyolefin and rubber, and an ultrahigh molecular weight polyolefin composition (B) layer. The ultrahigh molecular weight polyolefin composition (B) having an intrinsic viscosity [η] of 5 to 40 dl / g measured in a decalin solvent at 135 ° C., and the thermoplastic elastomer (A) Wherein the ultrahigh molecular weight polyolefin is 1% based on 100% by weight of the total weight of the ultrahigh molecular weight polyolefin and the thermoplastic elastomer (A).
5 to 40% by weight, and the melt flow rate of the ultrahigh molecular weight polyolefin composition (B) (230
C., 2.16 kg load) is 5 g / 10 minutes or less.

The thermoplastic elastomer (A) preferably used in the present invention comprises 70 to 10 parts by weight of a crystalline polypropylene (a) and ethylene-propylene copolymer rubber or ethylene-propylene-diene copolymer rubber. 30 to 90 parts by weight of rubber (b) [component (a)
And the total amount of (b) is 100 parts by weight], and the rubber (b) is obtained by dynamically heat-treating the mixture in the presence of an organic peroxide. Elastomers.

[0008]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the thermoplastic elastomer laminate according to the present invention will be specifically described. The thermoplastic elastomer laminate according to the present invention comprises a thermoplastic elastomer (A) layer and an ultrahigh molecular weight polyolefin composition (B).
And layers.

Thermoplastic Elastomer (A) The thermoplastic elastomer (A) used in the present invention comprises a crystalline polyolefin and a rubber.

The crystalline polyolefin used in the present invention includes a homopolymer or copolymer of an α-olefin having 2 to 20 carbon atoms. Specific examples of the crystalline polyolefin include the following (co) polymers. (1) Ethylene homopolymer (The production method may be either a low-pressure method or a high-pressure method.) (2) Copolymerization of ethylene with 10 mol% or less of other α-olefins or vinyl monomers such as vinyl acetate and ethyl acrylate. Polymer (3) Propylene homopolymer (4) Random copolymer of propylene and 10% or less of other α-olefin (5) Block copolymer of propylene and 30% or less of other α-olefin (6) 1-butene homopolymer (7) Random copolymer of 1-butene and 10% by mole or less of other α-olefin (8) 4-methyl-1-pentene homopolymer (9) 4 -Methyl-1-pentene and less than 20 mol% of other α
-Random copolymer with olefin As the α-olefin, specifically, ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-
Hexene, 1-octene and the like.

The rubber used in the present invention is not particularly limited, but is preferably an olefin copolymer rubber. The olefin-based copolymer rubber has 2 to 20 carbon atoms.
Amorphous random elastic copolymer containing α-olefin as a main component, which is an amorphous α-olefin copolymer composed of two or more α-olefins and non-conjugated with two or more α-olefins Α-olefin / non-conjugated diene copolymer comprising diene.

Specific examples of such an olefin copolymer rubber include the following rubbers. (1) Ethylene / α-olefin copolymer rubber [ethylene / α-olefin (molar ratio) = about 90/10 to 50/50] (2) Ethylene / α-olefin / non-conjugated diene copolymer rubber [ethylene / Α-olefin (molar ratio) = about 90/10 to 50/50] (3) Propylene / α-olefin copolymer rubber [propylene / α-olefin (molar ratio) = about 90/10 to 50/50] (4) Butene / α-olefin copolymer rubber [butene / α-olefin (molar ratio) = about 90/10 to 50/50] As the α-olefin, specifically, the above-mentioned crystalline polyolefin is used. The same α-olefin as the specific examples of the constituent α-olefin may be mentioned.

As the non-conjugated diene, specifically,
Examples thereof include dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, and ethylidene norbornene.

The Mooney viscosity ML of these copolymer rubbers
_{1 + 4} (100 ° C.) is from 10 to 250, especially from 40 to 150
Is preferred. The iodine value when the non-conjugated diene is copolymerized is preferably 25 or less.

The above-mentioned olefin copolymer rubber can exist in the thermoplastic elastomer in all cross-linked states such as uncross-linked, partially cross-linked, and totally cross-linked. Preferably it is present.

The rubber used in the present invention includes:
In addition to the above olefin copolymer rubber, other rubber,
For example, styrene-butadiene rubber (SBR), nitrile rubber (NBR), natural rubber (NR), butyl rubber (I
IR) and the like, diene rubbers, SEBS, polyisobutylene and the like.

In the thermoplastic elastomer used in the present invention, the weight ratio of the crystalline polyolefin to the rubber (crystalline polyolefin / rubber) is usually from 90/10.
The range is 5/95, preferably 70/30 to 10/90.

When an olefin copolymer rubber and another rubber are used in combination as the rubber, the other rubber has a total amount of crystalline polyolefin and rubber of 1%.
40 parts by weight or less, preferably 5 to 100 parts by weight
It is blended at a ratio of 20 parts by weight.

The thermoplastic elastomer preferably used in the present invention comprises crystalline polypropylene, ethylene-α-
It consists of an olefin copolymer rubber or an ethylene / α-olefin / non-conjugated diene copolymer rubber, exists in a thermoplastic elastomer in a partially cross-linked state, and has a weight blend of crystalline polypropylene and rubber. The ratio (crystalline polypropylene / rubber) is 70 / 30-1
It is in the range of 0/90.

If necessary, additives such as a mineral oil softener, a heat stabilizer, an antistatic agent, a weather stabilizer, an antioxidant, a filler, a coloring agent and a lubricant may be added to the thermoplastic elastomer. Can be blended within a range that does not impair the object of the present invention.

More specific examples of the thermoplastic elastomer preferably used in the present invention include: 60 to 10 parts by weight of a crystalline polypropylene (a), an ethylene / propylene copolymer rubber or an ethylene / propylene / diene copolymer. 40 to 90 parts by weight of rubber (b) made of rubber [total amount of components (a) and (b) is 100 parts by weight]
And a rubber (c) other than the rubber (b) and / or 5-100 parts by weight of a mineral oil-based softener (d), which is dynamically heat-treated in the presence of an organic peroxide to obtain a mixture. A thermoplastic elastomer obtained by partially cross-linking the rubber (b) is exemplified.

As the above-mentioned organic peroxide, specifically, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy)
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-butylperoxybenzoate, tert-butylperbenzoate, tert-butylperoxyisopropyl carbonate, Diacetyl peroxide, lauroyl peroxide, tert-butylcumyl peroxide and the like.

Of these, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane and 2,5-dimethyl-2,5-di-, in terms 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 1,3-bis (tert-butylperoxyisopropyl) benzene is most preferred.

In the present invention, the organic peroxide is
It is used in an amount of 0.05 to 3% by weight, preferably 0.1 to 1% by weight, based on 100% by weight of the total amount of the crystalline polyolefin and the rubber.

In the partial crosslinking treatment with the above organic peroxide, sulfur, p-quinonedioxime, p, p'-dibenzoylquinonedioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, triphenyl Peroxy crosslinking aids such as methylolpropane-N, N'-m-phenylenedimaleimide, or divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate , Polyfunctional methacrylate monomers such as allyl methacrylate, and polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate.

By using a compound as described above,
A uniform and mild crosslinking reaction can be expected. Particularly, in the present invention, divinylbenzene is most preferred. Divinylbenzene is easy to handle, has good compatibility with the crystalline polyolefin and rubber, which are the main components of the above-mentioned crosslinked product, and has an action of solubilizing the organic peroxide. Therefore, a thermoplastic elastomer having a uniform cross-linking effect by heat treatment and a good balance between fluidity and physical properties can be obtained.

The above-mentioned cross-linking aid or polyfunctional vinyl monomer is used for the whole of the above-mentioned cross-linked material.
It is preferably used in a proportion of 0.1 to 2% by weight, particularly 0.3 to 1% by weight. If the compounding ratio of the crosslinking aid or the polyfunctional vinyl monomer exceeds 2% by weight, the crosslinking reaction proceeds too quickly if the compounding amount of the organic peroxide is large, so that the obtained thermoplastic elastomer has poor fluidity. On the other hand, when the blending amount of the organic peroxide is small, the crosslinking aid and the polyfunctional vinyl monomer remain as unreacted monomers in the thermoplastic elastomer, and the thermoplastic elastomer becomes hot during processing and molding. Changes in physical properties due to history may occur. Therefore, the co-agent and the polyfunctional vinyl monomer should not be compounded in excess.

The term "dynamically heat-treating" refers to kneading the above components in a molten state. 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, or the like is used. Of these, a non-open type kneading apparatus 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 170
To 240 ° C., and the kneading time is 1 to 20 minutes, preferably 3 to 10 minutes. The applied shear force is
The shear rate is 10 sec ^-1 or more, preferably 100 to
It is determined within the range of 10,000 sec ^-1 .

The preferred thermoplastic elastomer used in the present invention is partially crosslinked, and the term "partially crosslinked" refers to a gel having a gel content of 20 to 98% as measured by the following method. In the present invention, the gel content is preferably in the range of 40 to 98%.

[Measurement Method of Gel Content] About 100 mg of a thermoplastic elastomer pellet was weighed as a sample, and a sufficient amount of 30 ml for the pellet was placed in a closed container.
In cyclohexane at 23 ° C. for 48 hours.

Next, this sample is taken out on a filter paper and dried at room temperature for 72 hours or more until the weight becomes constant. The gel content is represented by the following equation. Gel content [%] = (dry weight after cyclohexane immersion)
÷ (weight before immersion in cyclohexane) × 100 The thermoplastic elastomer (A) constituting one layer of the thermoplastic elastomer laminate according to the present invention is composed of crystalline polyolefin and rubber, and thus has excellent fluidity.

[0033] Specific examples of ultra high molecular weight polyolefin composition (B) ultra high molecular weight polyolefin composition (B) used in the present invention include the ultra-high molecular weight polyolefin composition as follows.

(1) The intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. is 5 to 40 dl / g, preferably 15 to 40 dl / g.
Consisting essentially of an ultra-high molecular weight polyolefin in the range of 35 dl / g and a thermoplastic elastomer (A),
The ultrahigh molecular weight polyolefin is present in a proportion of 15 to 40% by weight based on 100% by weight of the total weight of the ultrahigh molecular weight polyolefin and the thermoplastic elastomer (A), and the melt flow rate of the ultrahigh molecular weight polyolefin composition (Based on MFR, ASTM D 1238, 230 ° C,
2.16 kg load) is 5 g / 10 min or less, preferably 1
g / 10 minutes or less, more preferably 0.2 g / 10 minutes or less.

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

The ultrahigh molecular weight polyolefin as described above includes, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene, It consists of a homopolymer or copolymer of α-olefin such as 3-methyl-1-pentene. In the present invention, an ethylene homopolymer and a copolymer containing ethylene as a main component and comprising ethylene and another α-olefin are preferred.

The thermoplastic elastomer (A) constituting these ultrahigh molecular weight polyolefin compositions is the same as the thermoplastic elastomer (A) described above, and is composed of crystalline polyolefin and rubber.

As the liquid lubricating oil used in the composition (2), petroleum-based lubricating oils, synthetic lubricating oils 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, cylinder oil, and the like.

Specific examples of the synthetic lubricating oil include synthetic hydrocarbon oil, polyglycol oil, polyphenyl ether oil, ester oil, phosphate ester oil, polychlorotrifluoroethylene oil, fluoroester oil, chlorinated biphenyl oil. Oil, silicone oil and the like are used.

As the solid lubricating oil used in the composition (2), graphite and molybdenum disulfide are mainly used. In addition, boron nitride, tungsten disulfide and lead oxide are also used. , Glass powder, metal soap, etc. can also be used. The solid lubricating oil can be used alone or in combination with a liquid lubricating oil. For example, the solid lubricating oil can be blended with the ultrahigh molecular weight polyolefin in the form of a powder, a sol, a gel, a suspensoid or the like.

The above ultrahigh molecular weight polyolefin composition may contain, if necessary, mineral oil softeners, heat stabilizers, antistatic agents, weathering stabilizers, antioxidants, fillers, coloring agents, lubricants and the like. Additives can be incorporated within a range that does not impair the purpose of the present invention.

The ultra-high molecular weight polyolefin compositions of the above (1) and (2) are
It can be obtained by dynamically heat-treating the thermoplastic elastomer (A) and the other components used as necessary. Here, “dynamically heat-treating” refers to kneading the above components in a molten state.

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, or the like is used. Of these, a non-open type kneading apparatus is preferable, and kneading is preferably performed in an atmosphere of an inert gas such as nitrogen gas or carbon dioxide gas.

The ultrahigh molecular weight polyolefin compositions (B) of (1) and (2) can be co-extruded and laminated with the thermoplastic elastomer (A). In production, the thermoplastic elastomer layer and the ultrahigh molecular weight polyolefin composition layer can be directly laminated without going through a film (sheet) molding step, which is economical.

On the other hand, the ultra-high molecular weight polyolefin alone, for example, the ultra-high molecular weight polyolefin alone having an intrinsic viscosity [η] of 5 to 40 dl / g measured in a decalin solvent at 135 ° C. in the above (1), requires only the thermoplastic Coextrusion lamination with the elastomer (A) cannot be performed, and therefore, at the time of laminating the thermoplastic elastomer layer and the ultra-high molecular weight polyolefin layer, at least one of them must be formed into a film (sheet) in advance. Yes, it is economically inferior to the case of the ultrahigh molecular weight polyolefin composition.

Thermoplastic Elastomer Laminate The thermoplastic elastomer laminate according to the present invention comprises a layer composed of the above thermoplastic elastomer (A) and a layer composed of the above ultrahigh molecular weight polyolefin composition (B). It is composed of The thermoplastic elastomer laminate according to the present invention can be obtained by laminating the above two layers.

The method of laminating the thermoplastic elastomer (A) layer (hereinafter abbreviated as (A) layer) and the ultra-high molecular weight polyolefin composition (B) layer (hereinafter abbreviated as (B) layer) is performed by the following method. Although it depends on the size and required physical properties and is not particularly limited, for example, the following laminating methods can be mentioned.

(1) A method of thermally fusing the previously formed layers (A) and (B) at a temperature higher than the temperature at which at least one of the layers is melted, using a calender roll forming machine, a compression molding machine, or the like. .

[0049] (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 extruded by a multilayer extruder and thermally fused (co-extrusion).

In the present invention, the thickness of the layer (A) is 0.1.
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, since the thermoplastic elastomer (A) layer is composed of crystalline polyolefin and rubber, it has excellent heat resistance, heat aging resistance, and rubber elasticity.

In the thermoplastic elastomer laminate according to the present invention, the ultrahigh molecular weight polyolefin composition (B) layer is excellent in abrasion resistance, scratch resistance, slidability and chemical resistance.

[0052]

The thermoplastic elastomer laminate according to the present invention has remarkably excellent interlayer adhesion between the thermoplastic elastomer (A) layer and the ultrahigh molecular weight polyolefin composition (B) layer. Further, the thermoplastic elastomer laminate according to the present invention is lighter in weight than a conventional composite material composed of vulcanized rubber and nylon fibers, or soft polyvinyl chloride, and has a sticky surface due to oozing out of a plasticizer and the like. Moreover, it is excellent in mechanical strength, heat resistance, heat aging resistance, weather resistance, abrasion resistance, scratch resistance, slidability and dimensional stability.

Therefore, the thermoplastic elastomer laminate according to the present invention can be used not only for automotive interior materials and sealing materials (especially glass run channels, belt line moldings, etc., which are required to have sliding properties with glass), but also Furniture, building materials,
Household appliances, bags, suitcases, sports equipment,
It can also be used effectively for office supplies and miscellaneous goods.

Hereinafter, the present invention will be described with reference to Examples.
The present invention is not limited to these examples.

[0055]

Example 1 Ethylene content 70 mol%, iodine value 1
2. 80 parts by weight of an ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber (hereinafter abbreviated as EPDM (1)) having a Mooney viscosity of ML _{1 + 4} (100 ° C.) 120;
MFR (ASTM D 1238-65T, 230 ° C)
13 g / 10 min, 20 parts by weight of polypropylene (hereinafter abbreviated as PP (1)) having a density of 0.91 g / cm ³ were mixed at a temperature of 180 ° C. in a nitrogen atmosphere at 180 ° C. using a Banbury mixer.
After kneading for minutes, the kneaded material was passed through a roll to form a sheet, which was cut with a sheet cutter to produce square pellets.

Next, this square pellet and 1,3-bis (t
0.3 parts by weight of tert-butylperoxyisopropyl) benzene [hereinafter abbreviated as peroxide (A)] and 0.5 part by weight of divinylbenzene [hereinafter abbreviated as DVB] were stirred and mixed with a Henschel mixer.

Next, this mixture was extruded at 220 ° C. in a nitrogen atmosphere using a single screw extruder having an L / D of 30 and a screw diameter of 50 mm to obtain a thermoplastic elastomer (a).

Then, the gel content of the copolymer rubber in the obtained thermoplastic elastomer (a) was measured by the above method. Table 1 shows the results. Further, the obtained thermoplastic elastomer (a) was compression-molded at 190 ° C. to prepare a sheet for measuring physical properties, and the tensile break stress (T _B ), torsional rigidity (flexibility) and melt flow rate (moldability) were measured. ) Was tested according to the following method.

The results are shown in Table 1. [Test Method] (1) Tensile breaking stress (T _B ) 200 mm / min according to JIS K6301
Tensile strength at break at a tensile speed of (T _B : kgf / unit
cm ² ) was measured.

(2) Torsional rigidity (flexibility) Torsional rigidity (unit: kgf / cm ² ) was determined in accordance with ASTM D1043, and the torsional rigidity was used as a measure of flexibility.

(3) Melt flow rate (moldability) Melt flow rate (MFR: unit g / 10 minutes, 230 ° C., 2.16 k) according to ASTM D1238
g) was determined, and the melt flow rate was used as a measure of moldability.

Next, the obtained thermoplastic elastomer (a) was extruded at a temperature of 230 ° C., and an ultrahigh molecular weight having an intrinsic viscosity [η] of 28 dl / g measured in a decalin solvent at 135 ° C. was formed on the surface thereof. Ultrahigh molecular weight polyethylene composition [MFR] obtained by dynamically heat-treating 23% by weight of polyethylene and 77% by weight of the obtained thermoplastic elastomer (a) in a Banbury mixer.
(230 ° C., 2.16 kg load) is 0.1 g / 10 min or less, and the density is 0.90 g / cm ³ ] at 250 ° C., and the thermoplastic elastomer (a) layer is 1.0 mm thick. A co-extruded laminate having an ultrahigh molecular weight polyethylene composition layer thickness of 0.1 mm was obtained.

With respect to the obtained laminate, the interlayer adhesive strength was measured according to the following method. Table 1 shows the results. [Interlayer adhesive strength test] Test method: 180 degree peeling Test piece: width 25 mm, length 100 mm Peeling speed: 25 mm / min Interlayer adhesive strength: value obtained by dividing the peeling load by the width of the test piece (unit: kgf / cm)

[0064]

Example 2 Example 1 was repeated except that the thermoplastic elastomer (b) was produced without using the peroxide (A) and DVB.

The ultra-high molecular weight polyethylene composition has the following composition:
When the intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. is 2
8 dl / g of ultra high molecular weight polyethylene 23% by weight and the thermoplastic elastomer (b) 77% by weight,
MFR is 0.1 g / 10 min or less and density is 0.90
g / cm ³ .

Table 1 shows the results.

[0067]

Example 3 In Example 1, in addition to EPDM (1) and PP (1), butyl rubber [IIR, manufactured by Esso Corporation]
-065, degree of unsaturation 0.8 mol%, hereinafter, IIR (1)
[Abbreviation] and 10 parts by weight of paraffin-based process oil [Diana Process Oil manufactured by Idemitsu Kosan Co., Ltd.] to produce thermoplastic elastomer (c).

The ultra-high molecular weight polyethylene composition comprises:
When the intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. is 2
8 dl / g of ultra-high molecular weight polyethylene 23% by weight and the thermoplastic elastomer (c) 77% by weight,
MFR is 0.1 g / 10 min or less and density is 0.90
g / cm ³ .

Table 1 shows the results.

[0070]

Example 4 Paraffin-based process oil is 40 PHR
Oil-extended ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber [ethylene content 78 mol%,
Iodine value 13, Mooney viscosity ML _{1 + 4} (100 ° C) 7
5, hereinafter abbreviated as EPDM (2)], 64 parts by weight and MF
R (ASTM D 1238-65T, 230 ° C) 11
g / 10 minutes, polypropylene having a density of 0.91 g / cm ³ [hereinafter abbreviated as PP (2)] 14 parts by weight, butyl rubber [Mooney viscosity ML _{1 + 4} (100 ° C.) 45, degree of unsaturation 1.0 mol] %, Hereinafter abbreviated as IIR (2)] 14 parts by weight and 8 parts by weight of a paraffinic process oil are kneaded at 180 ° C. for 5 minutes in a nitrogen atmosphere using a Banbury mixer, and the kneaded material is rolled. To form a sheet, which was cut with a sheet cutter to produce square pellets.

Next, the square pellets and a solution obtained by dissolving and dispersing 0.4 parts by weight of peroxide (A) in 0.4 parts by weight of DVB were stirred and mixed by a tumbler blender, and the solution was uniformly spread on the surface of the square pellets. Attached.

Next, the pellets were extruded using an extruder.
The mixture was extruded at 210 ° C. in a nitrogen atmosphere to obtain a pellet-shaped thermoplastic elastomer (d). Hereinafter, it carried out similarly to Example 1. The ultra-high molecular weight polyethylene composition has 1
The intrinsic viscosity [η] measured in a decalin solvent at 35 ° C. is 28
dl / g of 23% by weight of ultrahigh molecular weight polyethylene and 77% by weight of the thermoplastic elastomer (d),
FR is 0.1 g / 10 min and density is 0.89 g / c
m ³ .

Table 1 shows the results.

[0074]

Example 5 In Example 1, instead of 80 parts by weight of EPDM (1) and 20 parts by weight of PP (1), an ethylene content of 82 mol%, an iodine value of 9, and a Mooney viscosity of ML _{1 + 4 were used.}
(100 ° C.) 25 ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber [hereinafter referred to as EPDM
(Abbreviated as (3)] 40 parts by weight, and MFR (ASTM
D1238-65T, 230 ° C.) polypropylene having a density of 0.91 g / cm ³ and a density of 0.91 g / cm ³ [hereinafter, PP
(Abbreviated as (3))], and the compounding amounts of peroxide (A) and DVB were each 0.2 parts by weight,
A thermoplastic elastomer (e) was obtained in the same manner as in Example 1 except that the amount was changed to 0.3 part by weight.

Then, regarding the obtained thermoplastic elastomer (e), the gel content, the tensile stress at break (T _B ),
The torsional stiffness and melt flow rate were tested as in Example 1.

Table 1 shows the results. Next, the obtained thermoplastic elastomer (e) is extruded at a temperature of 180 ° C., and an ultrahigh molecular weight polyethylene having an intrinsic viscosity [η] of 7.2 dl / g measured in a decalin solvent at 135 ° C. is formed on the surface thereof. Ultra-high molecular weight polyethylene composition [MFR (230 ° C., 2.16 kg load) obtained by dynamically heat-treating 18% by weight and 82% by weight of the obtained thermoplastic elastomer (e) in a Banbury mixer. )
Is 0.2 g / 10 min and the density is 0.88 g / cm ³ ].
Coextrusion lamination was performed at 30 ° C. to obtain a coextrusion laminate in which the thickness of the thermoplastic elastomer (e) layer was 1.0 mm and the thickness of the ultrahigh molecular weight polyethylene composition layer was 0.1 mm.

With respect to the obtained laminate, the interlayer adhesive strength was measured in the same manner as in Example 1. Table 1 shows the results.

[0078]

[Table 1]

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Kyoko Kobayashi 3 Chigusa Coast, Ichihara-shi, Chiba Mitsui Petrochemical Industry Co., Ltd. (56) References JP-A-5-170934 (JP, A) 2-220844 (JP, A) JP-A-2-89639 (JP, A) JP-A-59-194841 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B32B 1/00 -35/00

Claims (3)

(57) [Claims] 1. An ultrahigh molecular weight polyolefin composition (B) comprising a thermoplastic elastomer (A) layer composed of a crystalline polyolefin and rubber, and an ultrahigh molecular weight polyolefin composition (B) layer. ) Is the intrinsic viscosity [η] 5 measured in a decalin solvent at 135 ° C.
An ultrahigh molecular weight polyolefin substantially in the range of 40 dl / g and the thermoplastic elastomer (A), wherein the ultrahigh molecular weight polyolefin is the total weight of the ultrahigh molecular weight polyolefin and the thermoplastic elastomer (A) It is present at a ratio of 15 to 40% by weight with respect to 100% by weight, and the melt flow rate (230 ° C., 2.16 kg load) of the ultrahigh molecular weight polyolefin composition (B) is 5 g / 10 minutes or less. A thermoplastic elastomer laminate characterized by the following. 2. A rubber (b) wherein said thermoplastic elastomer (A) comprises 70 to 10 parts by weight of crystalline polypropylene (a) and ethylene-propylene copolymer rubber or ethylene-propylene-diene copolymer rubber. 30
-90 parts by weight [total of components (a) and (b) is 1
Wherein the rubber (b) is a partially crosslinked thermoplastic elastomer obtained by dynamically heat-treating a mixture of the rubber and the rubber (b) in the presence of an organic peroxide. Item 4. The thermoplastic elastomer laminate according to Item 1. 3. The ultrahigh molecular weight polyolefin composition (B) contains 1 to 20% by weight of a liquid or solid lubricating oil based on the ultrahigh molecular weight polyolefin composition (B). Item 3. The thermoplastic elastomer laminate according to Item 1 or 2.