JP2001232723A - Olefinic thermoplastic elastomer laminate and glass run channel for car - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an olefinic thermoplastic elastomer laminate having recyclability and excellent in appearance, abrasion resistance, durability, slide characteristics, mechanical strength and rubbery elasticity, and a glass run channel. SOLUTION: The glass run channel for a car comprises a laminate wherein a skin layer comprising an elastomer composition, prepared by adding 0.1-20 parts by weight of organopolysiloxane, 0.1-10 parts by weight of a fluoroplastic polymer and 0.1-10 parts by weight of an antistatic agent to 100 parts by weight of an olefinic thermoplastic elastomer, on a base material layer comprising an olefinic thermoplastic elastomer satisfying the formula: 9<=Y-0.43X<=27 [wherein X is JIS A hardness based upon JIS K6301 and Y is compression permanent strain (%) measured under a condition of 70 deg.C×22 based on JIS K6301] and characterized by that tensile strength measured based on JIS K6301 is 5-30 MPa and permanent elongation measured based on JIS K6301 is 18% or less.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an olefin-based thermoplastic elastomer laminate in which a skin layer made of an olefin-based thermoplastic elastomer composition is laminated on a base material layer made of an olefin-based thermoplastic elastomer, and to a laminate comprising the laminate. It relates to a glass run channel for automobiles.

[0002]

2. Description of the Related Art Various materials are conventionally used for parts or parts requiring rubber elasticity used in automobile parts, industrial machine parts, electric / electronic parts, building materials and the like. For example, a glass run channel is an example of such an automobile part. The glass run channel is a guide member provided between the window glass and the window frame. The glass run channel facilitates the raising and lowering operation of the window glass and tightly (liquid-tight) sealing between the window glass and the window frame. Operation is required.

[0003] A conventional glass run channel is formed on a surface of a base material such as a soft synthetic resin such as a soft vinyl chloride resin or ethylene-propylene-diene copolymer rubber on a surface layer of a nylon film or the like for sliding with a window glass. Are laminated by an adhesive. In order to reduce the contact area with the window glass, embossing is performed before or after laminating a nylon film or the like. In such a glass run channel, since the skin layer is laminated by the adhesive, there is a disadvantage that peeling is easily caused between the base material layer and the skin layer, and there is a problem that the number of steps is large and complicated. .

Further, since the soft vinyl chloride resin is inferior in rubber elasticity, there is a tendency that the function as a glass run channel is liable to be deteriorated such as settling or large deformation due to long-term use. In addition, since the vulcanized rubber is a thermosetting rubber, there is also a problem that it cannot be recycled.

[0005] The present inventors have focused on recyclable olefin-based thermoplastic elastomers in order to solve the above-mentioned problems of the glass run channel. However, when an olefin-based thermoplastic elastomer is used as a single layer for the glass run channel, the sliding property with the window glass is poor, severe abrasion occurs, and the amount of die residue generated on the die at the time of extrusion molding is a general resin. As a result, there is a problem in that, for example, eye dust adheres to the molded product, resulting in poor appearance.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems associated with the prior art as described above, and is intended to be easily manufactured using a recyclable olefinic thermoplastic elastomer as a material. It is an object of the present invention to provide an olefin-based thermoplastic elastomer laminate which can be used and has excellent appearance, abrasion resistance, durability, sliding characteristics, mechanical strength and rubber elasticity. Another subject of the present invention is:
A glass run channel for automobiles composed of an olefin-based thermoplastic elastomer laminate, which has excellent appearance, abrasion resistance, durability, sliding characteristics, mechanical strength and rubber elasticity, and is long-lasting. The goal is to provide an automotive glass run channel that does not occur.

[0007]

The present invention relates to the following olefin-based thermoplastic elastomer laminate and a glass run channel for an automobile. (1) The following, and 9 ≦ Y−0.43X ≦ 27 (1) (In the formula (1), X is the JI of the olefinic thermoplastic elastomer (A) measured according to JIS K6301.
SA hardness (no unit), Y is JIS K6301
Is the compression set (unit:%) of the olefinic thermoplastic elastomer (A) measured at 70 ° C. for 22 hours. A) a base layer made of an olefin-based thermoplastic elastomer (A) having a tensile strength measured according to JIS K 6301 of 5 to 30 MPa and a permanent elongation of 18% or less measured according to JIS K 6301; Based on 100 parts by weight of the olefinic thermoplastic elastomer (B), 0.5 to 20 parts by weight of the organopolysiloxane (C), 0.5 to 10 parts by weight of the fluoropolymer (D), and 0 of the antistatic agent (E) .
An olefin-based thermoplastic elastomer laminate characterized by being laminated with a skin layer composed of an olefin-based thermoplastic elastomer composition (X) containing at least one selected from the group consisting of 5 to 10 parts by weight in the above ratio. body. (2) The skin layer comprises 0.5 to 20 parts by weight of the organopolysiloxane (C) and 100 parts by weight of the olefin-based thermoplastic elastomer (B), and the fluorine-based polymer (D).
0.5 to 10 parts by weight and antistatic agent (E) 0.5 to 1
At least one selected from the group consisting of 0 parts by weight is contained in the above ratio, and the polyolefin resin (F) is contained in an amount of 5 to 1
The laminate according to the above (1), which is a skin layer comprising the olefin-based thermoplastic elastomer composition (X) containing 50 parts by weight. (3) The olefin-based thermoplastic elastomer (A)
5 to 60 parts by weight of a polyethylene resin (a-1), an ethylene / α-olefin copolymer (a-70) having a Mooney viscosity ML _{1 + 4} (100 ° C.) of 90 to 250 and an ethylene content of 70 to 95 mol%. 2) 40 to 95 parts by weight [where (a-
The total amount of 1) and (a-2) is 100 parts by weight. ] Is an olefin-based thermoplastic elastomer obtained by dynamically heat-treating the laminated body according to the above (1) or (2). (4) The olefin-based thermoplastic elastomer (A)
A mixture containing the polypropylene resin (a-3) in a proportion of 30 parts by weight or less based on 100 parts by weight of the total of the polyethylene resin (a-1) and the ethylene / α-olefin-based copolymer (a-2). The laminate according to the above (3), which is an olefin-based thermoplastic elastomer obtained by dynamic heat treatment. (5) The olefin-based thermoplastic elastomer (A)
The laminate according to the above (3) or (4), which is obtained by dynamically heat-treating in the absence of a crosslinking agent. (6) The olefin-based thermoplastic elastomer (B) is
Crystalline polyolefin resin (b-1) and rubber (b-2)
The laminate according to any one of the above (1) to (5), which is an olefin-based thermoplastic elastomer obtained by dynamically heat-treating a mixture containing: (7) An automotive glass run channel comprising the laminate according to any one of (1) to (6).

As the olefin-based thermoplastic elastomer (A) used as a raw material of the substrate layer of the present invention, olefin-based elastomers having the following characteristics can be used without limitation. 9 ≦ Y−0.43X ≦ 27 (1) Preferably, 9 ≦ Y−0.43X ≦ 26 (1 ′) More preferably, 10 ≦ Y−0.43X ≦ 26 (1 ″) (Formula 1) In (1), (1 ') and (1 "), X is JIS K
JIS A hardness of olefinic thermoplastic elastomer (A) measured according to 6301 (no unit), Y
Is the compression set (unit:%) of the olefinic thermoplastic elastomer (A) measured under the conditions of 70 ° C. × 22 hours in accordance with JIS K6301. )

The tensile strength measured according to JIS K 6301 is 5 to 30 MPa, preferably 8 to 30 M
Pa, more preferably 12 to 30 MPa. The permanent elongation measured according to JIS K 6301 is 18% or less, preferably 0.5 to 15%, more preferably 0.5 to 12%.

The method for measuring the above characteristics is as follows. JIS A hardness: JIS K 6301, instantaneous value by spring type hardness tester A type Compression set: JIS K 6301, thickness 12.7 m
m, using a cylindrical sample having a diameter of 29.0 mm, 25
% Compression, residual strain after 70 ° C. × 22 hours Tensile strength: Tensile strength obtained by performing a tensile test at a tensile speed of 200 mm / min using a JIS K 6301 dumbbell Permanent elongation: JIS K 6301 100% stretch and hold for 10 minutes, residual strain 10 minutes after load removal

The olefin thermoplastic elastomer (A) used in the present invention is preferably a polyethylene resin (a-
1) and an ethylene / α-olefin copolymer (a-
Elastomer obtained by dynamically heat-treating 2), or dynamically heat-treating polyethylene resin (a-1), ethylene / α-olefin copolymer (a-2) and polypropylene resin (a-3). It is an elastomer obtained by:

As the polyethylene resin (a-1), known polyethylene resins such as high density polyethylene, medium density polyethylene, linear low density polyethylene and low density polyethylene can be used without limitation.
Linear low-density polyethylene is preferred, and linear low-density polyethylene polymerized using a metallocene catalyst is particularly preferred.

The polyethylene resin (a-1) has a melt flow rate (MFR; ASTM D1238, 190 ° C.)
2.16 kg load) is 0.01 to 100 g / 10 min, preferably 0.01 to 50 g / 10 min. The ultrahigh molecular weight polyethylene having an MFR of less than 0.1 g / 10 min usually has an intrinsic viscosity [η] of 7 to 4 measured in decalin (decahydronaphthalene) at 135 ° C.
0 dl / g, and when such an ultrahigh molecular weight polyethylene is used as the polyethylene resin (a-1),
The intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.
15 to 40% by weight of a low to high molecular weight polyethylene of 1 to 5 dl / g and an intrinsic viscosity [η] of 7 to 40 dl / g.
g of ultrahigh molecular weight polyethylene in the form of an ultrahigh molecular weight polyethylene resin composition containing 85 to 60% by weight, and the intrinsic viscosity [η] of the entire ultrahigh molecular weight polyethylene resin composition is 3.5 to 3.5%. It is preferably 8.3 dl / g.

The polyethylene resin (a-1) has a density of 0.3.
880-0.980 g / cm ³ , preferably 0.900
It is desirably 0.950 g / cm ³ . When a linear low-density polyethylene is used as the polyethylene resin (a-1), MFR (ASTM D1238, 19
0 ° C, 2.16 kg load) 0.1 to 30 g / 10 min,
Preferably 0.2 to 20 g / 10 min, density 0.880
０．９0.950 g / cm ³ , preferably 0.910-0.
It is desirable to use 940 g / cm ³ linear low density polyethylene.

When a linear low-density polyethylene is used as the polyethylene resin (a-1), the substrate layer is less likely to be rough and has less stickiness on the surface than when a high-density polyethylene or a medium-density polyethylene is used. Can be obtained.

The polyethylene resin (a-1) may be a homopolymer of ethylene or a copolymer of ethylene and a small amount, for example, 10 mol% or less of another monomer. Other monomers include α-olefins having 3 to 20, preferably 3 to 8 carbon atoms; vinyl monomers such as vinyl acetate and ethyl acrylate.
As the α-olefin used as another monomer, for example, propylene, 1-butene, 4-methyl-1-
Examples include pentene, 1-hexene and 1-octene. Other monomers can be used alone or in combination of two or more. The polyethylene resin (a-1) can be used alone or in combination of two or more.

The ethylene / α-olefin copolymer (a-2) is composed of ethylene and C 3-20, preferably 3-3 carbon atoms.
To α-8-olefins, or a monomer other than α-olefins may be copolymerized. Examples of the monomer other than the α-olefin include a non-conjugated polyene. Also ethylene / α
-The olefin-based copolymer (a-2) may be a random copolymer or a block copolymer.

An ethylene / α-olefin copolymer (a
Specific examples of -2) include ethylene / α-olefin copolymers and ethylene / α-olefin / non-conjugated polyene copolymers. Among them, ethylene / α-olefin / non-conjugated polyene copolymer is preferred.

An ethylene / α-olefin copolymer (a
In -2), the α-olefin copolymerized with ethylene includes, for example, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene and 1-octene. The α-olefin can be used alone or in combination of two or more.

The ethylene / α-olefin copolymer (a
In -2), examples of the non-conjugated polyene copolymerized with ethylene and α-olefin include non-conjugated dienes such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, and ethylidene norbornene. . The non-conjugated polyene can be used alone or in combination of two or more. The iodine value of the ethylene / α-olefin / non-conjugated polyene copolymer is usually 0.1
-50, preferably 5-30, more preferably 5-2
5 is desirable.

The ethylene / α-olefin copolymer (a)
-2) is Mooney viscosity ML _{1 + 4}(100 ° C)
90-250, preferably 100-200, more preferably
Or 110-180, ethylene content 70-95 mol
%, Preferably 75 to 90 mol%, more preferably 7%
5-85 mol% ethylene / α-olefin copolymer
Are preferred, and among such copolymers, the iodine value is preferably
0.1-50, preferably 5-30, more preferably
5 to 25 ethylene / α-olefin copolymers are particularly preferred.
preferable. Here, the ethylene content is the total α-olefin
(Including ethylene). Etch
The len-α-olefin-based copolymer (a-2) is a single compound.
Can be used in combination with two or more.
Can also be used.

As the olefin thermoplastic elastomer (A) used in the present invention, the polyethylene resin (a-
1) 5 to 60 parts by weight, preferably 10 to 50 parts by weight, more preferably 10 to 45 parts by weight, 40 to 95 parts by weight of ethylene / α-olefin copolymer (a-2), preferably 50 to 90 parts by weight Parts by weight, more preferably 55 to 90 parts by weight [wherein (a-1) and (a-2)
Is 100 parts by weight. ], As described below,
Elastomers obtained by dynamic heat treatment in the absence of a crosslinking agent are preferred. When the content ratio of the polyethylene resin (a-1) and the ethylene / α-olefin copolymer (a-2) is within the above range, excellent rubber elasticity is exhibited.

The olefin thermoplastic elastomer (A) used in the present invention may contain a polypropylene resin (a-3). This polypropylene resin (a-3)
Any known polypropylene resin can be used without limitation. Specific examples include the following polypropylene resins.

1) Propylene homopolymer 2) Random copolymer of propylene of 90 mol% or more and less than 10 mol% of other α-olefin (propylene
α-olefin random copolymer) 3) 70% by mole or more of a block copolymer of propylene and less than 30% by mole of another α-olefin (propylene.
α-Olefin block copolymer) Specific examples of the other α-olefin copolymerized with propylene include ethylene, 1-butene, and 4-methyl-
Examples thereof include α-olefins having 2 to 20 carbon atoms, preferably 2 to 8 carbon atoms, such as 1-pentene, 1-hexene, and 1-octene.

As the polypropylene resin (a-3),
The propylene homopolymer (1) and the propylene / α-olefin random copolymer (2) are preferred, and particularly, MFR (ASTM D1238, 230 ° C, 2.16)
(kg load) is preferably 0.1 to 50 g / 10 min. The polypropylene resin (a-3) can be used alone or in combination of two or more.

The content of the polypropylene resin (a-3) in the olefin thermoplastic elastomer (A) used in the present invention depends on the polyethylene resin (a-1) and the ethylene / α-olefin copolymer (a- 30 parts by weight or less, preferably 2 to 3 parts by weight, based on 100 parts by weight in total of 2)
The proportion is preferably 0 parts by weight, more preferably 5 to 20 parts by weight. When the content of the polypropylene resin (a-3) is in the above range, it is possible to obtain a substrate layer which is less likely to be rough and has less stickiness.

The olefin-based thermoplastic elastomer (A) as described above has excellent rubber elasticity without being crosslinked (vulcanized) using a crosslinking agent or a crosslinking aid. Further, the olefin-based thermoplastic elastomer (A) forming the base layer in the laminate of the present invention is not a thermosetting elastic material such as a conventional vulcanized rubber but a thermoplastic elastomer, so that it can be easily recycled. It is. In addition, a cross-linking agent or the like is not required, so that a kneading step of the cross-linking agent or the like is not required, and the process can be easily and efficiently obtained by one step of dynamically heat-treating, so that the cost is low.

The olefin-based thermoplastic elastomer (A) used in the present invention may contain, if necessary, a known softener, heat stabilizer, anti-aging agent, weather stabilizer, or the like, as long as the object of the present invention is not impaired. Additives such as an antistatic agent, a filler, a colorant, and a lubricant can be blended. As the softener, a mineral oil softener is preferably used. As such a mineral oil-based softener, a paraffin-based, naphthene-based, aromatic-based softener and the like usually used for rubber are suitable.

The olefin-based thermoplastic elastomer (A) as described above is preferably used in the absence of a cross-linking agent in the presence of the polyethylene resin (a-1) and the ethylene / α-olefin-based copolymer (a-2). And, if necessary, the polypropylene resin (a-3), other resins and additives are mixed at the above-described specific ratio, and the mixture can be dynamically heat-treated.

The above-mentioned "dynamically heat-treating" means the above-mentioned polyethylene resin (a-1) and ethylene / α-olefin copolymer (a-2), and optionally a polypropylene resin (a-3). ), And kneading other resins and additives in a molten (melted) state. This dynamic heat treatment can be performed using a kneading device such as a mixing roll, an intensive mixer (for example, a Banbury mixer, a kneader), a continuous mixer, a single-screw extruder, and a twin-screw extruder. It is preferable to carry out. The dynamic heat treatment is preferably performed in a closed kneading apparatus. It is preferable to carry out the reaction in an inert gas such as nitrogen or carbon dioxide.

The conditions for the dynamic heat treatment are as follows: the kneading temperature is usually 150 to 280 ° C., preferably 170 to 240 ° C.
It is desirable that the kneading time is usually 1 to 20 minutes, preferably 1 to 5 minutes. Further, the shear force applied during kneading is usually 10 to 10 ⁴ sec ^-1 shear rate, and preferably 10 ² ~10 ⁴ sec ^-1.

When the dynamic heat treatment is performed using a twin-screw extruder, the following formula (2), preferably formula (2 ′),
More preferably, the reaction is performed under the condition satisfying the expression (2 ″).

4.8 <[(T−130) / 100] +2.2 log P + log Q−log R <7.0 (2) 5.0 <[(T−130) / 100] +2.2 log P + log Q−log R <6 .8 (2 ') 5.3 <[(T-130) / 100] + 2.2logP + logQ-logR <6.6 (2 ") (in formulas (2), (2') and (2")) , T is the resin temperature (° C.) at the die outlet of the twin-screw extruder, P is the screw diameter (mm) of the twin-screw extruder, Q is the maximum shear rate (sec ⁻¹ ) received in the twin-screw extruder, R Is the output of the twin screw extruder (k
g / h). The maximum shear rate Q (sec ^-1 ) is
Q = (P × π × S) / U. here,
P is the screw diameter (mm) of the twin-screw extruder, S is the screw rotation speed per second (rps), and U is the narrowest clearance (gap) between the barrel inner wall and the kneading segment (kneading segment). It is the distance (mm) of the part. )

The olefin-based thermoplastic elastomer (A) obtained by dynamically heat-treating using a twin-screw extruder in the absence of a crosslinking agent under the conditions satisfying the above formula (2) has a tensile strength and a permanent elongation. Excellent in compression set and molded appearance.

In the method for producing the olefin-based thermoplastic elastomer (A) as described above, a crosslinking agent such as an organic peroxide, a vulcanization aid such as a divinyl compound, and the like, which have been conventionally used for producing a vulcanized rubber, are used. The above-mentioned polyethylene resin (a-1) and ethylene / α-olefin-based copolymer (a-2), and optionally a polypropylene resin (a-3), other resins and additives without using Is mixed at the specific ratio described above and dynamically treated, whereby an olefin-based thermoplastic elastomer (A) having excellent rubber elasticity can be easily and efficiently produced in one step. In addition, since there is no need to use a crosslinking agent or a vulcanization aid, and a complicated vulcanization step is not required, it can be manufactured at low cost.

As the olefin-based thermoplastic elastomer (B) used in the present invention, an olefin-based thermoplastic elastomer can be used without limitation, and the olefin-based thermoplastic elastomer (A) can be used. A thermoplastic elastomer containing the resin (b-1) and the rubber (b-2) is preferable. Among them, the thermoplastic elastomer is obtained by dynamically heat-treating the crystalline polyolefin resin (b-1) and the rubber (b-2). Elastomers are preferred, especially crystalline polyolefin resin (b-1) and rubber (b-2)
And an elastomer obtained by dynamically heat-treating in the presence of a crosslinking agent.

The above-mentioned crystalline polyolefin resin (b-1)
Examples thereof include homopolymers or copolymers of α-olefins having 2 to 20 carbon atoms, preferably 2 to 8 carbon atoms. Specific examples of the crystalline polyolefin resin (b-1) include the following (co) polymers.

1) Ethylene homopolymer (manufacturing method may be either low pressure method or high pressure method) 2) Ethylene and 10 mol% or less of other α-olefin or vinyl monomer such as vinyl acetate and ethyl acrylate Copolymer 3) Propylene homopolymer 4) Random copolymer of propylene and 10 mol% or less of other α-olefin 5) Block copolymer of propylene and 30 mol% 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 random copolymer of 20 mol% or less of other α-olefin

As the above α-olefin, specifically, ethylene, propylene, 1-butene, 4-methyl-
1-pentene, 1-hexene, 1-octene and the like can be mentioned. As the crystalline polyolefin resin (b-1), the crystalline polypropylene resin (b-
1-1) is preferred.

The rubber (b-2) used in the present invention is not particularly limited, but may be an olefin copolymer rubber (b-
2-1) is preferred. The olefin-based copolymer rubber (b-2-1) is an amorphous random elastic copolymer mainly composed of an α-olefin having 2 to 20 carbon atoms, preferably 2 to 8 carbon atoms, Amorphous α-olefin copolymer comprising two or more α-olefins, two or more α-olefins
Α-olefin comprising an olefin and a non-conjugated diene
Non-conjugated diene copolymers and the like can be mentioned.

The olefin copolymer rubber (b)
Specific examples of -2-1) include the following rubbers. 1) Ethylene / α-olefin copolymer rubber [ethylene / α-olefin (molar ratio) = about 90/10 to 50/5
0] 2) Ethylene / α-olefin / non-conjugated diene copolymer rubber [ethylene / α-olefin (molar ratio) = about 90 /
3) Propylene / α-olefin copolymer rubber [propylene / α-olefin (molar ratio) = about 90 / 10-50]
/ 50] 4) Butene / α-olefin copolymer rubber [butene / α
-Olefin (molar ratio) = about 90/10 to 50/50]

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

These olefin copolymer rubbers (b-
The Mooney viscosity ML _{1 + 4} (100 ° C.) of 2-1) is 10 to 10.
It is desirably 250, preferably 40-150.
When the non-conjugated diene is copolymerized, the iodine value is preferably 25 or less, more preferably 5 to 23.

The olefin copolymer rubber (b-2)
-1) can exist in all cross-linked states such as uncross-linked, partially cross-linked and completely cross-linked in the olefin-based thermoplastic elastomer (B), but in the present invention, it exists in a cross-linked state. It is particularly preferred that they exist in a partially crosslinked state.

Rubber (b-2) used in the present invention
As the olefin-based copolymer rubber (b-2-
In addition to 1), other rubbers such as diene rubbers such as styrene-butadiene rubber (SBR), nitrile rubber (NBR), natural rubber (NR), and butyl rubber (IIR);
EBS, polyisobutylene and the like can be mentioned.

In the olefin thermoplastic elastomer (B) used in the present invention, the weight ratio of the crystalline polyolefin resin (b-1) to the rubber (b-2) (crystalline polyolefin resin (b-1) / The rubber (b-2))
Usually 90/10 to 5/95, preferably 70/30 to 1
It is desirable to be in the range of 0/90. In addition, rubber (b-
2) As olefin copolymer rubber (b-2-1)
When the other rubber is used in combination, the other rubber is not more than 40 parts by weight, preferably not more than 40 parts by weight, based on 100 parts by weight of the total amount of the crystalline polyolefin resin (b-1) and the rubber (b-2). It is desirable to mix in a ratio of 5 to 20 parts by weight.

The olefin thermoplastic elastomer (B) most preferably used in the present invention comprises a crystalline polypropylene resin (b-1-1) and an ethylene / α-olefin copolymer rubber or ethylene / α-olefin / non-olefin. Olefin copolymer rubbers such as conjugated diene copolymer rubbers (b
-2-1), which are present in the olefin-based thermoplastic elastomer (B) in a partially crosslinked state, and are crystalline polypropylene resin (b-1-1).
And the olefin copolymer rubber (b-2-1) in a weight ratio (crystalline polypropylene resin (b-1-1) / olefin copolymer rubber (b-2-1)) of 70 / 30
〜１０10 / 90, preferably 60 / 40〜１０10 / 90.

Olefinic thermoplastic elastomer (B)
If necessary, additives such as mineral oil-based softener, heat stabilizer, weather stabilizer, anti-aging agent, filler, coloring agent, lubricant and the like may be blended within a range that does not impair the purpose of the present invention. Can be.

More specific examples of the olefin thermoplastic elastomer (B) preferably used in the present invention include crystalline polypropylene resins (b-1-1) 70 to 1
0 parts by weight, preferably 60 to 10 parts by weight, ethylene
Propylene copolymer rubber or ethylene propylene
Olefin copolymer rubbers such as diene copolymer rubbers (b
-2-1) 30 to 90 parts by weight, preferably 40 to 90 parts by weight (the total amount of components (b-1-1) and (b-2-1) is 100 parts by weight), A mixture of a rubber other than the copolymer rubber (b-2-1) and / or 5 to 100 parts by weight, preferably 5 to 80 parts by weight of a mineral oil-based softener is dynamically added in the presence of a crosslinking agent. It is an olefin-based thermoplastic elastomer obtained by heat treatment.
An olefin-based thermoplastic elastomer in which the olefin-based copolymer rubber (b-2-1) is cross-linked by such dynamic heat treatment can be given.

Examples of the crosslinking agent include organic peroxides. As the 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
-Butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert
-Butylcumyl peroxide and the like.

Among these, 2,5-dimethyl-2.5-di- (tert-butylperoxy) hexane and 2,5-dimethyl-2,5-, in terms of odor and scorch stability.
Di- (tert-butylperoxy) hexine-3,
1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-
Butyl-4,4-bis (tert-butylperoxy)
Valerate is preferred, and among them, 1,3-bis (tert
-Butylperoxyisopropyl) benzene is most preferred. The organic peroxide is used in an amount of preferably 0.05 to 3 parts by weight, more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the total of the crystalline polyolefin and the rubber.

In the dynamic heat treatment using the above organic peroxide, sulfur, p-quinone dioxime, p, p'-dibenzoylquinone dioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenyl Peroxy crosslinking aids such as guanidine, trimethylolpropane-N, N'-m-phenylenedimaleimide, or divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylol Polyfunctional methacrylate monomers such as propane trimethacrylate and allyl methacrylate, and polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate can be blended.

By using the 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, and the crystalline polyolefin (b-1) and rubber (b-
2) It has good compatibility with (2) and has a function of solubilizing organic peroxide, and works as a dispersant for organic peroxide. Therefore, the cross-linking effect by heat treatment is uniform and the fluidity and physical properties are balanced. An olefin-based thermoplastic elastomer (B) is obtained.

The above-mentioned crosslinking aid or polyfunctional vinyl monomer is used in an amount of 0.1 to the whole of the above-mentioned object to be crosslinked.
２2% by weight, preferably 0.3-1% by weight. When the amount of the crosslinking aid or the polyfunctional vinyl monomer used is within the above range, the crosslinking reaction proceeds moderately, so that the obtained thermoplastic elastomer has excellent fluidity, and unreacted compounds do not remain. The obtained thermoplastic elastomer does not cause any change in physical properties due to the heat history at the time of processing and molding.

The term "dynamically heat-treating" has the same meaning as in the case of the olefin-based thermoplastic elastomer (A), and means that the above-mentioned components are kneaded in a molten (melted) state. . The operation is the same as in the case of the olefin-based thermoplastic elastomer (A). The kneading is preferably performed 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,
The temperature is preferably 170 to 240 ° C, and the kneading time is 1 to 2
It is desirably 0 minutes, preferably 3 to 10 minutes.
The applied shearing force is 100 sec ^-1 as a shear rate.
As described above, preferably, it is determined within the range of 500 to 10,000 sec ^-1 .

The olefinic thermoplastic elastomer (B) particularly preferably used in the present invention is partially crosslinked, and the term "partially crosslinked" means that the gel content measured by the following method is used. When the gel content is in the range of 20 to 98% by weight, the gel content is 40 to 9 in the present invention.
It is preferably in the range of 8% by weight.

[Measurement Method of Gel Content] A thermoplastic elastomer sample was weighed to about 100 mg and weighed 0.5 mm × 0.5 m
It is cut into small pieces of m × 0.5 mm, and the obtained small pieces are immersed in 30 ml of cyclohexane at 23 ° C. for 48 hours in a closed container. Next, the sample is taken out on a filter paper and dried at room temperature for 72 hours or more until the weight becomes constant. The value obtained by subtracting the weight of the cyclohexane-insoluble component (fibrous filler, filler, pigment, etc.) other than the polymer component from the weight of the dried residue is defined as “corrected final weight (Y)”.

On the other hand, the value obtained by subtracting the weight of the cyclohexane-soluble component (eg, softener) other than the polymer component and the weight of the cyclohexane-insoluble component (fibrous filler, filler, pigment, etc.) other than the polymer component from the weight of the sample is used. ,
This is referred to as “corrected initial weight (X)”.

Here, the gel content (cyclohexane insoluble content) is determined by the following equation (3).

## EQU2 ## Gel content (% by weight) = [corrected final weight (Y)] ÷ [corrected initial weight (X)] × 100 (3)

As described above, the olefin thermoplastic elastomer (B) obtained by dynamically heat-treating the crystalline polyolefin resin (b-1) and the rubber (b-2) in the presence of a crosslinking agent is as follows: Excellent fluidity. Further, the olefin-based thermoplastic elastomer (B) can be easily molded by using a conventionally used molding apparatus such as compression molding, transfer molding, injection molding, and extrusion molding.

As the organopolysiloxane (C) used in the present invention, a known organopolysiloxane having a -Si-O- bond in the main chain can be used without limitation.
By blending the organopolysiloxane (C),
A skin layer having excellent slidability and abrasion resistance is obtained.

As the organopolysiloxane (C),
Specific examples include dimethylpolysiloxane, methylphenylpolysiloxane, fluoropolysiloxane, tetramethyltetraphenylpolysiloxane, methylhydrogenpolysiloxane, and modified products thereof. Examples of the modified products include modified polysiloxanes such as epoxy-modified, alkyl-modified, amino-modified, carboxyl-modified, alcohol-modified, fluorine-modified, alkylaralkyl-polyether-modified, and epoxy-polyether-modified. Of these, dimethylpolysiloxane is preferred. The organopolysiloxane (C) can be used alone or in combination of two or more.

The organopolysiloxane (C) has a viscosity [JIS K 2283, 25 ° C.] of 10 to 10 ⁷ cS.
t's are preferred. Among these, the viscosity [JIS
K2283, 25 ° C.] is 10 ⁶ cSt or more, since it has a very high viscosity, so that it may be used as a master batch with an olefin resin in order to enhance the dispersibility in the olefin thermoplastic elastomer (B). Good. As the olefin resin used in this case, the crystalline polyolefin resin used for producing the olefin thermoplastic elastomer (B), specifically, an ethylene homopolymer or a copolymer of ethylene and another α-olefin is used. Examples thereof include a polymer, a propylene homopolymer, and a copolymer of propylene and another α-olefin.

Further, the organopolysiloxane (C) can be used singly depending on its viscosity.
Two or more kinds can be used in combination. Particularly when two or more kinds are used in combination, the viscosity is 10 to 10 ⁶
Low viscosity organopolysiloxane of cSt and 10 ⁶ to 10 ⁷
It is preferable to use in combination with a high viscosity organopolysiloxane of cSt.

The organopolysiloxane (C) is used in an amount of 0.5 to 20 parts by weight, preferably 1 to 18 parts by weight, based on 100 parts by weight of the olefinic thermoplastic elastomer (B). When the content of the organopolysiloxane (C) is in the above range, the molded article has excellent slidability, and the organopolysiloxane (C) does not cause problems such as stickiness of the surface.

As the fluoropolymer (D) used in the present invention, known fluoropolymers containing a fluorine atom can be used without any limitation. By blending the fluorine-based polymer (D), a skin layer having excellent slidability and abrasion resistance can be obtained.

The fluoropolymer (D) used in the present invention includes polytetrafluoroethylene, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / perfluorovinyl ether copolymer, and tetrafluoroethylene / ethylene copolymer. Coalescence, vinylidene fluoride polymer, vinyl fluoride polymer and the like. The fluoropolymer (D) can be used alone or in combination of two or more.

In order to enhance the dispersibility of the fluoropolymer (D) with the olefinic thermoplastic elastomer (B) or to further enhance the effect of improving the sliding abrasion, the olefinic polymer and / or the inorganic resin are used in advance. It may be a masterbatch with a system filler. The olefin-based resin used here may be the same as the olefin-based resin used in the organopolysiloxane (C) masterbatch. Examples of the inorganic filler include calcium carbonate, titanium oxide, talc, clay and the like.

The fluoropolymer (D) is added in an amount of 0.1 to 100 parts by weight of the olefinic thermoplastic elastomer (B).
It is used in a proportion of 5 to 10 parts by weight, preferably 1 to 8 parts by weight. When the content of the fluoropolymer (D) is in the above range, the molded product has excellent slidability.

The antistatic agent (E) used in the present invention comprises:
Known antistatic agents generally used for resins can be used without limitation, and examples thereof include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. Antistatic agent (E)
, A skin layer having excellent slidability and abrasion resistance can be obtained.

Specific examples of the antistatic agent (E) include lauryl diethanolamine, N, N-bis (2-
(Hydroxyethyl) stearylamine, stearyl monoglyceride, distearyl glyceride, tristearyl glyceride, polyoxyethylene laurylamine caprylic ester, stearyldiethanolamine monostearate and the like. Antistatic agent (E) is 1
The seeds can be used alone or in combination of two or more.

The antistatic agent (E) is used in advance to improve the dispersibility with the olefinic thermoplastic elastomer (B), or to further enhance the effect of improving the sliding wear property, in advance with the olefinic resin and / or the olefinic resin. It may be a masterbatch with an inorganic filler. As the olefin-based resin and the inorganic filler used here, the same as described above can be used.

The antistatic agent (E) is used in an amount of 0.5 to 1 based on 100 parts by weight of the olefinic thermoplastic elastomer (B).
0 parts by weight, preferably 1 to 8 parts by weight. When the content of the antistatic agent (E) is in the above range,
The molded article has excellent slidability, and does not cause problems such as precipitation of the antistatic agent (E) on the surface and whitening (bleed-out).

The organopolysiloxane (C), the fluoropolymer (D) and the antistatic agent (E) can be used alone or in combination of two or more. Optional.

The olefinic thermoplastic elastomer composition (X) used as a raw material of the skin layer in the present invention is selected from the group consisting of an organopolysiloxane (C), a fluoropolymer (D) and an antistatic agent (E). In addition to at least one of the above, a polyolefin resin (F) can be further compounded. By blending the polyolefin resin (F), a skin layer having excellent slidability and abrasion resistance and good moldability can be obtained.

As the polyolefin resin (F), the crystalline polyolefin (b-1) used in the olefin-based thermoplastic elastomer (B) is preferable. Another preferred example of the polyolefin resin (F) used in the present invention is a polyolefin resin having an intrinsic viscosity [η] in a range of 3.5 to 8.3 dl / g measured in decalin at 135 ° C. It is. Such a polyolefin resin may be a single type of polyolefin resin or a composition or a mixture of two or more types of polyolefin resins having different intrinsic viscosities [η]. A polyolefin composition comprising a molecular weight polyolefin is preferred. More preferably, the intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 10 to 40 dl / g, and the intrinsic viscosity [η] measured in decalin at 135 ° C. is 0. It may be a blend of a low molecular weight to a high molecular weight polyolefin in the range of 1 to 5 dl / g, and the blend may include an ultrahigh molecular weight polyolefin, an ultrahigh molecular weight polyolefin, and a low molecular weight to high molecular weight polyolefin. Is preferably present in a proportion of 15 to 40 parts by weight with respect to 100 parts by weight of the total weight of

The ultrahigh molecular weight polyolefins and polyolefins as described above include, for example, ethylene, propylene,
Homopolymers or copolymers of α-olefins such as 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene and 3-methyl-1-pentene Consists of a polymer. In the present invention, an ethylene homopolymer and a copolymer containing ethylene and another α-olefin and containing ethylene as a main component are preferable.

The ultrahigh molecular weight polyolefin composition contains 1 to 20 parts by weight of a liquid or solid softener (lubricating oil) based on 100 parts by weight of the total amount of the ultrahigh molecular weight polyolefin and the polyolefin. You may. As such a liquid softener, a mineral oil-based softener, a synthetic softener and the like are used. As the mineral oil-based softener, specifically, petroleum-based lubricating oils such as paraffin, naphthenic, liquid paraffin, spindle oil, refrigeration oil, dynamo oil, turbine oil, machine oil, cylinder oil, etc. are used. . As the synthetic softener, specifically, 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.

Further, as the solid softener, specifically,
Graphite and molybdenum disulfide are mainly used, but boron nitride, tungsten disulfide, lead oxide, glass powder, metallic soap and the like can also be used. The solid softening agent can be used alone or in combination with a liquid softening agent. For example, the solid softening agent can be blended with the ultrahigh molecular weight polyolefin in the form of powder, sol, gel, suspensoid or the like.

If necessary, additives such as heat stabilizers, antistatic agents, weathering stabilizers, antioxidants, fillers, coloring agents, lubricants and the like may be added to the ultrahigh molecular weight polyolefin composition.
It can be blended within a range that does not impair the purpose of the present invention. The polyolefin resin (F) is used in an amount of 5 to 150 parts by weight per 100 parts by weight of the olefin-based thermoplastic elastomer (B).
It is desirable to use it in a proportion of 30 parts by weight, preferably 30 to 100 parts by weight.

The olefin-based thermoplastic elastomer composition (X) as a raw material of the skin layer may contain a mineral oil-based softening agent, a heat stabilizer, a weather stabilizer, an antioxidant, a filler, a coloring agent, if necessary. Additives such as lubricants can be blended within a range that does not impair the purpose of the present invention.

The olefin-based thermoplastic elastomer composition (X) can be produced by a known method. For example, an olefin-based thermoplastic elastomer (B), an organopolysiloxane (C), a fluorine-based polymer (D) and a charged polymer It can be obtained by kneading at least one selected from the group consisting of the inhibitor (E), the polyolefin resin (F) and other additives that are blended if necessary.

The olefin-based thermoplastic elastomer laminate of the present invention comprises a base layer made of the olefin-based thermoplastic elastomer (A) and a skin layer made of the olefin-based thermoplastic elastomer composition (X). It is a laminated body. The skin layer may be laminated on the entire surface of the substrate layer, may be laminated on only a part of the substrate layer, or may be laminated with another layer. The skin layer may be laminated on one side of the base material layer, or may be laminated on both sides. When the skin layer is laminated only on a part of the base material layer, the base material layer may be exposed on the surface where the skin layer is not laminated. The base layer and the skin layer may be laminated with an adhesive, but are preferably fused. Although the thickness of the laminate is not particularly limited, the thickness of the base material layer is 0.1 to
It is desirable that the thickness is 50 mm, preferably 0.5 to 45 mm, and the thickness of the skin layer is 5 μm to 10 mm, preferably 10 μm to 8 mm.

The olefin-based thermoplastic elastomer laminate of the present invention is obtained by laminating the above-mentioned olefin-based thermoplastic elastomer (A) as a base layer and the above-mentioned olefin-based thermoplastic elastomer composition (X) as a skin layer. Is obtained by The lamination method varies depending on the shape, size, and required physical properties of the final product, and is not particularly limited. For example, there is a method in which a base material layer and a skin layer are simultaneously extruded by a multilayer extruder and heat-sealed. Such a heat-sealing method does not require an adhesive, a laminate can be easily obtained in one simple step, and the interlayer adhesion between the base material layer and the skin layer is strong. In addition, there is little eye drop generated during extrusion molding, and the appearance is excellent.

The olefin-based thermoplastic elastomer laminate of the present invention is excellent in appearance, abrasion resistance, durability, sliding characteristics, mechanical strength and rubber elasticity. Further, the laminate of the present invention can be easily produced and can be recycled, so that it is economically excellent.

The olefin-based thermoplastic elastomer laminate of the present invention can be used for automobile parts and the like. For example, it can be suitably used for automobile parts such as a glass run channel, a window molding, and a side molding, particularly, an automobile glass run channel.

FIG. 1 is a vertical sectional view of the olefin-based thermoplastic elastomer laminate of the present invention. The laminate 1 has a base material layer 2 composed of the olefin-based thermoplastic elastomer (A) and the olefin-based thermoplastic elastomer composition. It is a laminate in which the skin layer 3 made of the product (X) is laminated.

The glass run channel for automobiles of the present invention is a glass run channel for automobiles comprising the olefin-based thermoplastic elastomer laminate of the present invention. The automotive glass run channel of the present invention is excellent in appearance, abrasion resistance, durability, sliding characteristics, mechanical strength and rubber elasticity, and does not cause settling even when used for a long time. Further, the glass run channel of the present invention can be easily produced and is recyclable, so that it is economically excellent.

FIG. 2 is a vertical sectional view of an example of the glass run channel for an automobile of the present invention, which is a vertical sectional view orthogonal to the longitudinal direction. The glass run channel 5 has a main body 6 and a drainer 7, and the main body 6 is provided with an engaging portion 8 for attaching a window frame. The main body 6 and the draining section 7 are made of an olefin-based thermoplastic elastomer (A), and an olefin-based thermoplastic elastomer composition (X) is laminated on a portion where the glass comes into contact, thereby forming a glass contact section 9. That is, the entire glass run channel 5 is constituted by the laminate of the present invention in which the skin layer is laminated on a part of the base material layer, and the laminated portion constitutes the glass contact portion 9. Such a glass run channel 5 comprises an olefin-based thermoplastic elastomer (A) and an olefin-based thermoplastic elastomer composition such that the olefin-based thermoplastic elastomer composition (X) is laminated only on the glass contact portion 9. It can be produced by coextrusion molding with (X). As shown in FIG. 3, such a glass run channel 5 is attached to a window frame 12 of a door 11 of an automobile, and is used as a guide member when opening and closing the window glass 13.

FIG. 4 is a sectional view taken along the line AA of FIG. 3, showing a state in which the glass run channel 5 is attached to the window frame 12. FIG. 4A shows the state before the window glass 13 is closed.
(B) shows a state after the window glass 13 is closed. The glass run channel 5 repeats the states of FIGS. 4A and 4B with the opening and closing operation of the window glass 13,
When the window glass 13 is opened and closed, the window glass 13 slides on the glass contact portion 9 of the draining portion 7. However, the glass run channel 5 of the present invention has abrasion resistance, durability, sliding characteristics, and mechanical strength. Also, since it is excellent in rubber elasticity and the like, even if the window glass 13 is repeatedly opened and closed for a long period of time, no settling or deformation occurs.

[0090]

The olefin-based thermoplastic elastomer laminate of the present invention comprises a base layer made of an olefin-based thermoplastic elastomer (A) having specific properties and an olefin-based thermoplastic elastomer (B) containing an organopolysiloxane (B). C), a skin layer made of an olefin-based thermoplastic elastomer composition (X) containing a specific ratio of at least one selected from the group consisting of a fluorine-based polymer (D) and an antistatic agent (E). Since it is a laminate, it is excellent in appearance, abrasion resistance, durability, sliding characteristics, mechanical strength and rubber elasticity. Further, the laminate of the present invention can be easily produced and can be recycled, so that it is economically excellent.

Since the glass run channel for an automobile of the present invention comprises the above-mentioned olefin-based thermoplastic elastomer laminate, it has excellent appearance, abrasion resistance, durability, sliding characteristics, mechanical strength and rubber elasticity. Also, no settling occurs even when used for a long time. Further, the glass run channel of the present invention can be easily produced and is recyclable, so that it is economically excellent.

[0092]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. The raw materials used for the olefin-based thermoplastic elastomer composition (X) for forming the skin layer are shown below.

● Organopolysiloxane (C-1) Silicone oil, S, manufactured by Dow Corning Toray Co., Ltd.
H200 (3000 cSt), trademark ● Organopolysiloxane (C-2) manufactured by Dow Corning Toray Co., Ltd., silicone oil-polypropylene master batch, BY27-002 (ultra high molecular weight silicone oil content 50% by weight), trademark

● Fluoropolymer (D-1) Dynamer FX-9613 manufactured by Sumitomo 3M Ltd.
(Fluorine polymer content 90%), Trademark ● Antistatic agent (E-1) Kao Corporation, Electrostripper TS-6B, Trademark ● Polyolefin resin (F-1) MFR (ASTM D 1238-65T, 230 ° C) ,
2.16 kg load) 13 g / 10 min, density 0.910 g
/ Cm ³ polypropylene resin

Example 1 Linear low density polyethylene (density = 0.920 g / cm)
³ , ASTM D 1238, 190 ° C, 2.16 kg
MFR measured by load = 2.1 g / 10 min, ethylene content = 97.0 mol%, 4-methyl-1-pentene content = 3.0 mol%), and 30 parts by weight of ethylene / propylene / dicyclopentadiene Copolymer rubber (ethylene content =
77 mol%, Mooney viscosity ML _{1 + 4} (100 ° C.) = 14
5, iodine value = 12) and 70 parts by weight were mixed with a Henschel mixer. Next, using a twin-screw extruder with L / D = 30 and a screw diameter of 50 mm in a nitrogen atmosphere,
The mixture was dynamically heat-treated at 0 ° C. and extruded to produce pellets of the olefin-based thermoplastic elastomer (A-1). In addition, a sample for measuring physical properties is created from the pellet,
Hardness (JIS A), compression set (CS), tensile strength,
The permanent elongation was measured. Table 1 shows the results.

On the other hand, ASTM D 1238-65T,
MFR measured at 230 ° C. under a load of 2.16 kg is 13
g / 10 minutes, 40 parts by weight of polypropylene having a density of 0.910 g / cm ³ , ethylene / propylene / 5-ethylidene having an ethylene content of 70 mol%, an iodine value of 12, and a Mooney viscosity of ML 1 _{+ 4} (100 ° C.) 120 After kneading 60 parts by weight of 2-norbornene copolymer rubber in a nitrogen atmosphere at 180 ° C. for 5 minutes using a Banbury mixer,
The kneaded material was passed through a roll to form a sheet, which was cut with a sheet cutter to produce square pellets. Then
The square pellet, 0.2 parts by weight of 1,3-bis (tert-butylperoxyisopropyl) benzene, and 0.2 parts by weight of divinylbenzene were stirred and mixed with a Henschel mixer. Next, this mixture was extruded at 220 ° C. in a nitrogen atmosphere using a twin screw extruder having an L / D = 40 and a screw diameter of 50 mm to obtain an olefin-based thermoplastic elastomer (B-1). The gel content of the obtained olefin-based thermoplastic elastomer (B-1) was determined by the above method according to the formula (3), and was found to be 78% by weight. Next, the olefinic thermoplastic elastomer (B-1) 100
Parts by weight and 2 parts by weight of the organopolysiloxane (C-1) were kneaded with a twin-screw extruder to obtain pellets of the olefin-based thermoplastic elastomer composition (X-1).

The olefin-based thermoplastic elastomer (A-1) was used as a base layer, and the olefin-based thermoplastic elastomer composition (X-1) obtained above was used as a skin layer.
The glass run channel shown in FIG. 2 was manufactured by co-extrusion at a temperature of 230 ° C. The average thickness of the skin layer of the obtained glass run channel was 30 μm.

The obtained glass run channel was mounted on a test window frame, fitted with a 3.2 mm-thick window glass, and subjected to a durability test in which the window glass was repeatedly slid up and down. As a result, the glass run channel maintained its function as a glass run channel without sagging or abrasion even after 50,000 repetitions of the windowpane vertical test.

Example 2 100 parts by weight of the olefinic thermoplastic elastomer (B-1) obtained in Example 1, 2 parts by weight of the organopolysiloxane (C-1), and 100 parts by weight of the organopolysiloxane (C-
2) 14 parts by weight were kneaded with a twin-screw extruder to obtain an olefin-based thermoplastic elastomer composition (X-2). The olefinic thermoplastic elastomer obtained in Example 1 (A-
Using 1) as a substrate layer and the olefin-based thermoplastic elastomer composition (X-2) as a skin layer, the same glass run channel as in Example 1 was produced, and a durability test was performed. As a result, the glass run channel withstood the repetition test of 50,000 times and maintained the function as the glass run channel.

Example 3 30 parts by weight of the linear low-density polyethylene used in Example 1, 70 parts by weight of the ethylene / propylene / dicyclopentadiene copolymer rubber used in Example 1, and a mineral oil softener (Paraffin oil; Idemitsu Kosan Co., Ltd., PW-3
80, trademark) and 40 parts by weight of olefinic thermoplastic elastomer (A-2) in the same manner as in Example 1.
I got The olefin-based thermoplastic elastomer (A-
Using 2) as a base layer and the olefin-based thermoplastic elastomer composition (X-2) obtained in Example 2 as a skin layer, the same glass run channel as in Example 1 was prepared and subjected to a durability test. As a result, this glass run channel is 50,
It survived 2,000 repetitions and maintained its function as a glass run channel.

Example 4 15 parts by weight of the linear low-density polyethylene used in Example 1, 85 parts by weight of the ethylene / propylene / dicyclopentadiene copolymer rubber used in Example 1, and a propylene homopolymer ( ASTM D 1238, 230 ° C, 2.1
MFR measured by 6 kg load = 1.5 g / 10
Olefin-based thermoplastic elastomer (A-3) was obtained in the same manner as in Example 1 except for using 20 parts by weight).
The same glass run channel as in Example 1 was prepared using the olefin-based thermoplastic elastomer (A-3) as a base layer and the olefin-based thermoplastic elastomer composition (X-2) obtained in Example 2 as a skin layer. Then, a durability test was performed.
As a result, the glass run channel withstood the repetition test of 50,000 times and maintained the function as the glass run channel.

Example 5 30 parts by weight of the linear low-density polyethylene used in Example 1 and 100 parts by weight of the ethylene / propylene / dicyclopentadiene copolymer rubber used in Example 1 were extended oil (paraffin oil). Oil-extended ethylene propylene containing 40 parts by weight of PW-380 (trade name, manufactured by Idemitsu Kosan Co., Ltd.)
An olefin-based thermoplastic elastomer (A-4) was obtained in the same manner as in Example 1 using 110 parts by weight of the dicyclopentadiene copolymer rubber. The olefin-based thermoplastic elastomer (A-4) was used as a base material layer, and the olefin-based thermoplastic elastomer composition (X-
Using 2) as a skin layer, the same glass run channel as in Example 1 was prepared and subjected to a durability test. As a result, the glass run channel withstood the repetition test of 50,000 times and maintained the function as the glass run channel.

Example 6 100 parts by weight of the olefin-based thermoplastic elastomer (B-1) obtained in Example 1, 2 parts by weight of the organopolysiloxane (C-1), and the organopolysiloxane (C-
2) 14 parts by weight and polyolefin resin (F-1) 30
Parts by weight with a twin-screw extruder to obtain an olefin-based thermoplastic elastomer composition (X-3). Using the olefin-based thermoplastic elastomer (A-1) obtained in Example 1 as a base layer and the olefin-based thermoplastic elastomer composition (X-3) as a skin layer, the same glass run channel as in Example 1 was produced. Then, a durability test was performed. As a result, the glass run channel withstood the repetition test of 50,000 times and maintained the function as the glass run channel.

Example 7 100 parts by weight of the olefin-based thermoplastic elastomer (B-1) obtained in Example 1 and a fluorine-based polymer (D-
1) 3 parts by weight were kneaded with a twin-screw extruder to obtain an olefin-based thermoplastic elastomer composition (X-4). Example 1
Olefinic thermoplastic elastomer (A-
Using 1) as a substrate layer and the olefin-based thermoplastic elastomer composition (X-4) as a skin layer, the same glass run channel as in Example 1 was produced, and a durability test was performed. As a result, the glass run channel withstood the repetition test of 50,000 times and maintained the function as the glass run channel.

Example 8 100 parts by weight of the olefinic thermoplastic elastomer (B-1) obtained in Example 1, 2 parts by weight of the organopolysiloxane (C-1), and the organopolysiloxane (C-
2) 14 parts by weight and 3 parts by weight of the fluorine-based polymer (D-1) were kneaded with a twin-screw extruder to obtain an olefin-based thermoplastic elastomer composition (X-5). The olefin thermoplastic elastomer (A-1) obtained in Example 1 was used as a base material layer, and the olefin thermoplastic elastomer composition (X
The same glass run channel as in Example 1 was prepared using -5) as a skin layer, and a durability test was performed. As a result, the glass run channel withstood the repetition test of 50,000 times and maintained the function as the glass run channel.

Example 9 100 parts by weight of the olefin-based thermoplastic elastomer (B-1) obtained in Example 1 and 3 parts by weight of an antistatic agent (E-1) were kneaded with a twin-screw extruder to obtain an olefin-based resin. A thermoplastic elastomer composition (X-6) was obtained. The olefin thermoplastic elastomer (A-1) obtained in Example 1 was used as a base material layer, and the olefin thermoplastic elastomer composition (X
The same glass run channel as in Example 1 was prepared using -6) as a skin layer, and a durability test was performed. As a result, the glass run channel withstood the repetition test of 50,000 times and maintained the function as the glass run channel.

Comparative Example 1 The same durability test as in Example 1 was performed using a conventional glass run channel (a laminated structure in which a nylon film was bonded to a soft vinyl chloride resin layer). As a result, 25,000
At 0 times, destruction occurred at the contact surface with the window glass, and the frictional resistance with the window glass increased significantly, making it unusable for use.

The olefinic thermoplastic elastomers (A-1), (A-2), (A-3) and (A-4)
Table 1 shows the conditions of the dynamic heat treatment in the production of the olefin-based thermoplastic elastomers and the characteristics of these olefinic thermoplastic elastomers.

[0109]

[Table 1]

Notes in Table 1 * 1 PE: linear low-density polyethylene * 2 EPDM: ethylene / propylene / dicyclopentadiene copolymer rubber * 3 EPDM with extended oil: ethylene / propylene / dicyclopentadiene copolymer rubber 100 parts by weight of paraffinic oil (PW-
380, a trademark) 40 parts by weight of an oil-extended ethylene-propylene-dicyclopentadiene copolymer rubber * 4 PP: propylene homopolymer * 5 Paraffin-based oil: mineral oil-based softener (manufactured by Idemitsu Kosan Co., Ltd. * 6 T: Resin temperature at die outlet of twin screw extruder (° C) * 7 P: Screw diameter of twin screw extruder (mm) * 8 Q: Maximum received in twin screw extruder Shear rate (sec)
^-1 ) * 9 R: Extrusion amount of twin screw extruder (kg / h) * 10 S: Number of screw rotations per second (rps) * 11 U: Between barrel inner wall and screw kneading segment (kneading segment) Clearance (gap)
Distance of the narrowest part of (mm) * 12 Equation (2): [(T-130) / 100] + 2.2 logP
+ LogQ-logR * 13 Formula (1): Y-0.43X * 14 JIS A hardness: JIS K 6301, instantaneous value by spring type hardness tester type A * 15 Compression set: JIS K 6301, thickness 1
Using a cylindrical sample having a diameter of 2.7 mm and a diameter of 29.0 mm, the residual strain after compression at 25% and at 70 ° C. for 22 hours * 16 Tensile strength: JIS K 6301, JIS No. 3 dumbbell at a pulling speed of 200 mm / min. * 17 Permanent elongation: JIS K 6301, JIS No. 3 dumbbell is stretched 100%, held for 10 minutes, and residual strain 10 minutes after load removal

[Brief description of the drawings]

FIG. 1 is a vertical sectional view of an olefin-based thermoplastic elastomer laminate of the present invention.

FIG. 2 is a vertical sectional view of an example of the glass run channel of the present invention.

FIG. 3 is a perspective view of an automobile door in which the glass run channel of the present invention is mounted on a window frame.

FIG. 4 is a sectional view taken along line AA of FIG. 3, wherein FIG. 4A shows a state before the window glass 13 is closed, and FIG. 4B shows a state after the window glass 13 is closed.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Laminated body 2 Base material layer 3 Skin layer 5 Glass run channel 6 Main body 7 Drain part 8 Engagement part 9 Window glass contact part 11 Automobile door 12 Window frame 13 Window glass

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/00 C08L 21/00 C08L 21/00 23/00 23/00 23/06 23/06 23/12 23/12 23/16 23/16 (C08L 23/00 // (C08L 23/00 83:04 83:04 27:12) 27:12) B60J 1/16 A F term (reference) 3D127 AA09 AA15 BB01 CB05 CC05 DE04 DE09 DE22 DE32 GG09 4F100 AK02 AK02J AK02K AK03A AK03B AK04 AK04A AK04J AK07 AK07J AK17B AK28 AK28J AK28K AK52B AK62A AK63 AK80 AL01 AL05B AL09A AL09B AN00B AN02 AN02J BA02 CA22B GB32 JA06A JA11B JA20A JB16A JB16B JK01 JK02A JK07 JK08A JK09 JK12A JK16 JL00 JL16 YY00A 4J002 BB03W BB03X BB05W BB12W BB123 BB14W BB14X BB143 BB15W BB15X BB153 BB17W BB17X BD134 BD144 BD154 BD164 BP02W CH055 CP033 CP043 CP053 CP083 CP093 CP183 EH046 EH056 FD106 FD020 FD106 FD020

Claims (7)

[Claims] 1. The following, and 9 ≦ Y−0.43X ≦ 27 (1) (in the formula (1), X is JI of the olefinic thermoplastic elastomer (A) measured according to JIS K6301)
SA hardness (no unit), Y is JIS K6301
Is the compression set (unit:%) of the olefinic thermoplastic elastomer (A) measured at 70 ° C. for 22 hours. A) a base layer made of an olefin-based thermoplastic elastomer (A) having a tensile strength measured according to JIS K 6301 of 5 to 30 MPa and a permanent elongation of 18% or less measured according to JIS K 6301; Based on 100 parts by weight of the olefinic thermoplastic elastomer (B), 0.5 to 20 parts by weight of the organopolysiloxane (C), 0.5 to 10 parts by weight of the fluoropolymer (D), and 0 of the antistatic agent (E) .
An olefin-based thermoplastic elastomer laminate characterized by being laminated with a skin layer composed of an olefin-based thermoplastic elastomer composition (X) containing at least one selected from the group consisting of 5 to 10 parts by weight in the above ratio. body. 2. A skin layer comprising 0.5 to 20 parts by weight of an organopolysiloxane (C) and 0.5 to 10 parts by weight of a fluoropolymer (D) based on 100 parts by weight of an olefin-based thermoplastic elastomer (B). Part and antistatic agent (E)
A skin layer comprising an olefin-based thermoplastic elastomer composition (X) containing at least one selected from the group consisting of 5 to 10 parts by weight in the above ratio, and further containing 5 to 150 parts by weight of a polyolefin resin (F). Claim 1
The laminate according to the above. 3. The olefin-based thermoplastic elastomer (A) has a polyethylene resin (a-1) of 5 to 60 parts by weight and a Mooney viscosity ML _{1 + 4} (100 ° C.) of 90 to 25.
0, ethylene-α- having an ethylene content of 70 to 95 mol%
40 to 95 parts by weight of the olefin-based copolymer (a-2) [here, the total amount of (a-1) and (a-2) is 100 parts by weight. Is an olefin-based thermoplastic elastomer obtained by dynamically heat-treating the laminate. 4. An olefin-based thermoplastic elastomer (A) comprising a polyethylene resin (a-1) and ethylene-α
-Olefin-based copolymer obtained by dynamically heat-treating a mixture containing 30 parts by weight or less of polypropylene resin (a-3) with respect to 100 parts by weight in total with olefin-based copolymer (a-2) The laminate according to claim 3, which is a thermoplastic elastomer. 5. The laminate according to claim 3, wherein the olefin-based thermoplastic elastomer (A) is obtained by dynamically heat-treating in the absence of a crosslinking agent. 6. An olefinic thermoplastic elastomer obtained by dynamically heat-treating a mixture containing a crystalline polyolefin resin (b-1) and a rubber (b-2), wherein the olefinic thermoplastic elastomer (B) is obtained. The laminate according to any one of claims 1 to 5, wherein 7. A glass run channel for an automobile, comprising the laminate according to any one of claims 1 to 6.