JP2003155386A - Olefinic thermoplastic elastomer, composite molded product and method for producing composite molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an olefinic thermoplastic elastomer having sufficient adhesive strength for vulcanized rubber even without through an adhesive layer and capable of forming a molded product causing matrix destruction during peeling, a composite molded product obtained by joining the thermoplastic elastomer to the vulcanized rubber and a method for producing the composite molded product. SOLUTION: This olefinic thermoplastic elastomer is obtained by cross-linking 5-40 pts.wt. of a crystalline ethylenic polymer (A) having >=10% crystallinity measured by differential scanning calorimetry (DSC), 5-70 pts.wt. of an ethylene-α-olefin (-nonconjugated polyene) copolymer rubber (B) composed of ethylene and a 3-20C α-olefin and, as necessary, the nonconjugated polyene and 5-40 pts.wt. of a polypropylene (C) [the total amount of the components (A), (B) and (C) is 100 pts.wt.]. The olefinic thermoplastic elastomer causes the matrix destruction when fusing and peeling tests for the vulcanized rubber molded product are carried out.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin-based thermoplastic elastomer, a composite molded article made of the olefin-based thermoplastic elastomer, its use and a method for producing the composite molded article, and more particularly, a weather strip for automobiles and a door trim. TECHNICAL FIELD The present invention relates to an olefin-based thermoplastic elastomer suitable for welding and forming corner irregular-shaped connecting portions and irregular-shaped terminal portions of the like, a composite molded article made of the olefin-based thermoplastic elastomer, its use, and a method for producing the composite molded article.

[0002]

BACKGROUND OF THE INVENTION In the past, the manufacture of weatherstrips with connections was generally made with ethylene-propylene-
An extrusion vulcanization molded product made of a rubber compound of a non-conjugated diene terpolymer (EPDM) is cut and set in a mold from one or both, and the EPD is formed in a cavity to be formed.
It is carried out by injecting a rubber molding material of the same type as the rubber compound of M and performing vulcanization molding.

On the other hand, as a molding material, ethylene / propylene / non-conjugated diene terpolymer (EPDM) is used.
From the standpoint of productivity, environmental friendliness, and weight saving, a thermoplastic elastomer (composition) that does not require a vulcanization step has begun to be used in place of the vulcanized rubber in which the rubber is used.

However, in general, the vulcanized rubber and the thermoplastic elastomer cannot be vulcanized and adhered to each other, so that they were integrated by using an adhesive, but they are sufficient in terms of productivity or environmental resistance. I can't say.

As a technique relating to the composition of a thermoplastic elastomer, a polar group-containing resin is added (Japanese Patent Laid-Open No. 2-1152 / 1990).
49, JP-A-8-244068, JP-A-1
No. 0-324200), the addition of a polar group-containing resin may result in a poor mold releasability of the molded product from the mold during molding, resulting in a long molding cycle.

Another technique is to add a specific ethylene / 1-octene copolymer before molding a thermoplastic elastomer (Japanese Patent Laid-Open No. 9-40814). Although the present inventors have confirmed that this technique is extremely effective in breaking the base material, the rubber elasticity of the molded product is lost due to the addition of the non-crosslinked ethylene polymer (ethylene / 1-octene copolymer). I will be destroyed.

Further, as a technique of the above vulcanized rubber, there is a technique of adding microcrystalline polypropylene in addition to the composition of the conventional vulcanized rubber (JP-A-10-7849).
However, when microcrystalline polypropylene such as atactic polypropylene is added, not only the rubber elasticity of the conventional vulcanized rubber is deteriorated, but also the stickiness of the molded product after aging may occur.

Not only the technique relating to the composition of the thermoplastic elastomer or the vulcanized rubber as described above, but also an attempt to obtain the anchor effect by cutting the vulcanized rubber and then making unevenness on the cut surface (Japanese Patent Application Laid-Open No. 9-29138). No. 118133), or a vulcanized rubber coated with a polyolefin resin powder on its cut surface (JP-A-6-47816).
All of them have the drawback that the productivity is lowered but the adhesiveness is not improved. Also, after cutting the vulcanized rubber, a method of preheating the cut surface with a heater in advance (JP-A-9-11)
No. 8134) has been proposed, but this does not significantly improve the adhesiveness.

Therefore, it exhibits sufficient adhesive strength to vulcanized rubber without interposing an adhesive layer, and the base material is broken at the time of peeling (not the peeling at the bonding interface, but the molded body).
An olefin-based thermoplastic elastomer capable of forming a molded body that produces a rubber, a composite molded body in which the elastomer is bonded to vulcanized rubber, and a lightweight composite molded body having sufficient hardness and rubber elasticity as a thermoplastic elastomer are formed. It is desired to provide an olefinic thermoplastic elastomer having excellent moldability and economy, and a composite molded body obtained by welding the elastomer to a vulcanized rubber.

[0010]

It is an object of the present invention to solve the problems associated with the prior art as described above, showing sufficient adhesive strength to vulcanized rubber without interposing an adhesive layer and at the time of peeling. An object of the present invention is to provide an olefin-based thermoplastic elastomer capable of forming a molded product that causes a base material fracture, a composite molded product obtained by welding the elastomer to a vulcanized rubber, and a method for producing the composite molded product.

[0011]

SUMMARY OF THE INVENTION The first olefinic thermoplastic elastomer according to the present invention has a crystallinity of 10 as measured by the DSC method.
% Or more, crystalline ethylene polymer (A) 5 to 40
Ethylene / α consisting of parts by weight, ethylene and α-olefin having 3 to 20 carbon atoms, and non-conjugated polyene as required.
-Olefin (/ non-conjugated polyene) copolymer rubber (B)
5 to 70 parts by weight, polypropylene (C) 5 to 40 parts by weight [the total amount of components (A), (B) and (C) is 100 parts by weight], and It is characterized in that the base material is broken when a welding peeling test is performed on the vulcanized rubber molded product.

In the first olefinic thermoplastic elastomer of the present invention, the compression set CS at 70 ° C. preferably satisfies the following relational expression: CS (NH) ≦ 70% CS (NH)- CS (H) ≧ 5% (In the formula, CS (NH) represents CS when the molded product is not subjected to heat treatment, and CS (H) is the molded product after the molded product is heat-treated at a temperature of 100 ° C. Of CS).

The second olefinic thermoplastic elastomer of the present invention has a crystallinity of 10% as measured by the DSC method.
The above-mentioned crystalline ethylene polymer (A) (5 to 40 parts by weight), ethylene, an α-olefin having 3 to 20 carbon atoms, and an ethylene / α-olefin (/ non-conjugated polyene, if necessary, a non-conjugated polyene) ) Copolymer rubber (B) 5
70 parts by weight and 5 to 40 parts by weight of polypropylene (C) [the total amount of components (A), (B) and (C) is 100 parts by weight], and a cross-linking agent (D) of 0. 01-
It is characterized by being obtained by dynamically performing heat treatment in the presence of 0.12 parts by weight.

The crosslinking agent (D) is preferably an organic peroxide.

The first and second olefinic thermoplastic elastomers according to the present invention can be suitably used for welding a vulcanized rubber to a molded body.

The first and second olefin-based thermoplastic elastomers are thermoplastic elastomers which, when subjected to a welding test of a vulcanized rubber to a press-molded product, cause a base material fracture during a tensile peel test. preferable.

The composite molded article according to the present invention comprises a molded article made of vulcanized rubber and a molded article made of a thermoplastic elastomer, which are joined together, and the thermoplastic elastomer has a crystallinity of 10 as measured by the DSC method. % Or more, crystalline ethylene polymer (crystallinity of 10 wt% or more) (A) 5 to 40 parts by weight, ethylene, C 3 to C 20 α-olefin, and optionally non-conjugated polyene Ethylene / α-
Olefin (/ non-conjugated polyene) copolymer rubber (B) 5
˜70 parts by weight and polypropylene (C) 5 to 40 parts by weight [the total amount of components (A), (B) and (C) is 100 parts by weight]. It is characterized by that.

In the above-mentioned composite molded article, the crosslinking is carried out by adding the crosslinking agent (D) to 100 parts of the components (A), (B) and (C).
It is preferable that the heat treatment is carried out by dynamically presenting it in a proportion of 0.01 to 0.12 parts by weight with respect to parts by weight.

Further, the crosslinked thermoplastic elastomer used in the above-mentioned composite molded body is preferably one which causes the base material to be broken when a welding peeling test to a vulcanized rubber molded body is conducted.

Further, in the composite molded article according to the present invention, it is preferable that the base material fracture is observed when a tensile peeling test is conducted on the joint between the vulcanized rubber and the thermoplastic elastomer.

Further, the composite molded article according to the present invention comprises a step of forming a joint between the molded article made of vulcanized rubber and the above-mentioned molded article made of the first or second thermoplastic elastomer, and the joined section. It is obtained through a step of heat-treating a molded product containing the above at a temperature of 80 ° C. or higher.

In the above-mentioned composite molded body, the molded body made of vulcanized rubber and the molded body made of the above-mentioned first or second thermoplastic elastomer are joined together by the molded body made of vulcanized rubber and the thermoplastic elastomer. It is preferable that the welding is performed by

In the composite molded article according to the present invention, the vulcanized rubber is preferably an ethylene / α-olefin / polyene copolymer rubber.

The composite molded article according to the present invention is preferably used for automobile interior and exterior materials, and more preferably a weather strip material.

The above-mentioned weather strip material is formed by joining a linear portion and a joining corner member, and the straight portion is made of the molded product of the vulcanized rubber, and the joining corner member according to the present invention. It is preferably formed from the first or second thermoplastic elastomer.

The composite molded article of the present invention is preferably obtained by insert molding.

The method for producing a composite molded article according to the present invention comprises a molded article made of vulcanized rubber, and the first or second invention according to the present invention.
The method is characterized by including a step of forming a joint with a molded body made of the thermoplastic elastomer, and a step of heat-treating the molded body including the joint at a temperature of 80 ° C. or higher.

In the method for producing a composite molded article according to the present invention, the formation of the above-mentioned joint portion includes a molded article made of vulcanized rubber,
It is preferable to weld it with the first or second thermoplastic elastomer according to the present invention.

In the method for producing a composite molded article of the present invention, it is preferable that the welding is performed by insert molding of a thermoplastic elastomer in the presence of vulcanized rubber.

The first and second olefinic thermoplastic elastomers according to the present invention exhibit a sufficient adhesive strength with respect to vulcanized rubber without interposing an adhesive layer and form a molded body which causes a base material fracture upon peeling. In addition, it is possible to form a lightweight molded product having sufficient hardness and rubber elasticity as a thermoplastic elastomer.

[0031]

DETAILED DESCRIPTION OF THE INVENTION The olefin-based thermoplastic elastomer according to the present invention, the composite molded article made of the olefin-based thermoplastic elastomer, its use, and the method for producing the composite molded article made of the olefin-based thermoplastic elastomer will be described below. To explain.

Thermoplastic elastomers have physical properties similar to rubbers, such as flexibility and impact resilience, and can be processed as thermoplastics in contrast to ordinary rubbers. For example, it is made in the macromolecule dictionary (Maruzen Co., Ltd., 1994).

First, the first and second olefinic thermoplastic elastomers according to the present invention will be described. Hereinafter, each component used in the olefin-based thermoplastic elastomer will be described.

Crystalline Ethylene Polymer (A) The crystalline ethylene polymer (A) used in the present invention is
The crystallinity measured by the DSC method is 10% or more.

The density (ASTM D 1505) is 0.870-
0.99 g / cm ³ , usually 0.880-0.970 g
/ Cm ³ , preferably 0.885 to 0.965 g / c
m ³ , more preferably 0.890 to 0.960 g / c
It is preferably m ³ .

This crystalline ethylene-based polymer (A) is an ethylene homopolymer (polyethylene) or crystalline ethylene / α-containing ethylene and an α-olefin having 3 to 20 carbon atoms, preferably 3 to 8 carbon atoms. It is an olefin copolymer. When comonomer is included, the comonomer content is small, not more than 25 mol% of the total.

The crystalline ethylene polymer (A) used in the present invention may have a crystallinity of 10% or more as measured by a differential scanning calorimeter (DSC), for example, high density polyethylene, Not only low-density polyethylene and linear low-density polyethylene, but also ethylene-butene-1 copolymer, ethylene-propylene copolymer, ethylene-octene copolymer, and the like, high-density polyethylene, low-density polyethylene, and It is preferably at least one selected from linear low-density polyethylene. For example, two or more blends may be used, and two or more blends of high-density polyethylene and low-density polyethylene may be used.
It may be composed of two kinds, low density polyethylene and linear low density polyethylene. Also, two or more kinds of high-density polyethylene, two or more kinds of low-density polyethylene, and two or more kinds of linear low-density polyethylene may be used. Among them, high density polyethylene and linear low density polyethylene are preferable. Further, the catalyst or the like used in the production of the crystalline ethylene polymer is not particularly limited, but it is produced by a general Ziegler-Natta catalyst, a metallocene catalyst or the like.

The crystalline ethylene polymer (A) used in the present invention has a melt flow rate (MFR; ASTM D 123).
8,190 ℃, load 2.16kg), preferably 0.01-50
It is preferably 0 g / 10 minutes or less, usually 0.1 to 100 g / 10 minutes, and more preferably 0.5 to 50 g / 10 minutes. When a crystalline ethylene polymer having an MFR within the above range is used, a thermoplastic elastomer composition having excellent moldability can be obtained.

The crystalline ethylene-based polymer (A) is the total amount of the crystalline ethylene-based polymer (A), the ethylene / α-olefin (/ non-conjugated polyene) copolymer rubber (B) and the polypropylene (C). 5-4 for 100 parts by weight
It is used in an amount of 0 part by weight, preferably 10 to 35 parts by weight, more preferably 15 to 30 parts by weight. When the crystalline ethylene polymer (A) is used in the above ratio, the rubber elasticity is excellent, and when the heat treatment is performed, the rubber elasticity is improved,
An inexpensive thermoplastic elastomer composition having excellent flexibility can be obtained, and at the same time, an inexpensive thermoplastic elastomer composition having excellent weldability to an extrusion molded article such as a weather strip made of vulcanized rubber for automobiles can be obtained. be able to.

Ethylene / α-olefin (/ non-conjugated poly
En) Copolymer rubber (B) The ethylene / α-olefin (/ non-conjugated polyene) copolymer rubber (B) used in the present invention is a copolymer of ethylene, α-olefin and, if necessary, a non-conjugated polyene. Examples of the polymer rubber include ethylene / α-olefin / non-conjugated polyene copolymer rubber (B-1) and ethylene / α-olefin copolymer rubber (B-2).

The ethylene / α-olefin / non-conjugated polyene copolymer rubber (B-1) used in the present invention is an olefinic rubber composed of ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene. is there.

Here, the "rubber" of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B-1) means D
It means a copolymer having a crystallinity of less than 10% as determined by the SC method.

As the α-olefin having 3 to 20 carbon atoms, specifically, propylene, 1-butene, 4-methylpentene-1,1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicosene, 9-
Methyldecene-1,11-methyldodecene-1,12-ethyltetradecene-1 and the like can be mentioned. Among them, propylene,
1-butene, 4-methylpentene-1,1-hexene and 1-octene are preferred. Especially, propylene is preferable.

These α-olefins may be used alone or in combination of two or more. Further, as the non-conjugated polyene, specifically, 1,4-hexadiene, 3-methyl
-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-
Methyl-1,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 8-methyl-4-ethylidene-1,7-nonadiene, 4-ethylidene-1, Chain non-conjugated dienes such as 7-undecadiene; methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-methylene-2
-Norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5
-Cyclic non-conjugated dienes such as isopropenyl-2-norbornene, 5-vinyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-isobutenyl-2-norbornene, cyclopentadiene, norbornadiene; 2,3-diisopropene Trienes such as lidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, 4-ethylidene-8-methyl-1,7-nanodiene and the like can be mentioned. Among them, 5-ethylidene-2
-Norbornene, 5-vinyl-2-norbornene, cyclopentadiene and 4-ethylidene-8-methyl-1,7-nanodiene are preferred.

The ethylene / α-olefin / non-conjugated polyene copolymer rubber (B-1) used in the present invention has a constitutional unit content (ethylene content) of 5 derived from ethylene.
0 mol% or more, usually 50 to 90 mol%, preferably 60
To 85 mol% and the content of the constituent unit derived from an α-olefin having 3 to 20 carbon atoms (α-olefin content) is 50 mol% or less, usually 50 to 10 mol%, preferably 40 to 15 mol%. And the iodine value of the non-conjugated polyene is usually 0.1 to 30, preferably 0.1 to 25. However, the total of the ethylene content and the α-olefin content is 100 mol%. The composition of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B-1) is determined by ¹³ C-NMR measurement.

The ethylene / α-olefin / non-conjugated polyene copolymer (B-1) used in the present invention is a so-called oil-added rubber containing a softening agent, preferably a mineral oil-based softening agent, in the production thereof. It may be. Examples of the mineral oil-based softening agent include conventionally known mineral oil-based softening agents such as paraffin-based process oil. Also, ethylene / α-
The Mooney viscosity [ML _{1 + 4} (100 ° C.)] of the olefin / non-conjugated polyene copolymer rubber (B-1) is usually 10 to 25.
It is 0, preferably 30 to 150.

The above-mentioned ethylene / α-olefin /
The non-conjugated polyene copolymer rubber (B-1) can be produced by a conventionally known method.

Ethylene / α-olefin / non-conjugated polyene copolymer rubber (B-1) includes high density polyethylene (A), ethylene / α-olefin / non-conjugated polyene copolymer rubber (B-1) and polypropylene. It is used in a proportion of 5 to 70 parts by weight, preferably 10 to 65 parts by weight, more preferably 20 to 60 parts by weight, based on 100 parts by weight of the total amount of (C). When this copolymer rubber (B-1) is used in a ratio within the above range, it has excellent weldability to an extruded product such as a weather strip made of vulcanized rubber and has appropriate softness (hardness). A thermoplastic elastomer composition having excellent moldability capable of forming a corner portion can be obtained.

Further, a copolymer rubber (B) of the present invention comprising ethylene, an α-olefin, and optionally a non-conjugated polyene
As the ethylene / α-olefin copolymer rubber (B-2) obtained by copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms, and more preferably 3 to 8 carbon atoms. You can also

Specific examples of the ethylene / α-olefin copolymer (B-2) include ethylene / propylene copolymer rubber (EPR) and ethylene / 1-butene copolymer rubber (EBR). , Ethylene / 1-octene copolymer rubber (EOR) and the like.

Melt flow rate (MFR; ASTM D 123) of ethylene / α-olefin copolymer rubber (B-2)
8,190 ℃, 2.16kg load) is usually 0.1-100g / 1
It is 0 minutes, preferably 0.2 to 50 g / 10 minutes, and more preferably 0.5 to 30 g / 10 minutes.

The α-olefin constituting the ethylene / α-olefin copolymer rubber (B-2) is ethylene / α-olefin.
-Olefin / non-conjugated polyene copolymer rubber (B-1)
It is the same as the α-olefin constituting the. The copolymer rubber (B-2) has a constitutional unit content (ethylene content) derived from ethylene of 50 mol% or more, usually 50 to 90 mol%, preferably 60 to 85 mol% and having 3 carbon atoms. The content of the constitutional unit derived from α-olefin of 20 to 50 (α-olefin content) is 50 mol% or less, usually 50 to 50%.
It is 10 mol%, preferably 40 to 15 mol%.

The copolymer rubber (B) of ethylene, α-olefin and, if necessary, non-conjugated polyene is only one or more ethylene / α-olefin / non-conjugated polyene copolymer rubber (B-1). Or at least one ethylene / α-olefin copolymer rubber (B-2), or (B-1) and (B-2) in combination. May be. In that case, (B-1) and (B-2)
There is no particular limitation on the ratio of the ethylene / α-olefin copolymer rubber (B-2) and the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B-1) and the ethylene / α-olefin copolymer rubber (B-1). It is used in an amount of 50 parts by weight or less, usually 10 to 50 parts by weight, based on 100 parts by weight of the total amount of the α-olefin copolymer rubber (B-2). However, the total blending amount of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B-1) and the ethylene / α-olefin copolymer rubber (B-2) is the crystalline ethylene polymer (A). , Ethylene / α-olefin / non-conjugated polyene copolymer rubber (B-1), polypropylene (C)
And ethylene / α-olefin copolymer rubber (B-
5 to 70 parts by weight based on 100 parts by weight of 2),
Preferably 10 to 65 parts by weight, more preferably 20 to
60 parts by weight. When the copolymer rubber (B-1) and the copolymer rubber (B-2) are used in the above proportions, they are excellent in weldability to an extruded product such as a weather strip made of vulcanized rubber and have an appropriate softness. A thermoplastic elastomer composition having excellent moldability capable of forming a corner portion having hardness (hardness) is obtained.

Polypropylene (C) The polypropylene (C) used in the present invention is an olefin resin, and is a propylene homopolymer, or propylene and ethylene and / or a random copolymer of ethylene and / or an α-olefin having 4 to 20 carbon atoms. Alternatively, it is a block-copolymerized propylene copolymer copolymer.

As the α-olefin having 4 to 20 carbon atoms, specifically, 1-butene, 4-methylpentene-1,1-
Hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicosene, 9-methyldecene
-1,11-Methyldodecene-1,12-Ethyltetradecene-1
And so on.

As the comonomer to be copolymerized with propylene, ethylene and 1-butene are preferable. These α-olefins may be used alone or in combination of two or more.

The constituent unit content (propylene content) derived from propylene in this propylene copolymer is
It is usually 50 to 90% by weight, and the content of constitutional units derived from a comonomer (comonomer content) is usually 50 to 10%.
%. The composition of the propylene copolymer is ¹³ C-
It is determined by measurement by NMR.

Polypropylene (C) has a melt flow rate (MFR; ASTM D 1238, 230 ° C., load 2.16 kg) of usually 0.01 to 100 g / 10 min, preferably 0.1 to 8 g.
0 g / 10 minutes, more preferably 0.3 to 60 g / 10
Minutes are desirable.

The melting point (Tm) of polypropylene (C) measured by DSC is usually 170 ° C. or lower.

The polypropylene (C) is based on 100 parts by weight of the crystalline ethylene polymer (A), the ethylene / α-olefin (/ non-conjugated polyene) copolymer rubber (B) and the polypropylene (C). 5 to 40 parts by weight, preferably 10 to 35 parts by weight, more preferably 1
It is used in a proportion of 5 to 30 parts by weight. When polypropylene (C) is used in a ratio within the above range, it is possible to form a corner portion having excellent weldability to an extrusion molded article such as a weather strip made of vulcanized rubber and having appropriate softness (hardness). A thermoplastic elastomer composition having excellent moldability is obtained.

Crosslinking Agent (D) The olefinic thermoplastic elastomer according to the present invention comprises a blended product of the above components (A), (B) and (C) in the presence of a crosslinking agent (D). It can be prepared by heat treatment dynamically.

Examples of the cross-linking agent (D) used in the present invention include organic peroxides, sulfur, sulfur compounds, and phenolic vulcanizing agents such as phenol resins. Among them, organic peroxides are preferably used. To be

Specific examples of the organic peroxide include dicumyl peroxide, di-tert-butyl peroxide and 2,5-
Dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-Dimethyl-2,5-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, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,
4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl perbenzoate,
tert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert
-Butyl cumyl peroxide and the like.

Among them, odor and scorch stability are 2,
5-Dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-Dimethyl-2,5-di (tert-butylperoxy)
Hexine-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane and n-butyl
-4,4-Bis (tert-butylperoxy) valerate is preferred, with 1,3-bis (tert-butylperoxyisopropyl) benzene being most preferred.

This organic peroxide is a crystalline ethylene polymer (A), ethylene / α-olefin (/ non-conjugated polyene) copolymer rubber (B) and polypropylene (C).
Of 0.01 to 0.1 per 100 parts by weight of the total amount of
It is used in a proportion of 2 parts by weight, preferably about 0.03 to 0.10 parts by weight. When the organic peroxide is used in the above ratio,
A thermoplastic elastomer composition in which the crystalline ethylene polymer (A) and the copolymer rubber (B) are cross-linked is obtained, and the rubber-like properties and strength such as heat resistance, tensile properties, elastic recovery and impact resilience are obtained. Can be obtained. Moreover, this composition is excellent in moldability.

In the present invention, sulfur, p-quinonedioxime, p, p'- are used in the crosslinking treatment with the organic peroxide.
Crosslinking aids such as dibenzoylquinone dioxime, N-methyl-N, 4-dinitrosoaniline, nitrobenzene, diphenylguanidine, trimethylolpropane-N, N'-m-phenylene dimaleimide, or divinylbenzene, triallyl sialic acid. Compounded with polyfunctional methacrylate monomers such as nurate, eletin glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate and allyl methacrylate, and polyfunctional vinyl monomers such as vinyl butyrate or vinyl stearate. be able to. With such a compound, a uniform and mild crosslinking reaction can be expected. In particular, in the present invention, when divinylbenzene is used, it is easy to handle and is compatible with the crystalline ethylene polymer (A), the copolymer rubber (B) and the polypropylene (C) which are the main components of the object to be treated. Is good, has an organic peroxide solubilizing action, and acts as a dispersion aid for organic peroxides, so that a cross-linking effect by heat treatment is uniform, and a composition with well-balanced fluidity and physical properties can be obtained. Most preferred.

In the present invention, the blending amount of such a crosslinking aid or polyfunctional vinyl monomer is such that the crystalline ethylene polymer (A), the ethylene / α-olefin (/ non-conjugated polyene) copolymer rubber are used. Usually, 0.0 is added to 100 parts by weight of the total amount of (B) and polypropylene (C).
The range of 1 to 0.4 parts by weight, particularly 0.03 to 0.2 parts by weight is preferable, and by adding a crosslinking aid or a polyfunctional vinyl monomer within this range, excellent fluidity and composition can be obtained. A composition that does not cause changes in physical properties due to heat history during processing and molding of the product can be obtained.

Other Components In the thermoplastic elastomer composition according to the present invention, if necessary, additives such as slip agents, fillers, antioxidants, weather resistance stabilizers and colorants may be added for the purpose of the present invention. It can be mixed within a range that does not impair it.

Examples of the slip agent include fatty acid amide, silicone oil, glycerin, wax and paraffin oil.

Examples of the filler include conventionally known fillers, specifically, carbon black, clay, talc, calcium carbonate, kaolin, diatomaceous earth, silica, alumina, graphite, glass fiber and the like.

In the first thermoplastic elastomer of the present invention, 5 to 40% by weight of a crystalline ethylene polymer (A) having a crystallinity of 10% or more measured by DSC,
Ethylene / α-olefin (/ non-conjugated polyene) copolymer rubber (B) 5 to 70% by weight, consisting of ethylene and α-olefin having 3 to 20 carbon atoms, and optionally non-conjugated polyene, polypropylene (C) It is formed by crosslinking a composition composed of 5 to 40% by weight. The crosslinking method is not particularly limited, but a method of dynamically heat-treating the crosslinking agent (D) in the presence of the above-described amount is exemplified.

Here, "dynamically heat-treating" means kneading in a molten state (hereinafter the same).

The dynamic heat treatment in the present invention is preferably performed in a non-open type apparatus, and is preferably performed in an atmosphere of an inert gas such as nitrogen or carbon dioxide.

The kneading temperature is usually 150 to 280 ° C.,
It is preferably 170 to 240 ° C. The kneading time is usually 1 to 20 minutes, preferably 3 to 10 minutes. Also,
The shear force applied is 10 to 100,0 as a shear rate.
It is 00 sec ^-1 , preferably 100 to 50,000 sec ^-1 .

As the kneading device, a mixing roll, an intensive mixer (for example, Banbury mixer, kneader), a single-screw or twin-screw extruder and the like can be used, but a non-open type device is preferable.

According to the present invention, the above-mentioned dynamic heat treatment gives a thermoplastic elastomer composition in which the crystalline ethylene polymer (A) and the copolymer rubber (B) are crosslinked.

Melt flow rate (MFR; ASTM D 1238, 230 ° C., 2.) of the first and second olefinic thermoplastic elastomers according to the present invention obtained as described above.
The load (16 kg) is usually 0.01 to 1000 g / 10 minutes, preferably 0.05 to 100 g / 10 minutes, and more preferably 0.1 to 70 g / 10 minutes. The thermoplastic elastomer having a melt flow rate within the above range has excellent moldability. Further, the thermoplastic elastomer of the present invention usually has a sea-island structure morphology. It is preferable that the sea phase is polypropylene (C) and the island phase is a crystalline ethylene polymer (A) and an ethylene / α-olefin (/ non-conjugated polyene) copolymer rubber (B).

In the first olefinic thermoplastic elastomer of the present invention, the compression set CS at 70 ° C. preferably satisfies the following relational expression: CS (NH) ≦ 70% CS (NH) -CS ( H) ≧ 5% (In the formula, CS (NH) represents CS in the case where the molded product is not subjected to heat treatment, and CS (H) is the CS of the molded product after the molded product is heat-treated at a temperature of 100 ° C. Represents).

Note that CS (NH) ≦ 70% means that
It may mean that it is crosslinked.

CS (NH) is preferably 70% or less, more preferably 65% or less, and further preferably 60% or less. There is no particular lower limit, but it is usually 30% or more.

CS (NH) -CS (H) is preferably 5% or more, more preferably 7% or more, still more preferably 10% or more. Within this range, rubber elasticity is generally excellent.

The heat treatment is not particularly limited as long as it is a temperature of 80 ° C. or higher, preferably 90 ° C., more preferably 100 ° C. or higher, and the upper limit is not particularly limited.
It is usually 130 ° C or lower. Here, the temperature refers to the temperature of the atmosphere.

The heat treatment time is not particularly limited, but is usually 1 hour or longer, preferably 5 hours or longer, more preferably 10 hours or longer, and the upper limit is usually 24 hours or shorter.

In the heat treatment, a heater, an oven or the like can be used as appropriate. A concrete measuring method of CS will be described in the section of Examples.

In a preferred embodiment, the second olefinic thermoplastic elastomer of the present invention preferably satisfies the relationship of CS (NH) ≤70% and CS (NH) -CS (H) ≥5% as described above. is there.

As the first and second olefinic thermoplastic elastomers according to the present invention, when the adhesion test of the vulcanized rubber to the press molded product is conducted, the base material is broken during the tensile peel test. It is preferable.

Now, a method for tensile peeling test of a welded product of a vulcanized rubber to a press-formed product (sheet) will be described. (Preparation of Vulcanized Rubber) The vulcanized rubber is 100 parts by weight of raw material rubber, 170 parts by weight of carbon black, 95 parts by weight of softening agent, 5 parts by weight of zinc white, 1 part by weight of stearic acid, and 1 part of activator.
Parts by weight, calcium oxide 50 parts by weight, sulfur 5 parts by weight,
2-mercaptobenzothiazole 15 parts by weight, dibenzothiazyl disulfide 5 parts by weight, zinc dibutyldithiocarbamate 20 parts by weight, zinc dimethyldithiocarbamate 5 parts by weight, ethylene urea 10 parts by weight and dithiodimorpholine 5 parts by weight, a rubber Prepare the formulation.

When the thermoplastic elastomer of the present invention is subjected to a tensile peel test after welding with a vulcanized rubber, ethylene / propylene / 5-ethylidene-2-norbornene random is used as a raw rubber for the vulcanized rubber. Copolymer rubber (ethylene content = 65 to 70 mol%, 135 ° C.
Intrinsic viscosity [η] measured in decalin = 2.5-3.0
dl / g, iodine value = 10 to 15 g / 100 g) is used. (Molding Method by Press) The above rubber compound is heated at 170 ° C. for 10 minutes using a 150 ton press to be vulcanized and molded, and a flat plate having a length of 12 cm, a width of 14.7 cm and a thickness of 2 mm is manufactured. In this way, a vulcanized rubber press sheet is obtained. (Adhesion Method for Pressed Product) Immediately before adhering to the corner material, the product is cut with a cutter so that the length is 2.5 cm, and set in a mold so that the thermoplastic elastomer adheres to the cut surface of the cutter. After that, the injection temperature is 230 ℃, the mold temperature is 5
The corner material is melt-bonded to the thermoplastic elastomer at 0 ° C, and the welded test piece is heated to 80 ° C or more x 5 in an oven.
After a lapse of time, a test piece for observing the peeled state is obtained. (Observation of peeling state) The joint portion of the test piece obtained as described above was punched out into a strip shape having a width of 2 cm, and the pulling speed was 20.
A tensile peel test is performed at 0 mm / min. Normally, the corner material is an uncolored product and the vulcanized rubber is a black colored product, and the cross section after the test is observed. The cross section was visually observed, and if the corner material remained on the cross section, the base material was destroyed, and if the corner material did not remain, interface peeling was performed.

Composite Molded Article A composite molded article according to the present invention is obtained by joining, preferably welding, the above-mentioned first and second olefinic thermoplastic elastomers according to the present invention to a molded article made of vulcanized rubber. .

Ethylene / α-olefin / polyene copolymer rubber is preferable as a vulcanized rubber for forming a molded product made of this vulcanized rubber from the viewpoint of weldability to the thermoplastic elastomer composition. As such a copolymer rubber, the above-mentioned ethylene / α-olefin (/ non-conjugated polyene) is used.
The copolymer rubber (B) is preferably used.

The vulcanized rubber mentioned here includes not only those crosslinked with sulfur but also those crosslinked with other crosslinking agents.

The vulcanized rubber used for the preparation of the above-mentioned vulcanized rubber molded article includes ethylene / α-olefin /
The non-conjugated polyene copolymer rubber is preferable, and as the α-olefin having 3 to 20 carbon atoms in the ethylene / α-olefin non-conjugated polyene copolymer rubber, propylene, 1-butene, 1-pentene, 1 -Hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene,
1-decene, 1-undecene, 1-dodecene, 1-tridecene,
1-tetradecene, 1-pentadecene, 1-hexadecene, 1-
Heptadecene, 1-nonadecene, 1-eicosene, 9-methyldecene-1,11-methyldodecene-1,12-ethyltetradecene-1 and the like can be mentioned. These α-olefins are
They can be used alone or in combination of two or more. Of these α-olefins, those containing 3 to 3 carbon atoms
8 α-olefins such as propylene, 1-butene,
4-Methylpentene-1,1-hexene and 1-octene are particularly preferred.

The ethylene / α-olefin / non-conjugated polyene copolymer rubber has heat aging resistance, strength characteristics, rubber elasticity,
In terms of obtaining a rubber composition capable of providing a vulcanized rubber molded product having excellent cold resistance and processability, (a) a unit derived from ethylene and (b) a unit derived from an α-olefin having 3 to 20 carbon atoms. 50/50 to 90/10
It is preferably contained in a molar ratio of [(a) / (b)]. This molar ratio is more preferably 65/35 to 90 /
10, more preferably 65/35 to 85/15, and particularly preferably 65/35 to 80/20.

Specific examples of the non-conjugated polyene include 1,4-hexadiene, 3-methyl-1,4-hexadiene,
4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 7-methyl-1,6
-Chain non-conjugated dienes such as octadiene, 8-methyl-4-ethylidene-1,7-nonadiene, 4-ethylidene-1,7-undecadiene; methyltetrahydroindene, 5-ethylidene
-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 5-vinyl-2- Cyclic non-conjugated dienes such as norbornene, 5-isopropenyl-2-norbornene, 5-isobutenyl-2-norbornene, cyclopentadiene, norbornadiene; 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene Examples thereof include trienes such as -5-norbornene, 2-propenyl-2,2-norbornadiene, and 4-ethylidene-8-methyl-1,7-nanodiene. Of these, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, cyclopentadiene and 4-ethylidene-8-methyl-1,7-nanodiene are preferable.

These non-conjugated polyenes can be used alone or in combination of two or more kinds.

The iodine value of the ethylene / α-olefin / non-conjugated polyene copolymer rubber is such that a rubber composition having a high crosslinking efficiency can be obtained and a vulcanized rubber molded article having excellent compression set resistance can be provided. Is obtained, and in terms of cost advantage, 1 to 40 is preferable, and 1 to 3 is preferable.
It is more preferably 0.

The intrinsic viscosity [η] of ethylene / α-olefin / non-conjugated polyene copolymer rubber measured in decalin at 135 ° C. is a vulcanized rubber molding excellent in strength properties, compression set resistance and processability. It is preferably 2.0 to 4.5 dl / g, and more preferably 2.2 to 4.0 dl / g, from the viewpoint of obtaining a rubber composition capable of providing a body. These ethylene / α-olefin / non-conjugated polyene copolymer rubbers may be used alone or in combination of two or more kinds.

In order to obtain an extrusion-molded vulcanized rubber molded product having sufficient mechanical strength, vulcanized rubber contains ethylene / α-
It is preferable to use 30 to 300 parts by weight of carbon black with respect to 100 parts by weight of the olefin / non-conjugated polyene copolymer rubber.

As carbon black, SRF, GP
F, FEF, MAF, HAF, ISAF, SAF, F
Carbon black such as T and MT can be used.
Carbon black preferably has a nitrogen adsorption specific surface area of 10 to 100 m ² / g from the viewpoint that a rubber composition capable of providing a vulcanized rubber molded product having excellent mechanical strength and product skin can be obtained.

In the vulcanized rubber, conventionally known compounds such as an antioxidant, a processing aid, a foaming agent, a foaming aid, a colorant, a dispersant, and a flame retardant may be incorporated into the vulcanized rubber depending on the intended use of the vulcanized product. The agent is blended.

An inorganic filler can be appropriately used as a reinforcing agent in the vulcanized rubber, depending on the application.
The maximum amount is 100 parts by weight with respect to 100 parts by weight of ethylene / α-olefin / non-conjugated polyene copolymer rubber.

Specific examples of the inorganic filler include silica, soft calcium carbonate, heavy calcium carbonate, talc and clay.

As the softening agent to be blended in the vulcanized rubber,
Any softener commonly used for rubber can be used. Specifically, petroleum-based softeners such as process oil, lubricating oil, paraffin, liquid paraffin, polyethylene wax, polypropylene wax, petroleum asphalt, and petrolatum; coal tar-based softeners such as coal tar and coal tar pitch; castor oil, Linseed oil, rapeseed oil, soybean oil,
Fatty oil softeners such as coconut oil; tall oil; sub, (factis); waxes such as beeswax, carnauba wax, lanolin; ricinoleic acid, palmitic acid, stearic acid, barium stearate, calcium stearate, zinc laurate, etc. Fatty acids and fatty acid salts; naphthenic acid; pine oil, rosin or derivatives thereof; synthetic polymer substances such as terpene resin, petroleum resin, coumarone indene resin, atactic polypropylene; esters such as dioctyl phthalate, dioctyl adipate, dioctyl sebacate System softeners: microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, liquid polyisoprene, terminal modified polyisoprene, hydrogenated terminal modified polyisoprene, liquid thiochol, hydrocarbon synthetic lubricating oil and the like. Among them, petroleum-based softeners, especially process oils are preferably used. The blending amount of these softening agents is appropriately selected depending on the use of the vulcanized product.

As the vulcanizing agent used for vulcanizing the vulcanized rubber,
Included are sulfur and sulfur compounds.

Specific examples of sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur and the like.

Specific examples of the sulfur compound include sulfur chloride, sulfur dichloride, and polymer polysulfide. Further, a sulfur compound that releases active sulfur at the vulcanization temperature and vulcanizes, such as morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, dipentamethylenethiuram tetrasulfide, and selenium dimethyldithiocarbamate can also be used.

Of these, sulfur is preferred.

The sulfur or sulfur compound is usually used in a proportion of 0.1 to 10 parts by weight based on 100 parts by weight of the copolymer rubber.

When sulfur or a sulfur compound is used as the vulcanizing agent, it is preferable to use a vulcanization accelerator together. Specific examples of the vulcanization accelerator include N-cyclohexyl-2-benzothiazole sulfenamide (CB
S), N-oxydiethylene-2-benzothiazole sulfenamide (OBS), Nt-butyl-2-benzothiazole sulfenamide (BBS), N, N-diisopropyl-2
-Sulfenamide compounds such as benzothiazole sulfenamide; 2-mercaptobenzothiazole (MB
T), 2- (2,4-dinitrophenyl) mercaptobenzothiazole, 2- (4-morpholinothio) benzothiazole,
Thiazole compounds such as 2- (2,6-diethyl-4-morpholinothio) benzothiazole and dibenzothiazyl disulfide; diphenylguanidine (DPG), triphenylguanidine, diorsonitrile guanidine (DOT)
G), orthotolylbaiguanide, guanidine compounds such as diphenylguanidine phthalate; acetaldehyde-aniline condensate, butyraldehyde-aniline condensate, hexamethylenetetramine (H), aldehyde amines or aldehydes such as acetaldehyde ammonia
-Ammonia compound; 2-mercaptoimidazoline and other imidazoline compounds; Thiocarbanilide, diethylthiourea (EUR), dibutylthiourea, trimethylthiourea, diorthotolylthiourea and other thiourea compounds; Tetramethylthiuram monosulfide (TM)
TM), tetramethylthiuram disulfide (TMT
D), thiuram-based compounds such as tetraethylthiuram disulfide, tetrabutylthiuram disulfide, tetrakis (2-ethylhexyl) thiuram disulfide (TOT), dipentamethylene thiuram tetrasulfide (TRA); zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, di -dithiocarbamate salts such as zinc n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate and tellurium dimethyldithiocarbamate; xanthate salts such as zinc dibutylxanthate. Examples include compounds such as zinc white (zinc oxide).

These vulcanization accelerators are usually used in a proportion of 0.1 to 20 parts by weight with respect to 100 parts by weight of the copolymer rubber.

Examples of the anti-aging agent used in the vulcanized rubber include amine-based, hindered phenol-based or sulfur-based anti-aging agents, etc., but these anti-aging agents do not impair the object of the present invention. Used in.

Examples of the amine anti-aging agent include diphenylamines and phenylenediamines.

As the sulfur anti-aging agent, the sulfur anti-aging agent usually used for rubber is used.

As the processing aid, the processing aids used in ordinary rubber processing can be used. Specific examples include higher fatty acids such as linoleic acid, ricinoleic acid, stearic acid, palmitic acid, and lauric acid; salts of higher fatty acids such as barium stearate, zinc stearate, and calcium stearate; esters of the above higher fatty acids. To be

Such a processing aid is usually used in an amount of 10 parts by weight or less with respect to 100 parts by weight of ethylene / α-olefin / non-conjugated polyene copolymer rubber. It is desirable to determine the optimum amount appropriately.

Specific examples of the foaming agent include inorganic foaming agents such as sodium bicarbonate (baking soda), sodium carbonate, ammonium bicarbonate, ammonium carbonate, ammonium nitrite; N, N'-dimethyl-N, N'-. Dinitrosoterephthalamide, N, N'-dinitrosopentamethylenetetramine (DP
T) and other nitroso compounds; azodicarbonamide (AD
CA), azobisisobutyronitrile (AZBN), azobiscyclohexylnitrile, azodiaminobenzene, barium azodicarboxylate, and other azo compounds;
Benzylsulfonylhydrazide (BSH), toluenesulfonylhydrazide (TSH), p, p'-oxybis (benzenesulfonylhydrazide) (OBSH), diphenylsulfone-3,3'-disulfonylhydrazide and other sulfonylhydrazide compounds; calcium azide, 4 Azide compounds such as 1,4-diphenyldisulfonyl azide and p-toluenesulphonyl azide may be mentioned.

Further, other known rubber or resin may be blended and used in the vulcanized rubber component.

Examples of such other rubbers include natural rubber (NR), isoprene rubber such as isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (N).
Examples thereof include conjugated diene rubbers such as BR) and chloroprene rubber (CR).

Examples of other resins include polyethylene, polypropylene, 1,2-polybutadiene, polybutene and the like.

[Preparation of Rubber Composition and Vulcanized Rubber Molded Article Thereof] The rubber composition used in the preparation of the vulcanized rubber molded article is an internal mixer (closed type, such as Banbury mixer, kneader, intermix). Mixer) to add additives such as ethylene / α-olefin / non-conjugated polyene copolymer rubber, carbon black, rubber reinforcing agent, inorganic filler and softening agent at a temperature of 80 to 170 ° C for 2 to 2
After kneading for 0 minutes, sulfur is used as a roll such as an open roll or a kneader, and if necessary, a vulcanization accelerator, a vulcanization aid, a foaming agent, and a foaming aid are additionally mixed,
It can be prepared by kneading at a roll temperature of 40 to 80 ° C. for 5 to 30 minutes and then dispensing.

The rubber composition prepared as described above is formed into an intended shape by, for example, an extruder, and at the same time as molding, or by introducing the molded product into a vulcanization tank,
Vulcanization can be performed by heating at a temperature of 300 ° C. for 1 to 20 minutes.

The vulcanization step is usually carried out continuously.
The heating method in the vulcanization tank includes hot air, a fluidized bed of glass beads, a molten salt tank (LCM), and a PCM (Powder Curi).
A heating means such as ngMedium or Powder Curing Method), UHF (Ultra High Frequency Electromagnetic Wave), and steam can be used.

The vulcanized rubber thus obtained is not particularly limited, but usually has very low fluidity or no fluidity, for example, melt flow rate (MF).
R: ASTM D 1238, 230 ° C, 10 kg load) is often impossible to measure.

The composite molded article according to the present invention is obtained by joining the molded article made of the vulcanized rubber as described above and the molded articles made of the first and second thermoplastic elastomers of the present invention. It has a feature.

For the composite molded article according to the present invention, for example, a molded article made of a vulcanized rubber and a molded article made of a thermoplastic elastomer are prepared in advance, and the interface is heated to melt and then contacted. However, it is preferable to bring a molten thermoplastic elastomer into contact with a molded body prepared from a vulcanized rubber prepared in advance to solidify the molded body. For example, there is a method in which a molded body made of vulcanized rubber is set in a mold, and then a molten material of a thermoplastic elastomer is injected and solidified to perform melt adhesion (fusion). Insert molding is particularly preferred in the present invention.

In the present invention, in addition to the step of forming a joint between the molded body made of vulcanized rubber and the molded body made of the first or second thermoplastic elastomer as described above, It is preferable to carry out a step of heat-treating the containing molded body at a temperature of 80 ° C. or higher.

The heat treatment is not particularly limited as long as it is a temperature of 80 ° C. or higher, preferably 90 ° C., more preferably 100 ° C. or higher, and the upper limit is not particularly limited.
It is usually 130 ° C or lower. Here, the temperature refers to the temperature of the atmosphere. The heat treatment time is not particularly limited, but is usually 1 hour or longer, preferably 5 hours or longer, more preferably 10 hours or longer, and the upper limit is usually 24 hours.
Less than an hour.

In the heat treatment, a heater, an oven or the like can be used as appropriate.

By doing so, a composite molded article having excellent adhesive strength can be obtained.

The composite molded article according to the present invention is suitably used for automobile interior / exterior materials, in which case the first and second
The olefinic thermoplastic elastomer is used as a joining member for joining, preferably welding to a vulcanized rubber molded product. When used as a weather strip, it is preferably used as a joining corner member of a corner portion of a weather strip for an automobile, for example.

For example, an extruded product of vulcanized rubber is cut,
In molding the corner portion of the weather strip connecting the obtained cut extrudates from different directions, the above-mentioned first and second olefinic thermoplastic elastomers (compositions) according to the present invention are injected at a temperature equal to or higher than the melting point. A weather strip can be obtained by molding and bringing it into contact with an extruded product of vulcanized rubber and welding. Insert molding is particularly preferable.

The weather strip having the joining corner member made of the first and second thermoplastic elastomers according to the present invention will be described more specifically with reference to FIG.

FIG. 1 is a schematic perspective view for explaining a weather strip (glass run channel) of an automobile and a method for forming the weather strip.

As shown in FIG. 1A, the weather strip is formed when the vulcanized rubber cut extruded products 1 and 2 are connected to the cut extruded products 1 and 2 from different directions. And the joining corner member 3 which is The cut and extruded products 1 and 2 are obtained by extruding a vulcanized rubber into a channel shape and then cutting it into a predetermined length. The cut and extruded products 1 and 2 have a linear shape in the longitudinal direction. In the present specification, this is called a linear portion. Also,
The term "joining corner member" as used herein refers to a portion formed when the cut and extruded products are connected from different directions.

Such a weatherstrip can be prepared as follows.

First, the injection molding die 4 is heated to a predetermined temperature in advance. Next, as shown in FIG. 1B, the cut extruded products 1 and 2 made of vulcanized rubber are inserted into the mold 4.

Next, although not shown, the first or second olefinic thermoplastic elastomer according to the present invention melted at a temperature equal to or higher than the melting point in the heating chamber (inside the screw) is provided with the cavity of the mold 4 and the core. The first or second olefinic thermoplastic elastomer according to the present invention, which has been melted at a temperature equal to or higher than the melting point, is joined (welded) to the end faces of the cut extrusion molded articles 1 and 2 by pouring into a space formed between the two. After that, the thermoplastic elastomer is cooled to obtain a weather strip having a joining corner member 3 as shown in FIG.

The above-mentioned joining is preferably welding of a molded body made of vulcanized rubber and a thermoplastic elastomer as described above. The welding is preferably insert molding of a thermoplastic elastomer in the presence of vulcanized rubber.

In the composite molded article of the present invention, it is preferable that the base material fracture is observed when the tensile peeling test of the bonded portion is performed. The tensile peeling test of the bonded portion is performed by the following method. A molded product in which a molded product of the vulcanized rubber as described in the section of the vulcanized rubber and a molded product of the thermoplastic elastomer composition are bonded, for example, a molded product having a joint portion such as a weather strip. About the body, grasping two places sandwiching the joint, pulling speed 200
Perform a tensile test at mm / min. Normally, the corner material is an uncolored product and the vulcanized rubber is a black colored product, and the cross section after the test is observed. The cross section was visually observed, and if the corner material remained on the cross section, the base material was destroyed, and if the corner material did not remain, interface peeling was performed.

There is no particular limitation on the shape of the vulcanized rubber molded body, the olefinic thermoplastic elastomer molded body and the shape of the composite molded body constituting the composite molded body of the present invention. The effects of the invention can be achieved. Although the weather strip has been described as an example here, the first and second olefinic thermoplastic elastomers according to the present invention can be used not only when forming a fusion-molded body on a vulcanized rubber molded body but also on a skin portion such as a door trim. It is also applicable to the case where is formed by a fusion-bonded skin layer.

[0141]

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

The melting points (T) of the crystalline ethylene polymers and polypropylene used in the examples and comparative examples were
m), the melt flow rate (MF) of the thermoplastic elastomer (TPE) compositions obtained in Examples and Comparative Examples.
R), tensile peel strength of molded articles made of the thermoplastic elastomer compositions obtained in Examples and Comparative Examples, and fracture mode at the time of peeling, hardness, tensile strength, elongation, compression set (CS), and moldability. The measurement or evaluation was performed according to the following method. (1) Melting point (Tm) and heat of fusion Annealing the pellets at 230 ° C for 10 minutes, then using a differential scanning calorimeter (DSC) to 10 ° C up to 30 ° C.
The temperature was lowered at a rate of / min, the temperature was held for 1 minute, the temperature was raised at a rate of 10 ° C./min, and the temperature at which the maximum amount of absorbed heat was absorbed was taken as the melting point (Tm). (2) The crystalline ethylene polymer was measured by crystallinity DSC, the endothermic peak area was calibrated with long-chain paraffin, and the heat of fusion of each sample was determined. The peak was determined and the crystallinity was obtained. The heat of fusion of completely crystalline polyethylene was calculated as 293 J / g. (3) Melt flow rate (MFR) The melt flow rate of the thermoplastic elastomer composition is
230 ° C according to ASTM D 1238-65T,
It was measured with a 2.16 kg load. (4) Tensile peel strength and fracture mode during peeling The vulcanized rubber press sheet (12 cm in length × 14.7 cm in width × 2 mm thick flat plate) obtained in [Reference Example] described below is cut with a cutter as an adherend. 2.5 cm x 14.
A vulcanized rubber molded product having a size of 7 cm × thickness of 2 mm and obtained as an adherend is attached to a mold for injection molding with a double-sided tape.

Then, the thermoplastic elastomer composition for welding is molded on the cut surface of the vulcanized rubber molded product by a 100 Ton injection molding machine so that it is melt-bonded to the adherend at the injection stage.

Further, the melt-bonded molded product was aged in an oven at 60 ° C. and 100 ° C. for 5 hours, respectively,
It cooled at normal temperature for 24 hours or more.

The heat-treated and non-heat-treated molded articles thus melt-bonded were punched into strips each having a width of 2 cm, and a peeling test was carried out at a pulling speed of 200 mm / min. At the same time as measuring the strength (adhesion peel strength), the peeling state during the peeling test is visually judged. (5) Hardness For the hardness, Shore A hardness was measured according to JIS K6301.

For the measurement, a sheet was prepared by a press molding machine, and a scale A was used to read the scale immediately after contact with the pressing needle. (6) Tensile strength and elongation According to JIS K6301, a tensile test was performed under the following conditions to measure the tensile strength and elongation at break.

In the test, a sheet was prepared by a press molding machine, a JIS No. 3 test piece was punched out, and a tensile speed was 200 mm /
It was carried out under the condition of minutes. (7) Compression set CSNH, CSH The compression set (CS) was measured under the following conditions in accordance with JIS K6301.

The measurement was carried out with a vertical injection molding machine to obtain a diameter of 29.0.
A cylindrical molded product having a thickness of 1 mm and a thickness of 12.7 mm is manufactured.
Further, after aging in an oven at 60 ° C. and 100 ° C. for 5 hours respectively, it was cooled at room temperature for 24 hours or more.

[0149] The thus heat-treated and non-heat-treated molded products were compressed in the thickness direction of 25% with a spacer at a temperature of 70 ° C, and after 22 hours, the thickness after release was measured. The compression set was calculated.

[Reference Example] [Preparation of Vulcanized Rubber Press Sheet] As a raw material rubber, ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber (ethylene content = 68 mol%, limit measured in decalin at 135 ° C.) Viscosity [η] = 2.8 dl / g, iodine value = 12) 100 parts by weight, FEF grade carbon black [Asahi Carbon Co., Ltd., trade name Asahi # 60G] 170 parts by weight, and softener [Idemitsu Kosan ( Co., Ltd., trade name Diana Process Oil ^TM PS-430] 95 parts by weight, stearic acid 1 part by weight, Zinc Hua No. 1 5 parts by weight, activator [Lion Co., Ltd., trade name ARCARD 2HT-F] ]
1 part by weight was kneaded with a Banbury mixer [manufactured by Kobe Steel, Ltd., BB-2 type mixer] having a volume of 1.7 liters.

The kneading method was as follows. First, the raw material rubber was masticated for 1 minute, then carbon black, a softening agent, stearic acid, zinc white No. 1 and an activator were added and kneaded for 2 minutes. Then, the ram was raised and cleaned, and kneaded for 2 minutes to obtain 1390 parts by weight of the rubber compound (I). This kneading was carried out at a filling rate of 75%, and kneading was carried out for 2 batches by the same procedure to obtain a total of 4170 parts by weight.

From the obtained rubber compound (I), 3670 parts by weight was weighed to obtain a 14-inch roll (Nippon Roll Co., Ltd.).
Manufactured) (the surface temperature of the front roll is 60 ° C., the surface temperature of the rear roll is 60 ° C., the rotation speed of the front roll is 16 rpm, and the rotation speed of the rear roll is 18 rpm), and the rubber compound (I) is used.
5 parts by weight of sulfur, 2-mercaptobenzothiazole [manufactured by Sanshin Chemical Industry Co., Ltd., trade name Suncellar M] 15
5 parts by weight, dibenzothiazyl disulfide [manufactured by Sanshin Chemical Industry Co., Ltd., trade name Suncellar DM) 5 parts by weight, zinc dibutyldithiocarbamate [manufactured by Sanshin Chemical Industry Co., Ltd., trade name Suncellar BZ] 20 parts by weight, dimethyl Zinc dithiocarbamate [manufactured by Sanshin Chemical Industry Co., Ltd., trade name Sancellar PZ] 5 parts by weight, ethylenethiourea [manufactured by Sanshin Chemical Industry Co., Ltd., trade name Sancellar 22C] 10 parts by weight,
Dithiodimorpholine [manufactured by Sanshin Chemical Industry Co., Ltd., trade name
14 parts of an open roll (Nippon Roll Co., Ltd.) was added with 5 parts by weight of Sanfer R] and 50 parts by weight of calcium oxide [Inoue Lime Industry Co., Ltd., trade name Vesta PP].
And a kneading process for 7 minutes at a roll temperature of 60 ° C.) to obtain a rubber compound (II).

A vulcanized rubber press sheet was obtained as described above using this rubber compound (II). At this time, a 150 ton press was used.

[Example 1] Low-density polyethylene [Crystallinity: 10% or more, MFR (ASTM D 1238, 190 ° C, 2.16 kg
Load: 7 g / 10 minutes, density (ASTM D 1505): 0.92
0 g / cm ³ , melting point (Tm): 108 ° C .; hereinafter, LDP
Abbreviated as E-1. ] 15 parts by weight and an oil-extended ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber as a rubber component [ethylene content: 78 mol%, propylene content: 22 mol%, iodine value: 13, Mooney viscosity [M
L _{1 + 4} (100 ° C.)] 74, oil extension: 100 parts by weight of rubber, paraffin-based process oil (Idemitsu Kosan Co., Ltd.)
Made by trade name PW-380) 40 parts by weight; hereinafter EP
Abbreviated as T. ] 47 parts by weight and propylene / ethylene / 1-butene terpolymer as polypropylene [MFR (AS
TM D 1238, 230 ℃, 2.16kg load): 7.0g / 10min,
Melting point (Tm): 136 ° C .; hereinafter abbreviated as PP-1. ) 3
8 parts by weight, 0.1 part by weight of a phenolic antioxidant [manufactured by Nippon Ciba-Geigy Co., Ltd., trade name Irganox 1010] as an antioxidant, and a diazo weathering stabilizer [manufactured by Nippon Ciba-Geigy Co., Ltd.] as a weathering agent , Trade name Tinuvin 326] 0.1 part by weight and HALS type weathering stabilizer [manufactured by Sankyo Co., Ltd., trade name Sanol LS-770] 0.0.
5 parts by weight, 0.08 parts by weight of an organic peroxide [Nippon Oil & Fats Co., Ltd., trade name Perhexa25B] as a crosslinking agent, and divinylbenzene (DVB) 0.0 as a crosslinking aid.
6 parts by weight were thoroughly mixed with a Henschel mixer, and the extruder [part number TEM-50, manufactured by Toshiba Machine Co., Ltd., L / D = 4] was used.
0, Cylinder temperature: C1-C2 120 ° C, C3-C
4140 ° C, C5-C6 180 ° C, C7-C820
0 ° C, C9 to C12 220 ° C, die temperature: 210
° C, screw rotation speed: 200 rpm, extrusion rate: 40 k
Granulation was performed while pouring 20 parts by weight of paraffin-based process oil [made by Idemitsu Kosan Co., Ltd., trade name PW-380] into the cylinder at g / h) to obtain pellets of the thermoplastic elastomer composition.

The pellet-shaped thermoplastic elastomer composition was injection-molded, and the obtained molded product was evaluated according to the method described above.

Then, the thermoplastic elastomer composition was molded on a cut surface of the vulcanized rubber press sheet by a 100 ton injection molding machine so that the thermoplastic elastomer composition was melt-bonded at the injection molding stage. Mold the melted and bonded product in the oven 6
After aging for 5 hours each at 0 ° C. and 100 ° C., it was cooled at room temperature for 24 hours or more.

[0157] The following tensile peeling test was carried out on the heat-treated molded articles which were melt-bonded in this way and those which were not heat-treated. [Tensile Peeling Test of Molded Article] Molded article in which a molded article of vulcanized rubber as described in the section of vulcanized rubber and a molded article of the above-mentioned thermoplastic elastomer composition are joined, for example, weather strip. With respect to a molded product having a large number of joints, two portions sandwiching the joints are grasped and the pulling speed is 20.
A tensile test is performed at 0 mm / min, and a cross section after the test is observed to confirm whether the base material is broken or the interface is separated. The result is first
Shown in the table.

Example 2 In Example 1, LDPE-
Instead of 1, the density (ASTM D 1505) is 0.915 g /
cm ³ , MFR (ASTM D 1238, 190 ° C, 2.16 kg load) 70 g / 10 minutes, melting point (Tm) 102 ° C, low density polyethylene with a crystallinity of 10% or more (hereinafter LDPE
-2 is abbreviated. ) Was used in the same manner as in Example 1 to obtain pellets of the thermoplastic elastomer composition.

The pellet-shaped thermoplastic elastomer composition was injection-molded, and the obtained molded product was evaluated according to the method described above. The results are shown in Table 1.

[Example 3] In Example 1, LDPE-
Instead of 1, linear low-density polyethylene [MFR (AS
TM D 1238, 190 ° C, 2.16 kg load): 8 g / 10 minutes, density (ASTM D 1505): 0.920 g / cm ³ , melting point (T
m): 120 ° C., crystallinity of 10% or more; below, LLD
Abbreviated as PE. ] A thermoplastic elastomer composition pellet was obtained in the same manner as in Example 1 except that the above was used.

This pellet-shaped thermoplastic elastomer composition was injection-molded, and the obtained molded product was evaluated according to the method described above. The results are shown in Table 1.

[Example 4] In Example 1, LDPE-
Instead of 1, high density polyethylene [MFR (ASTM D 1
238, 190 ℃, 2.16kg load): 6g / 10min, density (ASTM
D 1505): 0.956 g / cm ³ , melting point (Tm): 12
7 ° C .; crystallinity is 10% or more; hereinafter abbreviated as HDPE. ] A thermoplastic elastomer composition pellet was obtained in the same manner as in Example 1 except that the above was used.

This pellet-shaped thermoplastic elastomer composition was injection-molded, and the obtained molded body was evaluated according to the method described above. The results are shown in Table 1.

Example 5 The rubber compound (II) prepared in the above [Reference Example] was cut into a ribbon from a roll.

This ribbon-shaped rubber compound (II) was placed in an extruder having an extruder head temperature of 80 ° C., and was 2 mm in length × 25 mm in width.
Extrusion molding was carried out at a speed of 2.5 m / min using a die of 1 type, and a molding line in which a microwave vulcanization tank (UHF) and a hot air vulcanization tank (HAV) were connected in series was used. Vulcanization was performed to obtain a vulcanized rubber molded body (III).

At this time, the UHF temperature was 200 ° C., and the output was adjusted so that the surface temperature of the extruded material was 190 ° C. at the UHF outlet. A 30 m HAV vulcanization tank was used and the temperature inside the tank was set to 250 ° C. Residence time in vulcanization tank is 5
It was a minute.

Then, using a 70 ton vertical injection molding machine, the preformed vulcanized rubber extruded product was cut at intervals of 20 cm, and a mold such as reference numeral 4 in FIG. It was set so that it could be welded. After that, injection temperature 230 ℃, mold temperature 50 ℃
Was melt-bonded to the thermoplastic elastomer obtained in Example 1 and heat-treated at 100 ° C. for 5 hours. As a result, fracture of the base material was observed.

Comparative Example 1 A thermoplastic elastomer composition was prepared in the same manner as in Example 1 except that the amounts of EPT and HDPE-1 were changed to 62 parts by weight and 0 parts by weight, respectively. Pellets were obtained.

The pellet-shaped thermoplastic elastomer composition was injection-molded, and the obtained molded product was evaluated according to the method described above. The results are shown in Table 1.

[Comparative Example 2] In Comparative Example 1, the amounts of the crosslinking agent (trade name: Perhexa 25B) and the crosslinking aid (divinylbenzene) were 0.24 parts by weight and 0.18 parts by weight, respectively.
Pellets of the thermoplastic elastomer composition were obtained in the same manner as in Example 1 except that the weight part was changed.

The pellet-shaped thermoplastic elastomer composition was injection-molded, and the obtained molded body was evaluated according to the above-mentioned method. The results are shown in Table 1.

Comparative Example 3 In Example 1, LDPE-
Instead of 1, ethylene-propylene random copolymer rubber [MFR (ASTM D 1238, 190 ° C, 2.16 kg load): 0.7
g / 10 minutes, density (ASTM D 1505): 0.869 g / c
m ³ , melting point (Tm): 33 ° C .; hereinafter, crystallinity is 5% or less, abbreviated as EPR. ] The pellets of the thermoplastic elastomer composition were obtained in the same manner as in Example 1 except that the above was changed.

The pellet-shaped thermoplastic elastomer composition was injection-molded, and the obtained molded product was evaluated according to the method described above. The results are shown in Table 1.

[Comparative Example 4] In Example 1, the blending amounts of the cross-linking agent (trade name: Perhexa 25B) and the cross-linking aid (divinylbenzene) were 0.24 parts by weight and 0.18 parts by weight, respectively.
Pellets of the thermoplastic elastomer composition were obtained in the same manner as in Example 1 except that the weight part was changed.

This pellet-shaped thermoplastic elastomer composition was injection-molded, and the obtained molded body was evaluated according to the method described above. The results are shown in Table 1.

[Comparative Example 5] With respect to the sample of Comparative Example 1,
A molded body was manufactured in the same manner as in Example 10 and subjected to a tensile peel test. As a result, no fracture of the base material was observed and interfacial peeling was observed.

In Table 1, the unit of composition of the TPE composition is parts by weight.

In addition, for components not listed as composition components in Table 1, Examples 1 to 9 and Comparative Examples 1 to 5
The amount of the slip agent is 0.3 part by weight, and the amount of the antioxidant and the weather resistance stabilizer is 0.1 part by weight, respectively.

[0179]

[Table 1]

[0180]

Industrial Applicability According to the present invention, a thermoplastic elastomer composition capable of forming a molded product that exhibits sufficient adhesive strength to a vulcanized rubber molded product without interposing an adhesive layer and causes a base material fracture upon peeling. You can provide things. The composite molded article of the present invention has good adhesive strength at the joint between the vulcanized rubber molded article and the thermoplastic elastomer molded article.

According to the method for producing a composite molded article of the present invention, it is possible to produce a composite molded article having good adhesive strength at the joint between the vulcanized rubber molded article and the thermoplastic elastomer molded article. .

[Brief description of drawings]

FIG. 1 (A) is a schematic perspective view showing an example of a weather strip for an automobile, in which a corner portion is formed from the thermoplastic elastomer composition according to the present invention,
FIG. 1B is a schematic perspective view for explaining a method of forming a corner portion of the weather strip.

[Explanation of symbols]

1, 2, ... Cutting extrusion 3 ... Joining corner member 4 ... Injection mold

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 5/14 C08K 5/14 C08L 23/10 C08L 23/10 // B29K 23:00 B29K 23:00 105 : 20 105: 20 105: 24 105: 24 B29L 9:00 B29L 9:00 F Term (reference) 4F070 AA13 AA15 AA16 AB11 AB21 AC20 AC44 AC45 AC56 AC63 AC65 AE08 GA05 GA06 GC01 GC06 4F071 AA15X AA16 AA18 AA19 AA20 AA20X AA21X AC08A AE02A AE03A AF13Y AF19 AG05 4F206 AA04 AA08 AA11 AA45 AB03 AD05 AG03 AG23 AH23 JA07 JB12 JB13 JL02 JN25 4F211 AA45 AD05 AH23 TA08 TC08 50686 EK06 EK06 TD06 TN064Y0 BB08W BB08W BB08W BB07W BB08W BB10W BB10W BB10W BB10W BB10W BB10W

Claims (20)

[Claims] 1. A crystalline ethylene polymer (A) having a crystallinity of 10% or more as measured by a DSC method, 5 to 40 parts by weight, ethylene and an α-olefin having 3 to 20 carbon atoms, which are necessary. Ethylene-α-olefin (/ non-conjugated polyene) copolymer rubber (B) 5 to 7 consisting of non-conjugated polyene according to
0 parts by weight, 5 to 40 parts by weight of polypropylene (C) [the total amount of components (A), (B) and (C) is 100 parts by weight], and the composition is crosslinked and vulcanized. An olefin-based thermoplastic elastomer characterized in that a base material is broken when a welding peeling test is performed on a rubber molded body. 2. The olefinic thermoplastic elastomer according to claim 1, wherein the compression set CS at 70 ° C. satisfies the following relational expression: CS (NH) ≦ 70% CS (NH) -CS (H) ≧ 5% (In the formula, CS (NH) represents CS in the case where the molded product is not subjected to heat treatment, and CS (H) represents the molded product after heat treatment at a temperature of 100 ° C. Stands for CS). 3. A crystalline ethylene polymer (A) having a crystallinity of 10% or more as measured by a DSC method, 5 to 40 parts by weight, ethylene, an α-olefin having 3 to 20 carbon atoms, and if necessary. And α-olefin (/ non-conjugated polyene) copolymer rubber (B) 5 to 7 consisting of non-conjugated polyene
0 parts by weight and 5 to 40 parts by weight of polypropylene (C) [the total amount of components (A), (B) and (C) is 100 parts by weight], the composition of components (A) and (B ) And (C) with respect to 100 parts by weight of the total amount, the crosslinking agent (D) is present in a proportion of 0.01 to 0.12 parts by weight and dynamically obtained by heat treatment. An olefinic thermoplastic elastomer. 4. The thermoplastic elastomer according to claim 3, wherein the crosslinking agent (D) is an organic peroxide. 5. The thermoplastic elastomer according to claim 1, which is used for welding to a vulcanized rubber. 6. The thermoplastic elastomer according to claim 3, wherein when the thermoplastic elastomer is used and a welding peeling test is performed on a vulcanized rubber molded body, the base material is broken. An olefinic thermoplastic elastomer. 7. A composite molded article comprising a molded article made of a vulcanized rubber and a molded article made of a thermoplastic elastomer joined together, wherein the thermoplastic elastomer is D
5 to 40 parts by weight of the crystalline ethylene polymer (A), which has a crystallinity of 10% or more as measured by the SC method, and ethylene,
Ethylene / α-olefin (/ non-conjugated polyene) copolymer rubber (B) 5 to 70 parts by weight, polypropylene (C) 5 to 40 consisting of α-olefin having 3 to 20 carbon atoms and, if necessary, non-conjugated polyene Parts by weight [components (A), (B)
And the total amount of (C) is 100 parts by weight].
Composite molded body. 8. Crosslinking agent (D) is present in an amount of 0.01 to 0.12 parts by weight per 100 parts by weight of the total amount of components (A), (B) and (C). The composite molded article according to claim 7, which is performed by dynamically heat-treating. 9. The composite molded article according to claim 7, wherein the thermoplastic elastomer is one in which the base material is broken when a welding peeling test is performed on the vulcanized rubber molded article. 10. A base material fracture is observed when a tensile peeling test of a bonded portion is performed.
10. The composite molded article according to any one of 1 to 9. 11. A molded body made of vulcanized rubber, and
4. The method is obtained through a step of forming a joint with a molded body made of the thermoplastic elastomer according to any one of 4 and a step of heat-treating the molded body including the joint at a temperature of 80 ° C. or higher. And a composite molded body. 12. The composite molding according to claim 11, wherein the joining is welding of a molded body made of vulcanized rubber and the thermoplastic elastomer according to any one of claims 1 to 4. body. 13. The composite molded article according to claim 7, wherein the vulcanized rubber comprises an ethylene / α-olefin / polyene copolymer rubber. 14. The composite molded article according to claim 7, which is used for interior and exterior materials of automobiles. 15. The composite molded article according to claim 14, wherein the automobile interior / exterior material is a weather strip material. 16. The weather strip material is formed by joining a linear portion and a joining corner member,
16. The linear portion is formed of a molded product of the vulcanized rubber, and the joint corner member is formed of the thermoplastic elastomer according to any one of claims 1 to 4. Composite molded body of. 17. The composite molded article according to claim 12, which is obtained by insert molding. 18. A molded body made of vulcanized rubber, and
4. A step of forming a joint with a molded body made of the thermoplastic elastomer according to any one of 4 and a step of heat-treating the molded body including the joint at a temperature of 80 ° C. or higher, Method for producing composite molded body. 19. The method according to claim 18, wherein the joint is formed by welding a molded body made of vulcanized rubber and the thermoplastic elastomer according to any one of claims 1 to 4. The method for producing a composite molded article. 20. The method for producing a composite molded article according to claim 19, wherein the welding is performed by insert molding of a thermoplastic elastomer in the presence of vulcanized rubber.