JP2001138440A - Thermoplastic elastomer laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer laminate without changing its surface and without generating stickiness even when it is exposed to a high temperature. SOLUTION: In the thermoplastic elastomer laminate comprising a front layer made of a polyolefin thermoplastic elastomer A containing an oil softener, and a polyolefin thermoplastic elastomer B containing an oil softener and laminated on the front layer, a ratio an of the softener to a noncrystalline component amount (the total amount of the noncrystalline component amount and a polylethylene in the case of containing the polyethylene) in the elastomer A and a ratio b of the softener to the noncrystalline component amount (the total amount of the noncrystalline component amount and a polyethylene in the case of containing the polyethylene) in the elastomer B satisfy the radio a the ratio b, the ratio a=5 to 200 wt.% and the ratio b=5 to 200 wt.%. A glass run channel and a roof molding, a side molding or window molding for an automobile made of the laminate are provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate obtained by laminating a polyolefin-based thermoplastic elastomer.

[0002]

2. Description of the Related Art In recent years, there has been a movement to abolish the use of polyvinyl chloride in terms of recyclability and the like. Thermoplastic elastomers are considered to be the most promising alternatives to polyvinyl chloride.

[0003] However, thermoplastic elastomers have problems such as lack of gloss and scratch resistance as compared with polyvinyl chloride, and in order to solve these problems, a polyolefin resin or an organopolysiloxane is blended. Attempts have been made to impart gloss and scratch resistance by doing so. At this time, since the organopolysiloxane is more expensive than the thermoplastic elastomer, it is conceivable that only the necessary surface layer is constituted by a material blended with the organopolysiloxane, and the lower layer is constituted by a conventional thermoplastic elastomer.

When such a configuration is applied to, for example, a roof molding or a wind molding of an automobile, the following restrictions occur. The roof molding is used for the roof of the automobile and the window molding is used for the window glass part. However, these places are exposed to sunlight when the automobile is actually used, and the surface temperature of those members becomes high. Therefore, these members are required to have no change in appearance or surface slip even at, for example, 80 ° C. for 400 hours. However, in these laminates, after the test at 80 ° C. for 400 hours, the surface became solid, the surface slippage was lost, and the appearance was sometimes changed.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a thermoplastic elastomer laminate which does not change its surface even when exposed to a high temperature and does not generate solid.

[0006]

The present invention includes the following inventions. (1) In a laminate in which a polyolefin-based thermoplastic elastomer (B) containing an oily softener is laminated on a surface layer made of a polyolefin-based thermoplastic elastomer (A) containing an oily softener, the thermoplastic elastomer (A) The ratio of the oily softener to the amount of the amorphous component (in the case of containing polyethylene, the amount of the amorphous component and the total amount of polyethylene when polyethylene is contained) (a) and the amount of the amorphous component in the thermoplastic elastomer (B) ( In the case of containing polyethylene, the ratio (b) of the oily softener to the amount of the amorphous component and the total amount of polyethylene) is as follows: Ratio (a) ≧ Ratio (b), Ratio (a) = 5 A laminate characterized by satisfying the following: 200% by weight, ratio (b) = 5 to 200% by weight.

(2) In the laminate according to (1), the polyolefin-based thermoplastic elastomer (A) and / or the polyolefin-based thermoplastic elastomer (B) contains polyethylene, and the thermoplastic elastomer (A) The ratio (a ′) of the oily softener to the amount of the amorphous component in the thermoplastic elastomer (B) and the ratio (b ′) of the oily softener to the amount of the amorphous component in the thermoplastic elastomer (B) are as follows: Ratio (a ′) ≧ 0.8 × rate (b ′), ratio (a ′) = 5 to 200% by weight, ratio (b ′) = 5 to 200% by weight. (3) A glass run channel comprising the laminate according to (1) or (2). (4) An automobile roof molding, side molding or wind molding comprising the laminate according to (1) or (2).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In the laminate of the present invention, the surface layer is made of a polyolefin-based thermoplastic elastomer (A) containing an oily softener, and if necessary, the surface scratch resistance can be improved by blending an organopolysiloxane or the like. is there. The lower layer of the laminate of the present invention comprises a polyolefin-based thermoplastic elastomer (B) containing an oily softener.

[0009] The laminate of the present invention is, for example, co-extruded by using two extruders to melt the surface layer material and the lower layer material by applying heat equal to or higher than the melting point of each material to form a two-layer laminate. Can be manufactured. In addition, it is also possible to apply a heat of the melting point or more to these materials and perform two-color injection molding to form a laminate.

[0010] In the laminate of the present invention, the polyolefin-based thermoplastic elastomer (A) forming the surface layer and the polyolefin-based thermoplastic elastomer (B) forming the lower layer include at least a polyolefin resin, ethylene, and 3 to 20 carbon atoms. Of an ethylene / α-olefin / non-conjugated polyene copolymer rubber composed of an α-olefin and a non-conjugated polyene, and an oily softener.

The polyolefin-based thermoplastic elastomer (A) and the polyolefin-based thermoplastic elastomer (B) forming the lower layer are preferably 10 to 60 parts by weight of a polyolefin resin (X) and ethylene / α-olefin / non-olefin. 30 to 70 parts by weight of a conjugated polyene copolymer rubber (or a rubber component obtained by adding other rubbers such as polyisobutylene, butyl rubber, and propylene / ethylene copolymer) (Y), and an oily softener (Z) 5 to 5 50 parts by weight [(X),
The sum of (Y) and (Z) is 100 parts by weight. Is dynamically heat-treated in the presence of a crosslinking agent.

[0012] The raw material olefin of the polyolefin resin (X) used in the polyolefin resin (X) The present invention, specifically, ethylene, propylene, 1
-Butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene And the like. These olefins are used alone or in combination of two or more. The polymerization mode may be a random type or a block type.

These polyolefin resins may be used alone or in combination of two or more. The polyolefin resin used for the polyolefin thermoplastic elastomer (A) forming the surface layer is polypropylene (propylene homopolymer). (Polymer).

MF of polyolefin resin used in the present invention
R (230 ° C., load 2.16 kg) is usually 0.1 to 5
0 g / 10 min, preferably 1 to 30 g / 10 min.
In the present invention, the polyolefin resin (X) is a polyolefin resin (X), an ethylene / α-olefin / non-conjugated polyene copolymer rubber (Y), and an oily softener (Z).
Is usually used at a ratio of 10 to 60 parts by weight with respect to 100 parts by weight of the total amount.

Ethylene / α-olefin / non-conjugated polyether
Copolymer rubber (Y) The ethylene / α-olefin / non-conjugated polyene copolymer rubber (Y) used in the present invention is prepared by the presence of a suitable catalyst such as a metallocene catalyst, a titanium nonmetallocene catalyst, and a vanadium catalyst. Below, it can be obtained by random copolymerizing ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene. The ethylene / α-olefin / non-conjugated polyene copolymer rubber (Y) may have either a linear or long-chain branched molecular structure.

As the α-olefin having 3 to 20 carbon atoms, for example, propylene, 1-butene, 1-pentene,
1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-
Tridecene, 1-tetradecene, 1-pentadecene, 1
-Hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1
-Butene, 3-methyl-1-pentene, 3-ethyl-1
-Pentene, 4-methyl-1-pentene, 4-methyl-
1-hexene, 4,4-dimethyl-1-hexene, 4,
4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-
And tetradecene, and combinations thereof.

Among these, α-α constituting the linear ethylene / α-olefin / non-conjugated polyene copolymer rubber
As the olefin, an α-olefin having 4 to 10 carbon atoms is preferable, and 1-butene, 1-hexene, 1-octene, 1-decene and the like are particularly preferably used. The α-olefin constituting the long-chain branched ethylene / α-olefin / non-conjugated polyene copolymer rubber is preferably an α-olefin having 3 to 10 carbon atoms, particularly propylene, 1-butene, 1- Hexene, 1-octene and the like are preferably used. Examples of the non-conjugated polyene constituting the ethylene / α-olefin / non-conjugated polyene copolymer rubber include an aliphatic polyene, an alicyclic polyene, and an aromatic polyene.

Specific examples of the aliphatic polyene include 1,4-hexadiene, 1,5-hexadiene,
1,6-heptadiene, 1,6-octadiene, 1,7
-Octadiene, 1,8-nonadiene, 1,9-decadiene, 1,13-tetradecadiene, 3-methyl-1,
4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4-ethyl-
1,4-hexadiene, 3-methyl-1,5-hexadiene, 3,3-dimethyl-1,4-hexadiene, 3,
4-dimethyl-1,5-hexadiene, 5-methyl-
1,4-heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5-heptadiene, 3-methyl- 1,6-heptadiene, 4-methyl-1,6-heptadiene, 4,4-dimethyl-1,6
Heptadiene, 4-methyl-1,6-heptadiene,
1,6-octadiene, 4-methyl-1,4-octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-octadiene, 5-methyl- 1,5-octadiene, 6-methyl-1,5-octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene, 6-methyl-1,6-octadiene, 7-methyl- 1,6-octadiene, 6-ethyl-1,6-octadiene, 6-
Propyl-1,6-octadiene, 6-butyl-1,6
-Octadiene, 4-methyl-1,4-nonadiene, 5
-Methyl-1,4-nonadiene, 4-ethyl-1,4-
Nonadiene, 5-ethyl-1,4-nonadiene, 5-methyl-1,5-nonadiene, 6-methyl-1,5-nonadiene, 5-ethyl-1,5-nonadiene, 6-ethyl-1,5- Nonadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-
1,6-nonadiene, 7-ethyl-1,6-nonadiene, 7-methyl-1,7-nonadiene, 8-methyl-
1,7-nonadiene, 7-ethyl-1,7-nonadiene, 5-methyl-1,4-decadiene, 5-ethyl-
1,4-decadiene, 5-methyl-1,5-decadiene, 6-methyl-1,5-decadiene, 5-ethyl-
1,5-decadiene, 6-ethyl-1,5-decadiene, 6-methyl-1,6-decadiene, 6-ethyl-
1,6-decadiene, 7-methyl-1,6-decadiene, 7-ethyl-1,6-decadiene, 7-methyl-
1,7-decadiene, 8-methyl-1,7-decadiene, 7-ethyl-1,7-decadiene, 8-ethyl-
1,7-decadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 8-ethyl-
Examples thereof include 1,8-decadiene, 6-methyl-1,6-undecadiene, and 9-methyl-1,8-undecadiene.

Specific examples of the alicyclic polyene include vinyl cyclohexene, vinyl norbornene, methylene norbornene, and ethylidene norbornene (for example,
-Ethylidene-2-norbornene), dicyclopentadiene, cyclooctadiene, 2,5-norbornadiene, 1,4-divinylcyclohexane, 1,3-divinylcyclohexane, 1,3-divinylcyclopentane,
1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane, 1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane, 1,5-
Diallylcyclooctane, 1-allyl-4-isopropenylcyclohexane, 1-isopropenyl-4-vinylcyclohexane, 1-isopropenyl-3-vinylcyclopentane, and the like.

Further, specific examples of the aromatic polyene include divinylbenzene and vinylisopropenylbenzene. Among these, non-conjugated polyenes having 7 or more carbon atoms are preferred, for example, methyloctadiene such as 7-methyl-1,6-octadiene,
Ethylidene norbornene such as ethylidene-2-norbornene, dicyclopentadiene and the like are preferably used.
These non-conjugated polyenes can be used alone or in combination of two or more. Linear ethylene / α-olefin / non-conjugated polyene copolymer rubber (Y) preferably used in the present invention (hereinafter referred to as “copolymer rubber (Y)”)
That. ) Has the following characteristics.

(1) Ethylene / α-olefin Component Ratio The copolymer rubber (Y) is composed of (a) a unit derived from ethylene and (b) an α-olefin having 3 to 20 carbon atoms (hereinafter referred to as “α-olefin”).
It may be simply referred to as “α-olefin”. Is derived from 40/60 to 95/5, preferably 4
0/60 to 90/10, more preferably 50/50 to 8
It is contained at a molar ratio of 5/15 [(a) / (b)].
Such an ethylene / α-olefin / non-conjugated polyene copolymer rubber having an ethylene component / α-olefin component ratio has excellent low-temperature flexibility and heat resistance.

(2) Iodine Value The copolymer rubber (Y) has an iodine value, which is an index of the amount of the non-conjugated polyene component, of 1 to 50, preferably 1 to 30. (3) Intrinsic viscosity [η] The intrinsic viscosity [η] of the copolymer rubber (Y) measured in decalin at 135 ° C. is 0.1 to 10 dl / g, preferably 1.5 to 7 dl / g. is there.

The above-mentioned linear or long-chain branched copolymer rubber (Y) can be prepared by reacting ethylene with ethylene in the presence of a suitable catalyst such as a metallocene catalyst, a titanium nonmetallocene catalyst, or a vanadium catalyst. It is produced by randomly copolymerizing an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene.

Examples of the metallocene catalyst include those described in, for example, JP-A-9-12790 and JP-A-9-137001. Catalysts for producing the copolymer rubber (Y) are not limited to metallocene catalysts, but may be other metallocene catalysts, group V transition metal compound catalysts such as vanadium catalysts, titanium-based non-metallocene catalysts. A catalyst or the like may be used.

As the vanadium catalyst, for example, JP-A-6
4-54010, specifically VOC
l ₂ (OC ₂ H ₅ ), VOCl ₃ , and
It may be used in combination with an organic aluminum compound such as a dialkylaluminum halide (for example, diethylaluminum chloride). Titanium-based nonmetallocene catalysts include:
For example, a catalyst described in JP-A-2-84404 is mentioned.

The copolymerization of ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene is usually carried out in a range of 40 to 20.
0 ° C, preferably 50 to 150 ° C, particularly preferably 60 ° C.
At to 120 ° C., atmospheric pressure to 100 kg / cm ^2, preferably atmospheric pressure to 50 kg / cm ^2, particularly preferably atmospheric pressure 30 kg / c
m ² can be performed.

This copolymerization reaction can be carried out by various polymerization methods, but is preferably carried out by solution polymerization. The copolymerization can be performed by any of a batch system, a semi-continuous system, and a continuous system, but is preferably performed by a continuous system. Further, the polymerization can be carried out in two or more stages by changing the reaction conditions.

The ethylene / α-olefin / non-conjugated polyene copolymer rubber (Y) can be obtained by the above-mentioned method, and the molecular weight of the copolymer rubber (Y) is as follows.
It can be adjusted by changing the polymerization conditions such as the polymerization temperature, and can also be adjusted by controlling the amount of hydrogen (molecular weight modifier) used.

Among the ethylene / α-olefin / non-conjugated polyene copolymer rubbers (Y), ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubbers are particularly excellent in heat resistance, tensile properties and elasticity. Is preferable because it gives an excellent thermoplastic elastomer.

As the ethylene / α-olefin / non-conjugated polyene copolymer rubber (Y), Mooney viscosity ML 1 + 4
A copolymer rubber having a (100 ° C.) (non-oil-extended state) of about 50 to 250 is generally used. In the thermoplastic elastomer used in the present invention, ethylene · α is used as the rubber component (Y).
-In addition to the olefin / non-conjugated polyene copolymer rubber,
Other rubbers such as polyisobutylene, butyl rubber and propylene / ethylene copolymer can be blended.

In the present invention, an ethylene / α-olefin / non-conjugated polyene copolymer rubber (or a rubber component obtained by adding other rubber such as polyisobutylene, butyl rubber, propylene / ethylene copolymer) (Y) Is usually 30 to 70 parts by weight, preferably 30 to 70 parts by weight, based on 100 parts by weight of the total amount of the polyolefin resin (X), the ethylene / α-olefin / non-conjugated polyene copolymer rubber (Y) and the oily softener (Z). It is used in a proportion of 40 to 60 parts by weight. The compounding amounts of other rubbers such as polyisobutylene, butyl rubber, propylene / ethylene copolymer are as follows: polyolefin resin (X), ethylene / α-olefin / non-conjugated polyene copolymer rubber (Y) and oily softener (Z) Total amount of 100
It is preferably 20 parts by weight or less based on parts by weight.

Oily softener (Z) Here, the oily softener refers to an ethylene / α-olefin / non-conjugated polyene copolymer rubber or another rubber such as polyisobutylene, butyl rubber, propylene / ethylene copolymer. A substance that has the effect of dissolving and lowering its viscosity, specifically, a petroleum softener such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, petrolatum; coal tar, coal tar pitch, etc. Coal tar softeners; fatty oil softeners such as castor oil, linseed oil, rapeseed oil, soybean oil, and coconut oil; tall oil; sub (factice); waxes such as beeswax, carnauba wax, and lanolin; , Palmitic acid, stearic acid and other fatty acids; naphthenic acid; pine oil, rosin or derivatives thereof; dioctyl phthalate, dioctyl Jipeto, ester softeners such as dioctyl sebacate; can be mentioned microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, liquid Thiokol, and hydrocarbon synthetic lubricating oils. In the present invention, the oily softener (Z) is used in an amount of 100 parts by weight based on the total amount of the polyolefin resin (X), the ethylene / α-olefin / non-conjugated polyene copolymer rubber (Y) and the oily softener (Z). And usually used at a ratio of 5 to 50 parts by weight.

Other Ingredients In addition to the polyolefin resin (X), ethylene / α-olefin / non-conjugated polyene copolymer rubber (Y) and oily softener (Z), the thermoplastic elastomer used in the present invention is required. According to the present invention, an organopolysiloxane, a slip agent, a softener other than the oily softener and / or an inorganic filler can be included.

Examples of the organopolysiloxane include dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane and the like, and epoxy-modified, alkyl-modified, amino-modified, carboxyl-modified, alcohol-modified, fluorine-modified and alkylaralkylpolyether-modified. And modified polysiloxanes such as epoxy-polyether-modified or polyether-modified, or a mixture of two or more of them.

Examples of the slip agent include fatty acids, fatty acid amides, fatty acid esters, glycerin, wax and the like. Examples of the softening agent other than the oily softening agent include, for example, fatty acid salts such as barium stearate, calcium stearate, and zinc laurate; synthetic polymer substances such as terpene resin, petroleum resin, atactic polypropylene, and cumarone indene resin. Can be mentioned.

Examples of the inorganic filler include calcium carbonate, calcium silicate, carbon black, clay, kaolin, talc, silica, diatomaceous earth, mica powder,
Asbestos, alumina, barium sulfate, aluminum sulfate, calcium sulfate, basic magnesium carbonate, molybdenum disulfide, graphite, glass fiber, glass sphere, shirasu balloon, basic magnesium sulfate whisker, calcium titanate whisker, aluminum borate whisker, etc. No.

In the present invention, the oily softener (Z) may be added at the time of the production of the thermoplastic elastomer, or may be oil-extended on the ethylene / α-olefin / non-conjugated polyene copolymer rubber (Y) in advance. May be. A known method can be used as the oil extension method. For example, using a device such as a roll or a Banbury mixer,
a method of oil-extending by mechanically kneading an α-olefin / non-conjugated polyene copolymer rubber (Y) and an oily softener (Z), or an ethylene / α-olefin / non-conjugated polyene copolymer rubber (Y )), A predetermined amount of an oily softener (Z) is added to the solution, and then the solvent is removed by a method such as steam stripping. Furthermore, in the thermoplastic elastomer used in the present invention, conventionally known heat-resistant stabilizers, anti-aging agents, weather-resistant stabilizers, antistatic agents, metal soaps, lubricants such as wax, etc., within a range that does not impair the object of the present invention. Can be added.

The thermoplastic elastomer used in the present invention comprises:
The polyolefin resin (X) described above and ethylene / α-
An olefin / non-conjugated polyene copolymer rubber (Y), an oily softener (Z), and an organopolysiloxane, a slip agent, and a softener and / or an inorganic filler other than the oily softener, if necessary. And the like, in the presence of a cross-linking agent, preferably an organic peroxide as described below, and dynamically heat-treated to cross-link the mixture. here,
"Dynamic heat treatment" refers to kneading in a molten state. In the present invention, upon preparing the thermoplastic elastomer, a polyolefin resin (X) and / or an oily softener (Z) may be further mixed with the thermoplastic elastomer dynamically heat-treated as described above.

As the organic peroxide used in the present invention, specifically, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane , 2,5-dimethyl-2,5-di- (te
rt-butylperoxy) hexyne-3,1,3-bis (tert-
Butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chloro Benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-
Butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butylcumyl peroxide and the like.

Such an organic peroxide is used for the whole object to be treated, that is, the polyolefin resin (X), the ethylene / α-olefin / non-conjugated polyene copolymer rubber (Y), the oily softener (Z) and 0.05 to 1 part by weight, preferably 0.1 to 0 part by weight, based on 100 parts by weight of other rubbers such as polyisobutylene, butyl rubber, propylene / ethylene copolymer rubber, etc. It is used in an amount of 0.5 parts by weight.

Further, a phenol resin can be used as the crosslinking agent. In this case, the amount of the phenolic resin used is the entire object to be treated, that is, the polyolefin resin (X),
Ethylene / α-olefin / non-conjugated polyene copolymer rubber (Y), oily softener (Z), and other rubbers, such as polyisobutylene, butyl rubber, propylene / ethylene copolymer rubber, which are blended as required. Is usually 1 to 20 parts by weight, preferably 2 to 15 parts by weight, more preferably 3 to 12 parts by weight based on 100 parts by weight of the total amount of

In the present invention, sulfur, p-quinonedioxime, p, p '
-Peroxy crosslinking aids such as dibenzoylquinone dioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, trimethylolpropane-N, N'-m-phenylenedimaleimide, or divinylbenzene , Triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate,
Polyfunctional methacrylate monomers such as trimethylolpropane trimethacrylate and allyl methacrylate, and polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate can be blended.

In order to accelerate the decomposition of organic peroxides, tertiary amines such as triethylamine, tributylamine, 2,4,6-tri (dimethylamino) phenol, aluminum, cobalt, vanadium, copper, calcium , A decomposition accelerator such as naphthenate such as zirconium, manganese, magnesium, lead, and mercury may be used. The dynamic heat treatment in the present invention is preferably performed using a twin screw extruder, and is preferably performed in an atmosphere of an inert gas such as nitrogen or carbon dioxide.

In the present invention, the term "crosslinked thermoplastic elastomer" means that the gel content measured by the following method is preferably 20% by weight or more, particularly preferably 45% by weight or more.

Method for measuring gel content: 100 mg of a sample of the thermoplastic elastomer composition was taken and 0.5 mm ×
A sample cut into 0.5 mm × 0.5 mm strips is immersed in 30 ml of cyclohexane at 23 ° C. for 48 hours in a closed container, and then the sample is taken out on a filter paper and kept at room temperature for 72 hours or more. Dry until dry. The value obtained by subtracting the weight of all the cyclohexane-insoluble components (fibrous filler, filler, pigment, etc.) other than the polymer component and the weight of the crystalline polyolefin resin (A) in the sample before immersion in cyclohexane from the weight of the dried residue. As “corrected final weight (Y)”. On the other hand, the weight of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (Y) in the sample is
This is referred to as “corrected initial weight (X)”. Here, the gel content is determined by the following equation.

[0046]

## EQU1 ## Gel content [% by weight] = [corrected final weight (Y) / corrected initial weight (X)] × 100

Method for producing thermoplastic elastomer (A) A preferred method for producing the thermoplastic elastomer (A) will be described. Partial crosslinking is performed by dynamic heat treatment to obtain a thermoplastic elastomer. Partial crosslinking by dynamic heat treatment
Usually, 0.05 to 1.0 parts by weight based on 100 parts by weight
Parts by weight, preferably 0.1 to 0.5 parts by weight of an organic peroxide or the like is added, and various kneading apparatuses are used, and a temperature at which the half life of the used organic peroxide is less than 1 minute, for example, Fifteen
0-280 ° C, preferably about 170-240 ° C, about 1
It is carried out by kneading under melting conditions for about 20 to 20 minutes, preferably about 2 to 10 minutes.

The thermoplastic elastomer (A) must have its MFR (2
(30 ° C., load 2.16 kg) is usually 0.1 to 100, preferably 1 to 50. Thermoplastic elastomer (A)
In order to form a surface layer with good appearance in injection molding, its MFR (230 ° C., load 2.16 kg) is usually 0.1 to 100, preferably 1 to 50.

A method for producing the thermoplastic elastomer (B) A preferred method for producing the thermoplastic elastomer (B) will be described. Partial crosslinking is performed by dynamic heat treatment to obtain a thermoplastic elastomer. Partial crosslinking by dynamic heat treatment
Usually, 0.05 to 1.0 parts by weight based on 100 parts by weight
Parts by weight, preferably 0.1 to 0.5 parts by weight of an organic peroxide or the like is added, and various kneading apparatuses are used, and a temperature at which the half life of the used organic peroxide is less than 1 minute, for example, Fifteen
0-280 ° C, preferably about 170-240 ° C, about 1
It is carried out by kneading under melting conditions for about 20 to 20 minutes, preferably about 2 to 10 minutes.

In order for the thermoplastic elastomer (B) to be extrudable, its MFR (230 ° C., load 1)
0 kg) is usually 5 to 100, preferably 10 to 50. In order for the thermoplastic elastomer (B) to be capable of injection molding, its MFR (230 ° C., load 2.16 k
g) is usually 0.1 to 100, preferably 1 to 50.

In the laminate of the present invention, the amount of the amorphous component in the thermoplastic elastomer (A) (when the polyethylene is contained, the amount of the amorphous component and (A) and the amount of an amorphous component in the thermoplastic elastomer (B) (in the case of containing polyethylene,
The ratio (b) of the oily softener to the amount of the amorphous component and the total amount of polyethylene) is as follows: Ratio (a) ≧ Ratio (b), Ratio (a) = 5 to 200% by weight, Ratio (b) = 5 It is necessary to satisfy ２００200% by weight. Further, in the laminate of the present invention, the polyolefin-based thermoplastic elastomer (A) and / or the polyolefin-based thermoplastic elastomer

(B) contains polyethylene, and the ratio (a ′) of the oily softener to the amorphous component in the thermoplastic elastomer (A) and the amount of the amorphous component in the thermoplastic elastomer (B) The proportion (b ') of the oily softening agent to the following is the proportion: proportion (a') ≥ 0.8 x proportion (b '), proportion (a') = 5 to 200% by weight, proportion (b ') = 5 Preferably, it satisfies ２００200% by weight. The ratio (a), the ratio (b), the ratio (a ′) and the ratio (b ′) are all 5
It is preferably in the range of ~ 150% by weight.

The amount of the amorphous component is defined as the ethylene / α-olefin / non-conjugated polyene copolymer rubber (Y), which is a rubber component in the thermoplastic elastomer (A) or the thermoplastic elastomer (B), and an oily softener. When a peroxide non-crosslinked hydrocarbon-based rubber-like substance such as polyisobutylene, butyl rubber, propylene / ethylene copolymer or the like is further added, the total amount of (Z) refers to the total amount including these used amounts. The laminate of the present invention is applied to a glass run channel, a roof molding for automobiles, a side molding, a wind molding and the like.

[0054]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Production Examples, Examples, and Comparative Examples, but these do not limit the scope of the present invention in any way. In the following, blending units are weight units unless otherwise specified. The methods for measuring physical properties performed in Examples and Comparative Examples are as follows.

(Solid test) 400 ° C. in an oven at 80 ° C.
After standing for a period of time, the presence or absence of solids on the surface layer was observed. (Production Example 1) Production of thermoplastic elastomer (a) A thermoplastic elastomer (a) (hereinafter, referred to as "TPO-a") was produced as follows.

Ethylene / propylene / 5-ethylidene-
2-norbornene copolymer rubber [ethylene / propylene (molar ratio) = 4/1, iodine value 13, intrinsic viscosity [η] measured in decalin at 135 ° C. 3.3 dl / g, Mooney viscosity ML 1 + 4 ( 100 ° C) (non-oil-extended state) 150]
(Hereinafter referred to as "EPDM") 48 parts by weight, 32 parts by weight of a petroleum softening agent (paraffin-based process oil manufactured by Idemitsu Kosan Co., Ltd .: trade name Diana Process PW-380) and propylene homopolymer (MFR10 (g / 10 min.) )) 2
0 parts by weight was put into a Banbury mixer, kneaded at 180 ° C. for 7 minutes, and then formed into a sheet through an open roll.
Square pellets were obtained by cutting with a sheet cutter. Then
An organic peroxide [2,5-dimethyl-
2,5-di- (tert-butylperoxy) hexane]
0.27 parts by weight and 0.4 of divinylbenzene (DVB)
After adding the parts by weight and sufficiently mixing in a Henschel mixer, the mixture was fed to a twin-screw extruder and subjected to dynamic heat treatment under the following conditions to obtain a thermoplastic elastomer (a) pellet. Set temperature of die outlet of twin screw extruder: 210 ° C Screw diameter of twin screw extruder: 50 mm Extrusion amount: 40 kg / h

(Production Example 2) Thermoplastic elastomer (b)
Production of a thermoplastic elastomer (b) (hereinafter referred to as “TPO-PEO”) in the same manner as in Production Example 1 except that the amounts of EPDM, petroleum softener and propylene homopolymer used were changed to the amounts shown in Table 1.
b ". ) Manufactured.

(Production Example 3) Thermoplastic elastomer (c)
Production of thermoplastic elastomer (c) (hereinafter referred to as “TPO-PEO”) in the same manner as in Production Example 1 except that the amounts of EPDM, petroleum softener and propylene homopolymer used were changed to the amounts shown in Table 1.
c ". ) Manufactured. T produced in Production Examples 1 to 3
Table 1 shows the composition of PO-a, TPO-b and TPO-c.

[0059]

[Table 1]

Example 1 70% by weight of TPO-a, 27.5% by weight of a propylene homopolymer (MFR10 (g / 10 minutes); the same applies hereinafter), and organopolysiloxane (viscosity of about 1,000,000 cSt; the same applies hereinafter) With respect to the surface layer (A) composed of 5% by weight, TPO-b was used as the lower layer (B), and a solid test was performed. No solid generation was observed on the surface layer (A). At this time, the concentration of the petroleum softener with respect to the amorphous component of the surface layer (A) was 40% by weight, the concentration of the petroleum softener with respect to the total amount of the amorphous component and polyethylene was 40% by weight, and the lower layer of TPO was used.
-B are 30% by weight and 30% by weight, respectively.
% By weight.

(Example 2) The surface layer (A) consisting of 70% by weight of TPO-b, 27.5% by weight of propylene homopolymer and 2.5% by weight of organopolysiloxane was used for the T layer.
PO-b was used as the lower layer (B), and a solid test was performed. No solid generation was observed on the surface layer (A). At this time, the concentration of the petroleum-based softening agent with respect to the amorphous component of the surface layer (A) was 30% by weight, the concentration of the petroleum-based softening agent with respect to the total amount of the amorphous component and polyethylene was 30% by weight, and the same petroleum-based softening of the lower layer TPO-b. The agent concentrations were 30% by weight and 30% by weight, respectively.

Example 3 TPO-b (70% by weight), propylene homopolymer (27.5% by weight), and organopolysiloxane (2.5% by weight) with respect to the surface layer (A)
PO-c was used as the lower layer (B), and a solid test was performed. No solid generation was observed on the surface layer (A). At this time, the concentration of the petroleum-based softening agent with respect to the amorphous component of the surface layer (A) was 30% by weight, the concentration of the petroleum-based softening agent with respect to the total amount of the amorphous component and polyethylene was 30% by weight, and the lower-layer TPO-c had the same petroleum-based softening ratio. The agent concentrations were 20% by weight and 20% by weight, respectively.

Example 4 70% by weight of TPO-c, 27.5% by weight of a propylene homopolymer, 2.5% by weight of an organopolysiloxane and 20% by weight of a post-added petroleum softener
TPO-b is applied to the lower layer (B) with respect to the surface layer (A)
And a solid test was performed. No solid generation was observed on the surface layer (A). At this time, the petroleum-based softening agent concentration relative to the amorphous component of the surface layer (A) was 41% by weight, the petroleum-based softening agent concentration relative to the total amount of the amorphous component and polyethylene was 41% by weight, and the petroleum-based softening of the lower layer TPO-b was the same. The agent concentrations were 30% by weight and 30% by weight, respectively.

Comparative Example 1 The surface layer (A) composed of 70% by weight of TPO-b, 27.5% by weight of a propylene homopolymer and 2.5% by weight of an organopolysiloxane was treated with T
PO-a was used as the lower layer (B), and a solid test was performed. Solid generation was observed on the surface layer (A). At this time, the concentration of the petroleum-based softening agent with respect to the amorphous component of the surface layer (A) was 30% by weight, the concentration of the petroleum-based softening agent with respect to the total amount of the amorphous component and polyethylene was 30% by weight, and the same petroleum-based softening of the lower layer TPO-a. The agent concentrations were 40% by weight and 40% by weight, respectively.

Comparative Example 2 70% by weight of TPO-b, polyethylene (MFR20 (190 ° C., load 2.16 k)
g)) 27.5% by weight and organopolysiloxane
With respect to the surface layer (A) composed of 5% by weight, TPO-b was used as the lower layer (B), and a solid test was performed. Solid generation was observed on the surface layer (A). At this time, the concentration of the petroleum-based softener with respect to the amorphous component of the surface layer (A) was 30% by weight, the concentration of the petroleum-based softener with respect to the total amount of the amorphous component and polyethylene was 20.1% by weight, and the lower layer of TPO-b had the same petroleum content. The system softener concentrations were 30% by weight and 30% by weight, respectively.

(Comparative Example 3) The surface layer (A) consisting of 70% by weight of TPO-c, 27.5% by weight of propylene homopolymer and 2.5% by weight of organopolysiloxane was added with T
PO-a was used as the lower layer (B), and a solid test was performed. Solid generation was observed on the surface layer (A). At this time, the concentration of the petroleum-based softener with respect to the amorphous component of the surface layer (A) was 20% by weight, the concentration of the petroleum-based softener with respect to the total amount of the amorphous component and polyethylene was 20% by weight, and the lower-layer TPO-a was petroleum-based softening. The agent concentrations were 40% by weight and 40% by weight, respectively.

Comparative Example 4 The surface layer (A) composed of 70% by weight of TPO-c, 27.5% by weight of a propylene homopolymer and 2.5% by weight of an organopolysiloxane was treated with T
PO-b was used as the lower layer (B), and a solid test was performed. Solid generation was observed on the surface layer (A). At this time, the concentration of the petroleum-based softening agent with respect to the amorphous component of the surface layer (A) was 20% by weight, the concentration of the petroleum-based softening agent with respect to the total amount of the amorphous component and polyethylene was 20% by weight, and the same petroleum-based softening of the lower layer TPO-b. The agent concentrations were 30% by weight and 30% by weight, respectively. Example 1
Table 2 shows the amounts and the results of the components used in Comparative Example 4 and Comparative Examples 1 to 4.

[0068]

[Table 2]

[0069]

As described above, the surface of the thermoplastic elastomer laminate of the present invention does not change even when it is exposed to a high temperature, and no solid occurs.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08L 23/08 C08L 91/00 91/00 B60J 1/16 A

Claims (4)

[Claims] 1. A laminate in which a polyolefin-based thermoplastic elastomer (B) containing an oil-based softener is laminated on a surface layer made of a polyolefin-based thermoplastic elastomer (A) containing an oil-based softener, A) Amount of amorphous component in A) (If polyethylene is contained, the amount of amorphous component and total amount of polyethylene)
(A) the ratio of the oily softener to the thermoplastic elastomer (B) and the ratio of the oily softener to the amount of the amorphous component (if polyethylene is contained, the amount of the amorphous component and the total amount of polyethylene) ( A laminate, wherein b) satisfies the following requirements: ratio (a) ≧ ratio (b), ratio (a) = 5 to 200% by weight, ratio (b) = 5 to 200% by weight. 2. The laminate according to claim 1, wherein the polyolefin-based thermoplastic elastomer (A) and / or the polyolefin-based thermoplastic elastomer (B) contain polyethylene, and The ratio of the oily softener to the amount of the crystalline component (a ′) and the ratio of the oily softener to the amount of the amorphous component in the thermoplastic elastomer (B) (b ′) are as follows: Ratio (a ′) ≧ 0. A laminate characterized by satisfying 8 × ratio (b ′), ratio (a ′) = 5 to 200% by weight, and ratio (b ′) = 5 to 200% by weight. 3. A glass run channel comprising the laminate according to claim 1. 4. A roof molding, side molding or wind molding for an automobile, comprising the laminate according to claim 1.