JPH0740508A - Olefinic rubber laminate - Google Patents

Abstract

PURPOSE:To obtain excellent weatherability, heat resistance, dimensional stability, sealability, abrasion resistance and slidability, in a laminate consisting of an olefinic vulcanized rubber layer and a B-layer of an ultrahigh mol.wt. polyolefin composition, by adding specific ultrahigh mol.wt. polyolefin and specific polyolefin to the B-layer. CONSTITUTION:An olefinic rubber laminate is constituted of an olefinic vulcanized rubber layer and a B-layer and the B-layer substantially consists of ultrahigh mol.wt. polyolefin whose intrinsic viscosity eta measured in a decalin solvent at 135 deg.C is 10-40dl/g and polyolefin whose intrinsic viscosity eta measured in a decalin solvent at 135 deg.C is 0.1-5dl/g. Ultrahigh mol.wt. polyolefin is contained in a ratio of 15-40wt.% with respect to 100wt.% of the total wt. of ultrahigh mol.wt. polyolefin and polyolefin. The intrinsic viscosity eta measured in a decalin solvent at 135 deg.C of the B-layer is set to 3.5-8.3dl/g.

Description

Detailed Description of the Invention

[0001]

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

[0002]

BACKGROUND OF THE INVENTION Conventionally, glass run channel, which is one of the important sealing materials used in automobiles, has weather resistance,
In addition to the sealing property, high wear resistance and slidability are required for the part that comes into contact with the glass. Therefore, the material for the glass run channel is (1) a composite consisting 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. Material, (2) a composite material composed of a vulcanized rubber containing ethylene / propylene / diene copolymer rubber as a main component, and an adhesive having excellent wear resistance, and (3) a soft polyvinyl chloride for profile extrusion molding. Can be mentioned.

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,
In the composite material (1), nylon short fibers are planted so that the abrasion resistance and the slidability are good, but when the short nylon fibers are planted, the surface treatment of the base rubber and the adhesive Since the work of applying and uniformly flocking nylon short fibers is required, the flocking process is complicated, and rainwater is easily retained in the flocked part, and this rainwater freezes in winter and glass slides. There is a problem of disappearing. on the other hand,
Since the composite material (2) requires various operations such as buffing the base rubber, degreasing, primer coating, adhesive coating, and heat curing treatment, the composite material (2) is manufactured in the same manner as the composite material (1). There is a problem that the process is complicated, and further, there is a problem that the abrasion resistance is insufficient.

Further, since the above composite material (3) is manufactured by subjecting soft polyvinyl chloride to profile extrusion molding, the manufacturing process is simplified, but the composite material (3) has heat resistance and dimensions. There is a problem that the stability is poor and the practical performance is inferior as compared with the composite materials (1) and (2).

Therefore, the advent of a laminate having excellent weather resistance, heat resistance, dimensional stability, sealability, abrasion resistance and slidability and capable of being manufactured by a simplified manufacturing process is desired. It is rare.

[0006]

It is an object of the present invention to solve the problems associated with the prior art as described above, and to improve weather resistance, heat resistance, dimensional stability, sealability, wear resistance and slidability. It is an object of the present invention to provide an olefin-based rubber laminate that is excellent and that can be manufactured by a simplified manufacturing process.

[0007]

The olefin rubber laminate according to the present invention is a laminate comprising an olefin vulcanized rubber (A) layer and an ultrahigh molecular weight polyolefin composition (B) layer. The high molecular weight polyolefin composition (B) is
Intrinsic viscosity [η] measured in decalin solvent at 135 ℃ is 1
Consisting essentially of an ultra high molecular weight polyolefin in the range of 0-40 dl / g and a polyolefin having an intrinsic viscosity [η] measured in a 135 ° C decalin solvent of 0.1-5 dl / g. The ultrahigh molecular weight polyolefin is present in a proportion of 15 to 40% by weight based on the total weight of the ultrahigh molecular weight polyolefin and the polyolefin of 100% by weight, and in the 135 ° C. decalin solvent of the ultrahigh molecular weight polyolefin composition (B). It is characterized in that the intrinsic viscosity [η] measured in step 3 is in the range of 3.5 to 8.3 dl / g.

The olefin-based vulcanizate (A) is a vulcanizate of an amorphous random elastic copolymer containing α-olefin having 2 to 20 carbon atoms as a main component. Is an amorphous α-olefin copolymer composed of two or more α-olefins, or an α-olefin / nonconjugated diene copolymer composed of two or more α-olefins and a non-conjugated diene. For example, ethylene
Vulcanized products such as propylene rubber and ethylene / butene rubber are preferably used.

In the present invention, particularly 100 parts by weight of the above-mentioned elastic copolymer, 5 to 40 parts by weight of low-density polyethylene having a melting point of 125 ° C. or less, and carbon black 10 are used.
A vulcanized product of a rubber composition comprising 0 to 200 parts by weight and 30 to 150 parts by weight of process oil is preferably used.

[0010]

DETAILED DESCRIPTION OF THE INVENTION The olefin rubber laminate according to the present invention will be specifically described below. The olefin rubber laminate according to the present invention is an olefin vulcanized rubber (A).
And an ultrahigh molecular weight polyolefin composition (B) layer.

Olefin-based vulcanized rubber (A) The olefin-based vulcanized rubber (A) preferably used in the present invention is an amorphous random elastic copolymer mainly containing an α-olefin having 2 to 20 carbon atoms. Or a vulcanized product of a rubber composition comprising the elastic copolymer and other components.

As such an amorphous random elastic copolymer, an amorphous α-olefin composed of two or more α-olefins is used.
-Olefin copolymer, an α-olefin / non-conjugated diene copolymer composed of two or more kinds of α-olefin and a non-conjugated diene, and the like.

Specific examples of the α-olefin include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene. Specific examples of the non-conjugated diene include dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene and ethylidene norbornene.

Specific examples of such a copolymer rubber include the following rubbers. (1) Ethylene / α-olefin copolymer rubber [ethylene / α-olefin (molar ratio) = about 90/10
To 50/50] (2) Propylene / α-olefin copolymer rubber [Propylene / α-olefin (molar ratio) = about 90/1
0-50 / 50] (3) Butene / α-olefin copolymer rubber [Butene / α-olefin (molar ratio) = about 90/10
50/50] (4) Ethylene / α-olefin / non-conjugated diene copolymer rubber [ethylene / α-olefin (molar ratio) = about 90/10
~ 50/50] The Mooney viscosity ML _{1 + 4} (100
C) is preferably 10 to 250, particularly preferably 40 to 150.
The iodine value of the α-olefin / non-conjugated diene copolymer rubber is preferably 25 or less.

As the olefin-based vulcanized rubber (A) used in the present invention, one kind of the above-mentioned copolymer rubber may be used, or two or more kinds thereof may be blended and used. This olefin-based vulcanized rubber (A) can be obtained by vulcanizing the above-mentioned copolymer rubber using a vulcanizing agent. This vulcanization is different from the vulcanization of ordinary rubber. Similarly, it is performed after once preparing an unvulcanized compounded rubber.

Examples of the vulcanizing agent include sulfur, organic peroxides, polyfunctional amines, polyols and triazine compounds. Examples of sulfur include pure sulfur, modified sulfur, and sulfur compounds that release active sulfur atoms in the vulcanization step.

In the present invention, sulfur is used in a proportion of 0.1 to 10 parts by weight, preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the elastic copolymer. Specific examples of the organic peroxide include dicumyl peroxide and dicumyl peroxide.
-tert-Butyl peroxide, 2,5-dimethyl-2,5-di- (t
ert-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-butyl peroxybenzoate,
Examples thereof include tert-butyl perbenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and tert-butyl cumyl peroxide.

In the present invention, the organic peroxide is
0.1-10 based on 100 parts by weight of the elastic copolymer
It is used in an amount of 0.5 part by weight, preferably 0.5 to 5 parts by weight. When sulfur is used as the vulcanizing agent, it is preferable to use a vulcanization accelerator together. As a vulcanization accelerator,
Specifically, N-cyclohexyl-2-benzothiazolsulfenamide, N-oxydiethylene-2-benzothiazolsulfenamide, N, N-diisopropyl-
2-Benzothiazole sulfenamide, 2-mercaptobenzothiazole, 2- (2,4-dinitrophenyl) mercaptobenzothiazole, 2- (2,6-diethyl-4-)
Thiazol compounds such as morpholinothio) benzothiazole and dibenzothiazyl disulfide; guanidine compounds such as diphenylguanidine, triphenylguanidine, diorsonitrile guanidine, orthonitrile biguanide, diphenylguanidine phthalate; acetaldehyde- Aniline reaction product, butyraldehyde-aniline condensate, hexamethylenetetramine, aldehyde amine such as acetaldehyde ammonia, or aldehyde-
Ammonia-based compound; 2-mercaptoimidazoline and other imidazoline-based compounds; Thiocarbanilide, diethylthiourea, dibutylthiourea, trimethylthiourea, diorsotolylthiourea and other thiourea-based compounds; tetramethylthiuram monosulfide, tetramethylthiuram disulfide, Thiuram compounds such as tetraethylthiuram disulfide, tetrabutylthiuram disulfide, pentamethylenethiuram tetrasulfide; zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate. , Sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, dimethyldithiocarbami Examples thereof include dithioate compounds such as telluric acid acid salts; xanthate compounds such as zinc dibutylxanthate; compounds such as zinc white. These vulcanization accelerators are used in an amount of 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the elastic copolymer.

When an organic peroxide is used as a vulcanizing agent, it is preferable to use a vulcanizing auxiliary together. Specific examples of the vulcanization aid include sulfur; quinonedioxime compounds such as p-quinonedioxime; polyethyleneglycol
Methacrylate compounds such as rudimethacrylate; allyl compounds such as diallyl phthalate and triallyl cyanurate; other maleimide compounds; and divinylbenzene. Such a vulcanization aid is used in an amount of 0.5 to 2 mol, preferably about equimolar, relative to 1 mol of the organic peroxide used.

In the present invention, when the above-mentioned olefin-based vulcanized rubber (A) is produced, the elastic copolymer 10 as described above is used.
It is desirable to use 5 to 30 parts by weight of low-density polyethylene having a melting point of 125 ° C. or less with respect to 0 parts by weight. When such low density polyethylene is used in the above proportion,
An olefin-based vulcanizate (A) having sufficient strength and excellent workability can be obtained.

As the low density polyethylene, polyethylene produced by a high pressure method or a medium and low pressure method is used. Specifically, a homopolymer consisting of ethylene alone, ethylene and propylene, 1-butene, 1-pentene,
Copolymers composed of 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene, 3-methyl-1-pentene and other α-olefins are used.

In the present invention, in addition to the above elastic copolymer and low density polyethylene, carbon black is used as a reinforcing material in a proportion of 50 to 150 parts by weight per 100 parts by weight of the above elastic copolymer. It is desirable to use. When carbon black is used in the above proportion,
An olefin-based vulcanized rubber (A) having high strength is obtained.

Specific examples of such carbon black include furnace black, channel black and the like, but SRF to FEF grade furnace black is particularly preferable.

As other reinforcing materials, silica, clay and calcium carbonate may be used if necessary. These reinforcing materials can be used alone or in combination.

In producing the olefin-based vulcanized rubber (A), in addition to the reinforcing material such as the elastic copolymer, low density polyethylene and carbon black, a softening agent is added to 100 parts by weight of the elastic copolymer. It is desirable to use it in a ratio of 30 to 150 parts by weight.

When the softening agent is used in the above proportion, an olefinic vulcanizate (A) having excellent processability can be obtained.
As a softening agent, various mineral oils usually used as process oils in rubber, for example, paraffin-based, naphthene-based,
Aromatic mineral oil, synthetic hydrocarbon oil, polyglycol oil,
Polyphenyl ether oil, ester oil, phosphate ester oil, polychlorotrifluoroethylene oil, fluoroester oil, chlorinated biphenyl oil, silicone oil and the like are used.

Among the above-mentioned softening agents, preferably paraffin-based process oil or naphthene-based process oil is added in an amount of 50 to 120 with respect to 100 parts by weight of the elastic copolymer.
It is recommended to use about parts by weight.

In addition, when the above olefin vulcanizate (A) is produced, an inexpensive extender may be added to reduce the compounding cost of the rubber. Specific examples of such extenders include heavy calcium carbonate, light calcium carbonate,
Cray etc. are mentioned.

Further, in the present invention, additives such as a heat resistance stabilizer, an antistatic agent, a weather resistance stabilizer, an antiaging agent, a colorant and a lubricant are added to the olefinic vulcanizate (A) as required. Can be added within a range that does not impair the object of the present invention.

[0030] 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 solvent of decalin at 135 ° C. is 10 to 40 dl / g, preferably 10
Ultra-high molecular weight polyolefin in the range of -30 dl / g and intrinsic viscosity [η] measured in 135 ° C decalin solvent is 0.1-5 dl / g, preferably 0.5-3 d.
consisting essentially of a polyolefin in the range of 1 / g, the ultrahigh molecular weight polyolefin being 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 polyolefin, and An ultrahigh molecular weight polyolefin composition in which the intrinsic viscosity [η] of the ultrahigh molecular weight polyolefin composition measured in a decalin solvent at 135 ° C. is in the range of 3.5 to 8.3 dl / g, preferably 5 to 8 dl / g .

(2) 1 to 20 per 100% by weight of the total amount of the above ultrahigh molecular weight polyolefin and polyolefin
An ultra-high molecular weight polyolefin composition comprising a weight percent of a liquid or solid lubricant.

Ultrahigh molecular weight polyolefins and polyolefins as described above include, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene,
It is composed of a homopolymer or copolymer of α-olefin such as 1-decene, 1-dodecene, 4-methyl-1-pentene, 3-methyl-1-pentene. In the present invention, ethylene homopolymers and ethylene-based copolymers composed of ethylene and other α-olefins are preferred.

As the liquid lubricating oil used in the composition (2), 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 the synthetic lubricating oil include synthetic hydrocarbon oil, polyglycol oil, polyphenyl ether oil, ester oil, phosphate ester oil, polychlorotrifluoroethylene oil, fluoroester oil and chlorinated biphenyl. Oil, silicone oil, etc. are used.

As the solid lubricating oil used in the composition (2) above, specifically, graphite and molybdenum disulfide are mainly used, but in addition, 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.

If necessary, the above ultrahigh molecular weight polyolefin composition may contain a mineral oil softener, a heat stabilizer, an antistatic agent, a weather stabilizer, an antiaging agent, a filler, a coloring agent, a lubricant, etc. Additives can be added within a range that does not impair the object of the present invention.

The ultrahigh molecular weight polyolefin composition (B) of the above (1) and (2) can be coextrusion laminated with the above olefinic vulcanized rubber (A), so that the olefinic rubber laminate of the present invention is laminated. When manufacturing the body, the olefin vulcanized rubber 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, an ultrahigh molecular weight polyolefin, for example, an ultrahigh molecular weight polyolefin having an intrinsic viscosity [η] measured in the solvent of decalin at 135 ° C. in the above (1) in the range of 10 to 40 dl / g is used alone. Coextrusion lamination processing with sulfur rubber (A) cannot be performed,
Therefore, when laminating the olefin-based vulcanized rubber layer and the ultrahigh molecular weight polyolefin layer, it is necessary to form the ultrahigh molecular weight polyolefin layer into a film (sheet) in advance. It is less economical than the others.

Olefin-based rubber laminate The olefin-based rubber laminate according to the present invention comprises a layer comprising the above-mentioned olefin-based vulcanized rubber (A) and a layer comprising the ultrahigh molecular weight polyolefin composition (B). Composed. The olefin rubber laminate according to the present invention can be obtained by laminating both the above layers.

The method for laminating the olefin-based vulcanized rubber (A) layer [hereinafter abbreviated as (A) layer] and the ultrahigh molecular weight polyolefin composition (B) layer [hereinafter abbreviated as (B) layer] is as follows. The method depends on the shape, size, and required physical properties and is not particularly limited, but examples thereof include the following laminating methods.

(1) A method of heat-sealing the preformed layers (A) and (B) using a calender roll molding machine, a compression molding machine or the like at a temperature higher than the melting temperature of the (B) layer. . (2) A method in which the (A) layer and the (B) layer are simultaneously extrusion-molded by a multilayer extrusion molding machine and heat-sealed (coextrusion molding).

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 olefin-based rubber laminate according to the present invention, the above-mentioned olefin-based vulcanized rubber (A) layer is very excellent in heat resistance, heat aging resistance and rubber elasticity.

Further, in the olefin rubber laminate according to the present invention, the above-mentioned ultrahigh molecular weight polyolefin composition (B) layer is excellent in abrasion resistance, scratch resistance, slidability and chemical resistance.

[0045]

The olefin rubber laminate according to the present invention has excellent interlayer adhesion between the olefin vulcanized rubber (A) layer and the ultrahigh molecular weight polyolefin composition (B) layer.
Further, the olefin rubber laminate according to the present invention has wear resistance and slidability equal to or higher than those of the conventional composite material composed of vulcanized rubber and nylon fiber, and yet retains moisture. There is no sticking of glass due to freezing. Further, the olefin rubber laminate according to the present invention has markedly superior wear resistance and slidability as compared with the composite material in which the surface of the vulcanized rubber is coated with the adhesive. Furthermore, the olefin-based rubber laminate according to the present invention has less stickiness on the surface due to leaching of a plasticizer and the like, as compared with soft polyvinyl chloride, and further has sealability, mechanical strength, heat resistance, and heat aging. It has excellent properties, weather resistance, abrasion resistance, scratch resistance, slidability and dimensional stability.

Therefore, the olefin rubber 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), It can also be effectively used for applications such as furniture, building materials, home appliances housings, suitcases, sports equipment, office supplies, and sundries.

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

[0048]

Example 1 Ethylene content 70 mol%, iodine value 1
2. 100 parts by weight of ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber [hereinafter referred to as EPDM] having a Mooney viscosity ML _{1 + 4} (100 ° C.) of 100 and a melting point of 106 ° C. polymerized by a high pressure method. , Density (ASTM D
1505) 0.921 g / cm ³ , MFR (ASTM
D 1238, 190 ° C, load 2.16kg) 1.6g
/ 10 min low-density polyethylene 20 parts by weight, stearic acid 1 part by weight, zinc white 5 parts by weight, FEF carbon black [Asahi Carbon Co., Ltd., trade name: Asahi 60] 150
80 parts by weight of paraffin oil [trade name: Diana Process Oil Pw-380, manufactured by Idemitsu Kosan Co., Ltd.] and 5 parts by weight of calcium oxide were kneaded for 5 minutes at 150 ° C. using a Banbury mixer. .

Next, the kneaded material thus obtained was mixed with 1.5 parts by weight of sulfur as a vulcanizing agent and MBT as a vulcanization accelerator with 100 parts by weight of EPDM [trade name: Nocceller M, Shin Ouchi Shinko]. Chemical Industry Co., Ltd.] 1.5 parts by weight, TeEDC [Product Name: Nox Cellar TTTE, Ouchi Shinko Chemical Industry Co., Ltd.] 0.5 parts by weight, ZnBDC [Product Name: Nox Cellar BZ, Ouchi Shinko Chemical Industry] Co., Ltd.]
5 parts by weight, 0.5 parts by weight of EU [trade name: Suncellar 22, manufactured by Sanshin Chemical Industry Co., Ltd.] and 0.5 parts by weight of DPTT [trade name: Noxceller TRA, manufactured by Ouchi Shinko Chemical Industry Co., Ltd.] Is added with a mixing roll and compound (a) is added.
Got

Then, the obtained compound (a) is
Using a 50 mm diameter T-die extrusion molding machine manufactured by Toshiba Machine Co., Ltd., screw is full flight, L / D = 28, T die is coat hanger die, extrusion temperature is 80 ° C., extrusion speed is 1.5 m / min. The sheet was extruded under the conditions of No. 1 and vulcanized for 5 minutes in a hot air vulcanizing tank at 250 ° C. Then, the ultra-high molecular weight polyethylene composition is extruded into a film at a temperature of 250 ° C. on the surface of the sheet-like vulcanized rubber in a molten state immediately after vulcanization, at a compound (a) extrusion speed of 1.5 m / min. Then, the vulcanized rubber and the ultra-high molecular weight polyethylene composition were laminated and passed through a pair of rolls and pressure-bonded to obtain an olefin-based rubber laminate.

The above ultrahigh molecular weight polyethylene composition has 1
Intrinsic viscosity [η] measured in decalin solvent at 35 ° C is 28
23% by weight of dl / g ultra high molecular weight polyethylene, 13
Intrinsic viscosity [η] measured in 5 ° C decalin solvent is 0.7
Consisting of 77 wt% of low-molecular-weight polyethylene of 3 dl / g, intrinsic viscosity [η] measured in decalin solvent at 135 ° C
Is 7.0 dl / g and the density is 0.965 g / cm ^3.
Is.

In the olefinic rubber laminate obtained as described above, the vulcanized product layer of the compound (a) had a thickness of 3.0 mm, and the ultrahigh molecular weight polyethylene composition layer had a thickness of 0.1 mm. there were.

With respect to the obtained laminate, the interlayer adhesive strength,
The dynamic friction coefficient and wear resistance (wear amount, change in surface condition of test piece) of the surface of the ultrahigh molecular weight polyethylene composition layer were tested according to the following methods.

[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) ) [Measurement Test of Dynamic Friction Coefficient] After measuring the weight of a 50 mm square test piece, it is set so that the surface of the test piece is in contact with the fixed horizontal glass surface. Then, after placing a weight adjusted to a weight of 1 kg with a cylinder having an outer diameter of about 50 mm in the center of the test piece, the test piece was moved parallel to the glass plate surface at a pulling speed of 100 mm / min. The maximum load (F ₁ ) is measured in the range in which the test piece moves 120 mm after being pulled and moved 30 mm, and the dynamic friction coefficient (μ) is determined from the following formula.

Μ = F ₁ [g] / (weight of test piece [g] + static load (1000 g)) The above glass plate is JIS R 3201 (a transparent plate glass defined as ordinary plate glass, which is reinforced, JIS
It is a normal plate tempered glass specified in R 3206 (tempered glass).

[Abrasion resistance test] Thickness 3.1 mm, length 2
After setting a 00 mm test piece in a horizontal wear tester, the chamfered end surface of the friction element below is pressed against the surface of the test piece to wear under a load of 1 kgf, an amplitude of 15 cm, and 60 cycles / min. The test was conducted.

Friction element: A glass plate having a width of 20 mm and a length of 45 mm, and one tip in the plane is rounded (R).
It has a semicircular shape with a length of 10 mm, and the end face of its tip is chamfered to have a radius (R) of 0.5 × (glass thickness).

Further, the Mooney viscosity ML _{1 + 4} (100 ° C.) of the compound (a) [unvulcanized rubber] is measured according to JIS K.
6300. Further, the compound (a) was press-vulcanized at 160 ° C. for 10 minutes to obtain a 2 mm vulcanized rubber sheet, and the tensile breaking point stress (T _B ) thereof was J
It was measured based on IS K 6301.

The results are shown in Table 1.

[0060]

[Comparative Example 1] In Example 1, the compound (a) of Example 1 was vulcanized in the same manner as in Example 1 to prepare a 3 mm thick ethylene-propylene rubber without using the ultra high molecular weight polyethylene composition. A vulcanized rubber sheet was obtained.

The vulcanized rubber sheet obtained as described above was tested for dynamic friction coefficient and abrasion resistance in the same manner as in Example 1. The results are shown in Table 1.

[0062]

Comparative Example 2 In Example 1, instead of the ultra high molecular weight polyethylene composition, a conventional high density polyethylene [copolymer of ethylene and propylene, ethylene content: 98 mol%, density (ASTM D 1505): 0. 957 g / c
m ³ , MFR (ASTM D1238, 190 ° C., load 2.16 kg): 0.05 g / 10 min] was used, and an olefin rubber laminate was obtained in the same manner as in Example 1.

Hereinafter, the same tests as in Example 1 were conducted.
The results are shown in Table 1.

[0064]

Comparative Example 3 Example 1 was repeated except that the ultrahigh molecular weight polyethylene having an intrinsic viscosity [η] of 28 dl / g measured in a decalin solvent at 135 ° C. was used in place of the ultrahigh molecular weight polyethylene composition. An attempt was made to obtain a laminate in the same manner as.

However, under the conditions of Example 1, this ultrahigh molecular weight polyethylene could not be extruded into a film.

[0066]

Example 2 A compound (b) was obtained in the same manner as in Example 1 except that the low density polyethylene which was a component of the compound (a) was not used. Hereinafter, an olefin rubber laminate was obtained in the same manner as in Example 1 except that this compound (b) was used instead of the compound (a).

The same test as in Example 1 was carried out on the obtained olefin rubber laminate. Further, the Mooney viscosity of the compound (b) and the tensile breaking point stress (T _B ) of the vulcanized rubber sheet made of the compound (b) were tested in the same manner as in Example 1.

The results are shown in Table 1.

[0069]

[Table 1]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Honma Sei 3 Chikusaigan, Ichihara, Chiba Mitsui Sekiyu Kagaku Kogyo Co., Ltd.

Claims (4)

[Claims] 1. A laminate comprising an olefin-based vulcanized rubber (A) layer and an ultrahigh molecular weight polyolefin composition (B) layer, wherein the ultrahigh molecular weight polyolefin composition (B) comprises: Intrinsic viscosity [η] measured in decalin solvent at 1 ℃ is 1
Consisting essentially of an ultra high molecular weight polyolefin in the range of 0-40 dl / g and a polyolefin having an intrinsic viscosity [η] measured in a 135 ° C decalin solvent of 0.1-5 dl / g. Ultra high molecular weight polyolefin is 1 based on 100% by weight of the total weight of the ultra high molecular weight polyolefin and the polyolefin.
The intrinsic viscosity [η] of the ultrahigh molecular weight polyolefin composition (B) measured in a decalin solvent at 135 ° C. is 3.5 to 8.3.
An olefin-based rubber laminate characterized by being in the range of dl / g. 2. The olefin-based vulcanized rubber (A) is a vulcanized product of an amorphous random elastic copolymer containing an α-olefin having 2 to 20 carbon atoms as a main component, and the elastic copolymer The combined product is an amorphous α-olefin copolymer composed of two or more α-olefins, or an α-olefin / nonconjugated diene copolymer composed of two or more α-olefins and a non-conjugated diene. The olefin-based rubber laminate according to claim 1, which is characterized in that. 3. From two or more kinds of α-olefins, wherein the olefin-based vulcanized rubber (A) is an amorphous random elastic copolymer mainly containing α-olefin having 2 to 20 carbon atoms. Amorphous α-olefin copolymer or α consisting of two or more types of α-olefins and non-conjugated dienes
-100 parts by weight of olefin / non-conjugated diene copolymer,
A vulcanized rubber composition comprising 5 to 40 parts by weight of low-density polyethylene having a melting point of 125 ° C. or less, 100 to 200 parts by weight of carbon black, and 30 to 150 parts by weight of process oil. The olefin rubber laminate according to claim 1. 4. The ultrahigh molecular weight polyolefin composition (B) contains 1 to 20% by weight of liquid or solid lubricating oil per 100% by weight of the total amount of the ultrahigh molecular weight polyolefin and the polyolefin. The olefin rubber laminate according to any one of claims 1 to 3.