JP2003147133A - Polyolefin thermoplastic elastomer, its production method, and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyolefin thermoplastic elastomer capable of forming a molded product which gives sufficient bonding strength to a vulcanized rubber (body material) even without using an adhesive layer and the breakage of the body material on peeling. SOLUTION: The polyolefin thermoplastic elastomer has an islands-sea structure, and the islands-phase has an average particle diameter of <=2 μm, a gel fraction of 0.5-15 wt.%, and a melting calorific value of <=125 deg.C of >=40% based on the total calorific value. This elastomer can be obtained, for example, by melt-kneading a blend containing a high density polyethylene having a density of >=0.940 g/cm<3> , an ethylene-α-olefin (-nonconjugated polyene) copolymer rubber composed of ethylene, a 3-20C α-olefin and, if necessary, a (nonconjugated polyene) and a polyproplylene at a specific ratio in the presence of a specified amount of a crosslinking agent. The molded product is obtained by joining, preferably fusing the thermoplastic elastomer to a molded product composed of the vulcanized rubber.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefinic thermoplastic elastomer, a method for producing the same, and its use, and more particularly, a welded corner irregular connection portion or irregular end portion of a weather strip, door trim or the like of an automobile. The present invention relates to an olefin-based thermoplastic elastomer suitable for, a method for producing the same, and uses thereof.

[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, vulcanized rubber and thermoplastic elastomer cannot be vulcanized and bonded, so that they were integrated by using an adhesive, but they cannot be said to be sufficient in terms of productivity or environmental friendliness. .

As a technique relating to the composition of the thermoplastic elastomer, the addition of a polar group-containing resin (Japanese Patent Laid-Open No. 2-1152)
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). It was confirmed by the present inventors that this technique is very effective in breaking the base material, but the addition of a non-crosslinked ethylene polymer (ethylene / 1-octene copolymer) causes the rubber elasticity of the molded product to be lost. I will be destroyed.

Further, as a technique of the 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 above-mentioned techniques relating to the composition of the thermoplastic elastomer and the vulcanized rubber, but also the one that attempts to obtain the anchor effect by cutting the vulcanized rubber and then making unevenness on the cut surface (Japanese Patent Laid-Open No. H9-9138). 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.

[0008] Therefore, a molded body is formed which has sufficient adhesive strength to vulcanized rubber without interposing an adhesive layer and causes the base material to be destroyed at the time of peeling (it is not peeled at the adhesive interface but broken by the molded body). An olefinic thermoplastic elastomer capable of forming a molded product obtained by welding the elastomer to a vulcanized rubber, and a lightweight molded product having sufficient hardness and rubber elasticity as a thermoplastic elastomer, moldability,
The appearance of an olefin-based thermoplastic elastomer having excellent economical efficiency and a molded article obtained by welding the elastomer to a vulcanized rubber is desired.

[0009]

SUMMARY OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, and has sufficient adhesive strength for vulcanized rubber without interposing an adhesive layer and a base material at the time of peeling. An olefin-based thermoplastic elastomer capable of forming a molded product that causes fracture and a molded product obtained by welding the elastomer to a vulcanized rubber, and a lightweight molded product having sufficient hardness and rubber elasticity as a thermoplastic elastomer can be formed. It is an object of the present invention to provide an olefinic thermoplastic elastomer excellent in moldability and economy and a molded product obtained by welding the elastomer to a vulcanized rubber.

Another object of the present invention is to provide a method for producing the above olefinic thermoplastic elastomer.

[0011]

SUMMARY OF THE INVENTION The first olefinic thermoplastic elastomer according to the present invention is an olefinic thermoplastic elastomer which forms a sea-island morphology, wherein the island phase has an average particle size of 2 μm or less and a gel fraction. Is 0.5-1
5% by weight, and the heat of fusion of 125 ° C. or less measured by a differential scanning calorimeter (DSC) is 4 of the total heat of fusion.
It is characterized by being 0% or more.

This thermoplastic elastomer comprises an olefin resin and an olefin rubber, and the olefin rubber is crosslinked. The first olefinic thermoplastic elastomer according to the present invention is a differential scanning calorimeter (DSC).
Calorific value for melting measured in (the same as the total calorific value for melting)
Is preferably 30 J / g or more.

In the first olefinic thermoplastic elastomer according to the present invention, the number of island phases having a ratio of major axis to minor axis of 2 or more is 3% or less with respect to the total number of island phases, and 70
The compression set (CS) at ° C is preferably 65% or less. This compression set at 70 ° C. can be used as an index of rubber elasticity. The first olefin-based thermoplastic elastomer according to the present invention is obtained by dynamically cross-linking an olefin-based resin and an olefin-based rubber in the presence of a cross-linking agent, and the total amount of the olefin-based resin and the olefin-based rubber is 100 (weight: Part) and the compression set C at 70 ° C. as an index of rubber elasticity
It is preferable that S (%) satisfies the relationship represented by the following formula A × CS <5.0.

The second olefinic thermoplastic elastomer according to the present invention has a density (ASTM D 1505) of 0.940 g.
High density polyethylene (A) 5 to 50 / cm ³ or more
Parts by weight, and ethylene-α-olefin (/ non-conjugated polyene) copolymer rubber (B) 5 to 70 parts by weight consisting of ethylene, an α-olefin having 3 to 20 carbon atoms and, if necessary, a non-conjugated polyene. , Polypropylene (C) 5-5
0 parts by weight [the total amount of components (A), (B) and (C) is 100 parts by weight] and having a gel fraction of 0.5 to 15% by weight. It is characterized by being.

In the second olefinic thermoplastic elastomer according to the present invention, the high-density polyethylene (A) has a melt flow rate (MFR; ASTM D 123) at 190 ° C.
8 (measured based on a load of 2.16 kg) is preferably 10 g / 10 minutes or less. The second olefin-based thermoplastic elastomer according to the present invention is an olefin-based thermoplastic elastomer that forms a morphology of a sea-island structure, and has an average particle size of the island phase of 2 μm or less and a gel fraction of 0.5 to. It is desirable that the amount of heat of fusion is 15% by weight and the amount of heat of fusion at 125 ° C. or less measured by a differential scanning calorimeter (DSC) is 40% or more of the total amount of heat of fusion. The second olefinic thermoplastic elastomer according to the present invention preferably further has a calorific value at the time of melting of 30 J / g or more as measured by a differential scanning calorimeter (DSC).

The second method for producing an olefinic thermoplastic elastomer according to the present invention comprises 5 to 50 parts by weight of high density polyethylene (A) having a density (ASTM D 1505) of 0.940 g / cm ³ or more, and ethylene. , 3 to 2 carbon atoms
0- [alpha] -olefin and optionally non-conjugated polyene ethylene / [alpha] -olefin (.non-conjugated polyene) copolymer rubber (B) 5 to 70 parts by weight and polypropylene (C) 5 to 50 parts by weight [ The total amount of components (A), (B) and (C) is 100 parts by weight], and a gel fraction of the blended product is melt-kneaded in the presence of the crosslinking agent (D). It is characterized by obtaining a thermoplastic elastomer of 5 to 15% 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 preferably thermoplastic elastomers in which the base material is broken during a tensile peel test when a welding test of a vulcanized rubber to a press molded product is performed.

The molded body according to the present invention is characterized in that the molded body made of vulcanized rubber is joined to the molded body made of the first or second olefinic thermoplastic elastomer of the present invention. I am trying. This molded body is preferably formed by welding the above-mentioned first or second olefinic thermoplastic elastomer to a molded body made of vulcanized rubber.

The vulcanized rubber is preferably ethylene / α-olefin / polyene copolymer rubber. The molded product according to the present invention is suitably used for interior and exterior materials of automobiles.
For example, it is preferably used as a weather strip material. Specifically, for example, in a weather strip material in which a linear portion and a joining corner member are joined, the linear portion is made of the molded product of the vulcanized rubber, and the corner member is the first or the second according to the present invention. A molded body formed from a second olefin-based thermoplastic elastomer.

A molded product obtained by welding the above-mentioned first or second olefinic thermoplastic elastomer according to the present invention to a molded product made of vulcanized rubber can be obtained, for example, by insert molding. The molded product according to the present invention is preferably a molded product in which a base material fracture is observed when a tensile peeling test is performed on a joint portion of the molded product.

The first or second olefinic thermoplastic elastomer according to the present invention forms a molded product which has sufficient adhesive strength to vulcanized rubber and causes the base material to break at the time of peeling even without an adhesive layer. It is also possible to form a lightweight molded article having sufficient hardness and rubber elasticity as a thermoplastic elastomer.

[0022]

DETAILED DESCRIPTION OF THE INVENTION The olefinic thermoplastic elastomer according to the present invention, the method for producing the same, and the use thereof will be specifically described below. Hereinafter, in the first and second olefin-based thermoplastic elastomers according to the present invention, “olefin-based thermoplastic elastomer” refers to a thermoplastic elastomer composed of an olefin-based resin and an olefin-based rubber.

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). The olefin resin is not particularly limited, and examples thereof include polypropylene (C) and high-density polyethylene (A) as described later in the section of the second olefin thermoplastic elastomer.

The olefin rubber is not particularly limited, but for example, ethylene / α-olefin / non-conjugated polyene copolymer (B) and other ethylene / olefins as described later in the section of the second olefin-based thermoplastic elastomer. Examples include α-olefin / polyene copolymers and ethylene / α-olefin copolymers. First, the first olefinic thermoplastic elastomer according to the present invention will be described.

First Olefin-Based Thermoplastic Elastomer The first olefin-based thermoplastic elastomer according to the present invention is a thermoplastic elastomer having a sea-island morphology, and the average particle size of the island phase is 2 μm or less. , Gel fraction 0.5 to 15% by weight, preferably 1 to 1
3% by weight, more preferably 2 to 11% by weight, and 125 ° C. measured by a differential scanning calorimeter (DSC).
The following heat of fusion is 40% or more of the total heat of fusion, usually 4
It is 0 to 70%, preferably 42 to 68%, more preferably 43 to 67%.

The sea-island structure refers to a phase structure in which dispersed particles are present in a matrix. The average particle diameter of the island phase can be measured by arbitrarily sampling from a photograph magnified 10,000 times with a transmission electron microscope. Specifically, the minor axis and major axis of all the island phases in the electron micrograph were added and averaged to obtain the average particle diameter of the island phase.

The method for measuring the gel fraction will be described in the section of the second olefinic thermoplastic elastomer according to the present invention. The method for measuring the heat of fusion below 125 ° C. and the total heat of fusion will be described in the section of Examples. In the first olefinic thermoplastic elastomer according to the present invention, the number of island phases having a ratio of major axis to minor axis of 2 or more is preferably 3% or less, more preferably 0.1% or less with respect to the total number of island phases. ˜3%, more preferably 0.2 to 2.0%, and the compression set (CS) at 70 ° C., which is an index of rubber elasticity of the elastomer, is preferably 65% or less, more preferably 20 to 65. %, More preferably 30 to 55%
Is.

In the first olefinic thermoplastic elastomer according to the present invention, the calorific value at the time of melting measured by a differential scanning calorimeter (DSC) is preferably 30 J / g or more, more preferably 30 to 80 J. / G, more preferably 35 to 70 J / g, particularly preferably 40 to 60 J / g
Is. The method for measuring the heat quantity at the time of melting (heat quantity of melting) will be described in the section of Examples.

Further, the first olefinic thermoplastic elastomer according to the present invention comprises an olefinic resin and an olefinic rubber, and the addition amount of the crosslinking agent is 100 parts by weight of the total amount of the olefinic resin and the olefinic rubber. It is preferable that A (parts by weight) and the compression set CS (%) at 70 ° C., which is an index of rubber elasticity, satisfy the relationship represented by the following formula A × CS <5.0.

The addition amount A of the cross-linking agent is preferably 0.01 to 0.12 parts by weight, and more preferably 0.1% by weight, based on 100 parts by weight of the total of the olefin resin and the olefin rubber.
It is preferably from 03 to 0.10 parts by weight. The parameter (A × CS <5.0) is the amount A of the cross-linking agent (peroxide) added when blending the components constituting the composition and the compression set which is an index of rubber elasticity. (C
It is a parameter consisting of the product of S). This parameter is satisfied only when the addition amount A of the peroxide is small and the compression set (CS) is small.

The first olefinic thermoplastic elastomer according to the present invention as described above has, for example, (1) a high density polyethylene (A) 5 having a density (ASTM D 1505) of 0.940 g / cm ³ or more. Up to 50 parts by weight of ethylene, an α-olefin having 3 to 20 carbon atoms, and optionally a non-conjugated polyene, an ethylene-α-olefin (.
Non-conjugated polyene) copolymer rubber (B) 5 to 70 parts by weight and polypropylene (C) 5 to 50 parts by weight [the total amount of components (A), (B) and (C) is 100 parts by weight]. An olefinic thermoplastic elastomer, characterized in that a blended product containing and is melt-kneaded in the presence of a crosslinking agent (D) to obtain a thermoplastic elastomer having a gel fraction of 0.5 to 15% by weight. It can be prepared by the manufacturing method of. That is, the first olefinic thermoplastic elastomer composition according to the present invention can be obtained by the second method for producing an olefinic thermoplastic elastomer according to the present invention, which will be described later.

Next, the second olefinic thermoplastic elastomer according to the present invention and the method for producing the same will be described. Second olefin-based thermoplastic elastomer The second olefin-based thermoplastic elastomer according to the present invention is a high-density polyethylene (A), an ethylene / α-olefin (/ non-conjugated polyene) copolymer rubber (B), It can be obtained by melt-kneading a blend comprising polypropylene (C) in the presence of a crosslinking agent (D).
In this elastomer, it is considered that the high-density polyethylene (A) and the copolymer rubber (B) are partially crosslinked.
It is a so-called partially crosslinked thermoplastic elastomer composition.

[High Density Polyethylene (A)] The high density polyethylene (A) used in the present invention is an olefin resin and has a density (ASTM D 1505) of 0.940 g / cm ^3.
As described above, it is usually 0.940 to 0.970 g / cm ³ , preferably 0.945 to 0.965 g / cm ³ , and more preferably 0.950 to 0.960 g / cm ³ .

This high-density polyethylene (A) is an ethylene homopolymer (polyethylene) or a crystalline ethylene / α-olefin copolymerization product consisting of ethylene and an α-olefin having 3 to 20 carbon atoms, preferably 3 to 8 carbon atoms. It is united. When comonomer is included, its comonomer content is small, not more than 10 mol% of the total. High density polyethylene (A) has a melt flow rate (MFR; ASTM
D 1238, 190 ℃, load 2.16kg), preferably 10g /
It is preferably 10 minutes or less, usually 0.01 to 10 g / 10 minutes, and more preferably 0.1 to 7 g / 10 minutes.
When the high-density polyethylene (A) having an MFR within the above range is used, a thermoplastic elastomer composition having excellent moldability can be obtained.

The melting point (Tm) of high-density polyethylene (A) measured by a differential scanning calorimeter (DSC) is usually 1
It is 40 ° C or lower. High-density polyethylene (A) includes high-density polyethylene (A), ethylene / α-olefin (・
Ratio of 5 to 50 parts by weight, preferably 10 to 40 parts by weight, more preferably 15 to 35 parts by weight, based on 100 parts by weight of the total amount of the non-conjugated polyene) copolymer rubber (B) and polypropylene (C). Used in. When the high-density polyethylene (A) is used in the above proportion, it is excellent in rubber elasticity and inexpensive heat having excellent weldability with extrusion molded articles such as weather strips made of thermoplastic elastomer for automobiles and weather strips made of vulcanized rubber. A plastic elastomer composition can be obtained.

[Ethylene / α-olefin (/ non-conjugated polyene) copolymer rubber (B)] The ethylene / α-olefin (/ non-conjugated polyene) copolymer rubber (B) used in the present invention is composed of ethylene and A copolymer rubber of an α-olefin and, if necessary, a non-conjugated polyene, such as ethylene / α-olefin / non-conjugated polyene copolymer rubber (B-1), an ethylene / α-olefin copolymer rubber (B-2) is mentioned.

The ethylene / α-olefin / non-conjugated polyene copolymer rubber (B-1) used in the present invention is an olefinic rubber comprising ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene. is there. The ethylene / α-olefin / non-conjugated polyene copolymer rubber (B-1) used in the present invention is preferably a copolymer having a crystallinity of less than 10% as determined by the DSC 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 point rubber in which a softening agent, preferably a mineral oil-based softening agent, is added during 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 /
5 to 70 per 100 parts by weight of the total amount of the non-conjugated polyene copolymer rubber (B-1) and polypropylene (C).
It is used in an amount of 10 parts by weight, preferably 10 to 65 parts by weight, more preferably 20 to 60 parts by weight. When this copolymer rubber (B-1) is used in a ratio within the above range, it has excellent weldability to extrusion molded articles such as weather strips made of thermoplastic elastomer for automobiles and weather strips made of vulcanized rubber, and moreover, A thermoplastic elastomer composition having excellent moldability capable of forming a corner portion having appropriate softness (hardness) is obtained.

A copolymer rubber (B) of the present invention containing 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),
Examples thereof include ethylene / 1-butene copolymer rubber (EBR) and ethylene / 1-octene copolymer rubber (EOR).

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.
Also, ethylene / α-olefin copolymer rubber (B-
As 2), the crystallinity determined by the DSC method is 1
Copolymers of less than 0% are desirable.

The α-olefin constituting the ethylene / α-olefin copolymer rubber (B-2) is ethylene / α
-Olefin (/ non-conjugated polyene) copolymer rubber (B)
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 optionally non-conjugated polyene is only one or more kinds of 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 ethylene / α-olefin / non-conjugated polyene copolymer rubber (B-1) and ethylene / α-olefin copolymer rubber (B-2) is high density polyethylene (A), ethylene 5 to 70 parts by weight per 100 parts by weight of the total amount of α-olefin / non-conjugated polyene copolymer rubber (B-1), polypropylene (C) and ethylene / α-olefin copolymer rubber (B-2). Parts, 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, the weldability to an extrusion molded article such as a weather strip made of a thermoplastic elastomer, a weather strip made of a vulcanized rubber, etc. It is possible to obtain a thermoplastic elastomer composition which is excellent in moldability and is capable of forming a corner portion having excellent softness (hardness).

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

Specific examples of the α-olefin having 4 to 20 carbon atoms include 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 propylene-derived structural unit content (propylene content) in the propylene copolymer is usually 50 to 90% by weight, and the comonomer-derived structural unit content (comonomer content) is usually 50 to 10% by weight. is there. The composition of the propylene copolymer is determined by measurement by ¹³ C-NMR.

The 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 minutes, preferably 0.1 to 8 g.
0 g / 10 minutes, more preferably 0.3 to 60 g / 10
Minutes are desirable. DS of polypropylene (C)
The melting point (Tm) measured at C is usually 170 ° C. or lower.

Polypropylene (C) is high density polyethylene (A), ethylene / α-olefin (/ non-conjugated polyene) copolymer rubber (B) and polypropylene (C).
5 to 50 parts by weight, preferably 10 to 45 parts by weight, and more preferably 15 to 40 parts by weight, based on 100 parts by weight of
Used in proportions by weight. When polypropylene (C) is used in a ratio within the above range, it has excellent weldability with an extrusion molded article such as a weather strip made of a thermoplastic elastomer and a weather strip made of a vulcanized rubber, and has an appropriate softness (hardness). It is possible to obtain a thermoplastic elastomer composition having excellent moldability capable of forming a corner portion having

[Crosslinking Agent (D)] Examples of the crosslinking agent (D) used in the present invention include organic peroxides, sulfur, sulfur compounds, and phenolic vulcanizing agents such as phenolic resins. Organic peroxides are preferably used. As the organic peroxide, specifically, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,
5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,
3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl Perbenzoate, tert
-Butyl peroxyisopropyl 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 based on 100 parts by weight of the total amount of high-density polyethylene (A), ethylene / α-olefin (/ non-conjugated polyene) copolymer rubber (B) and polypropylene (C). It is used in a proportion of 0.01 to 0.12 part by weight, preferably about 0.03 to 0.10 part by weight. When the organic peroxide is used in the above ratio, a thermoplastic elastomer composition in which the copolymer rubber (B) is crosslinked is obtained, and rubber properties such as heat resistance, tensile properties, elastic recovery properties and impact resilience, and A molded article having sufficient strength 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 has good compatibility with the high-density polyethylene (A), the copolymer rubber (B) and the polypropylene (C) which are the main components of the object to be treated. It also has an organic peroxide solubilizing effect, and acts as a dispersion aid for organic peroxides, so that a cross-linking effect by heat treatment is uniform, and a composition in which fluidity and physical properties are well balanced is obtained most. preferable.

In the present invention, the blending amount of such a crosslinking aid or polyfunctional vinyl monomer is such that high density polyethylene (A) and ethylene / α-olefin (/ non-conjugated polyene) copolymer rubber (B) are used. And, based on 100% by weight of the total amount of polypropylene (C), usually 0.01
To 0.4% by weight, particularly preferably 0.03 to 0.2% by weight, and by adding a crosslinking aid or a polyfunctional vinyl monomer within this range, the composition has excellent fluidity and composition. A composition that does not cause changes in physical properties due to the heat history during processing and molding can be obtained.

[Other Components] If necessary, additives such as a slip agent, a filler, an antioxidant, a weathering stabilizer, and a colorant may be added to the second olefinic thermoplastic elastomer according to the present invention. It can be blended within a range that does not impair the object of the present invention. Examples of the slip agent include fatty acid amide, silicone oil, glycerin, wax,
Examples include 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. [Second Olefinic Thermoplastic Elastomer] The second olefinic thermoplastic elastomer according to the present invention is a high density polyethylene (A), an ethylene / α-olefin (
It is prepared by mixing the non-conjugated polyene) copolymer rubber (B) and the polypropylene (C) in the above-mentioned specific proportions, and then dynamically heat-treating them in the presence of the above-mentioned specific amount of the crosslinking agent (D). be able to. At the time of this mixing, the above-mentioned additives such as slip agents and antioxidants can be added.

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 gas. The kneading temperature is usually 15
The temperature is 0 to 280 ° C, preferably 170 to 240 ° C. The kneading time is usually 1 to 20 minutes, preferably 3 to 10 minutes. The applied shearing force is 1 as the shearing rate.
0 to 100,000 sec ^-1 , preferably 100 to 50,
It is 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 can be used, but a non-open type device is preferable. According to the present invention, a thermoplastic elastomer composition in a state where the copolymer rubber (B) is crosslinked is obtained by the above-mentioned dynamic heat treatment. It is considered that this thermoplastic elastomer has a high-density polyethylene (A) and a copolymer rubber (B) cross-linked, and in the present invention, the gel fraction measured by the following method is 15% by weight or less, Is in the range of 0.5 to 15% by weight, preferably 1 to 13% by weight, more preferably 2 to 11% by weight. [Method for measuring gel fraction] About 100 mg of a pellet of a thermoplastic elastomer composition was weighed as a sample, wrapped in a 325 mesh screen, and 30 ml of p- which was a sufficient amount for this pellet in a closed container. 1 for xylene
Immerse at 40 ° C. for 24 hours.

Next, this sample was taken out on a filter paper and
Dry at ℃ for 2 hours or more until constant weight. The gel fraction is expressed by the following equation. Gel fraction [wt%] = [Sample dry weight after immersion in p-xylene / Sample weight before immersion in p-xylene] × 100 Second olefinic thermoplastic elastomer according to the present invention obtained as described above Melt flow rate (M
FR; ASTM D 1238, 230 ° C, 2.16 kg load) is usually 0.
01 to 1000 g / 10 minutes, preferably 0.05 to 50
0 g / 10 minutes, more preferably 0.1 to 100 g / 1
0 minutes. The thermoplastic elastomer having a melt flow rate within the above range has excellent moldability.

Such a second olefinic thermoplastic elastomer usually has a sea-island structure morphology, and has a high density polyethylene (A) and ethylene / α.
-Olefin (/ non-conjugated polyene) copolymer rubber (B)
It is preferable that the phase is an island phase and the polypropylene (C) phase is the sea. The second olefinic thermoplastic elastomer according to the present invention obtained as described above is preferably the above-mentioned first olefinic thermoplastic elastomer according to the present invention.

That is, the second olefinic thermoplastic elastomer has a sea-island structure, and the average particle size of the island phase is 2 μm.
It is below, the gel fraction is 0.5 to 15% by weight, and 125 ° C measured by a differential scanning calorimeter (DSC).
The following heat of fusion is preferably 40% or more of the total heat of fusion. In the second olefinic thermoplastic elastomer, the number of island phases having a major axis to minor axis ratio of 2 or more is preferably 3% or less, more preferably 0.1 to 3 with respect to the total number of island phases. %, And the compression set (CS) at 70 ° C., which is an index of rubber elasticity, is preferably 65% or less, more preferably 20 to 65%.

Further, the second olefinic thermoplastic elastomer has a calorific value upon fusion measured by a differential scanning calorimeter (DSC) of 30 J / g or more, usually 30 to 80 J / g.
It is preferably g. Furthermore, the second olefin-based thermoplastic elastomer is an index of rubber elasticity and the addition amount A (parts by weight) of the crosslinking agent to 100 (parts by weight) of the total amount of olefin resin and olefin rubber.
The compression set CS (%) at 0 ° C. preferably satisfies the relationship represented by the following formula A × CS <5.0.

The second olefinic thermoplastic elastomer according to the present invention is a thermoplastic elastomer that causes a base material fracture during a tensile peel test when a welding test of a vulcanized rubber to a press molded product is conducted. Preferably there is. Here, 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 member, 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 member is melt-bonded to the thermoplastic elastomer at 0 ° C. to obtain a test piece for observing the peeled state. (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, and the cross section after the test is visually observed to observe whether the base material is broken or the interface is peeled.

Molded Product A molded product of the present invention is a composite product obtained by joining, preferably by welding, the above-mentioned first or second olefinic thermoplastic elastomer of the present invention to a molded product of vulcanized rubber. It is a molded body. Such a composite molded body, for example,
A vulcanized rubber molded product and a thermoplastic elastomer molded product can be prepared in advance, and the interface can be heated to melt and then contacted. A method in which a molded body made of rubber and a molten thermoplastic elastomer are brought into contact with each other to solidify them is preferable. 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 a vulcanized rubber and the molded body made of the thermoplastic elastomer according to the present invention, a molding containing the jointed portion. It is preferable to carry out the step of heat-treating the body at a temperature of 80 ° C. or higher. For heat treatment,
The temperature is usually 80 ° C. or higher, but is not particularly limited, preferably 90 ° C. or higher, more preferably 100 ° C. or higher, and the upper limit is not particularly limited, but 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. Further, in the heat treatment, a heating device such as a heater or an oven can be appropriately used.

By the method as described above, a composite molded article having excellent adhesive strength can be obtained. As the vulcanized rubber forming the molded body, ethylene / α-olefin / polyene copolymer rubber is preferable from the viewpoint of weldability with the thermoplastic elastomer composition. As such a copolymer rubber, the above-mentioned ethylene / α-olefin (/ non-conjugated polyene) 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 first and second olefinic thermoplastic elastomers according to the present invention are used for the interior and exterior materials of vehicles, and are used for the vulcanized rubber molding (preferably polyolefin vulcanized rubber molding). It is preferably used for the corner portion (corner material) of a weather strip. Specifically, the extruded product of a polyolefin-based vulcanized rubber is cut, and in the molding of a corner portion that connects the obtained cut extruded products from different directions,
The first to second olefinic thermoplastic elastomers (compositions) according to the present invention described above are injection-molded at a temperature equal to or higher than the melting point, and are brought into contact with an extruded product of vulcanized rubber to be welded, whereby a weather strip. Can be obtained.

The weather strip having the corner molded body 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 illustrating a weather strip (glass run channel) of an automobile and a molding method thereof. As shown in FIG. 1 (A), the weather strip is a cut extruded product 1 or 2 made of vulcanized rubber and a joining corner formed when the cut extruded products 1 and 2 are connected from different directions. And the member 3. 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. Further, the "joining corner member" referred to here is a portion made of a thermoplastic elastomer formed when the cut 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 to third olefinic thermoplastic elastomers according to the present invention, which are melted at a temperature equal to or higher than the melting point in the heating chamber (screw), are provided between the cavity of the mold 4 and the core. Inject into the space that can be formed, and on the end faces of the cut extrusion molded products 1 and 2,
After welding the first and second olefinic thermoplastic elastomers according to the present invention, which are melted at a temperature equal to or higher than the melting point, the thermoplastic elastomer is cooled and the corner member 3 as shown in FIG. To obtain a weatherstrip having

The vulcanized rubber used in the preparation of the above-mentioned cut extrudates 1 and 2 includes ethylene / α-olefin /
It is preferable that the non-conjugated polyene copolymer rubber is the main component, 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, Examples thereof include 11-methyldodecene-1 and 12-ethyltetradecene-1. These α-olefins can be used alone or in combination of two or more. Among these α-olefins, α-olefins having 3 to 8 carbon atoms, such as propylene, 1-butene, 4-methylpentene-1,1-hexene and 1-octene are particularly preferable.

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. Regarding the iodine value of ethylene / α-olefin / non-conjugated polyene copolymer rubber, a rubber composition having a high crosslinking efficiency can be obtained, and a rubber composition capable of providing a vulcanized rubber molded article having excellent compression set resistance can be obtained. And, in terms of cost advantage, 1 to
It is preferably 40, more preferably 1 to 30.

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 characteristics, 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, GPF, FEF, MAF, HAF, ISAF,
Carbon black such as SAF, FT and MT can be used. Carbon black has a nitrogen adsorption specific surface area of 10 to 100 m from the viewpoint that a rubber composition capable of providing a vulcanized rubber molded product having good mechanical strength and product skin is obtained.
It is preferably ² / g.

In the vulcanized rubber, conventionally known compounds such as an antioxidant, a processing aid, a foaming agent, a foaming aid, a coloring agent, a dispersant, and a flame retardant are incorporated into the vulcanized rubber depending on the intended use of the vulcanized product. The agent is blended. Further, an inorganic filler can be appropriately used as a reinforcing agent in the vulcanized rubber depending on the application, but usually, an ethylene / α-olefin / non-conjugated polyene copolymer rubber 100 is used.
The maximum is 100 parts by weight with respect to parts by weight.

Specific examples of the inorganic filler include silica, soft calcium carbonate, heavy calcium carbonate, talc and clay. As the softening agent blended in the vulcanized rubber, the softening agent usually used for rubber can be used. Specifically, process oil, lubricating oil,
Paraffin, liquid paraffin, polyethylene wax,
Petroleum softeners such as polypropylene wax, petroleum asphalt, petrolatum; coal tar softeners such as coal tar and coal tar pitch; fatty oil softeners such as castor oil, linseed oil, rapeseed oil, soybean oil and coconut oil; Tall oil;
Waxes such as beeswax, carnauba wax and lanolin; fatty acids and fatty acid salts such as ricinoleic acid, palmitic acid, stearic acid, barium stearate, calcium stearate and zinc laurate; naphthenic acid; pine oil, rosin Or derivatives thereof; synthetic polymer substances such as terpene resin, petroleum resin, coumarone indene resin, atactic polypropylene; ester softeners such as dioctyl phthalate, dioctyl adipate, dioctyl sebacate; microcrystalline wax, liquid polybutadiene, modified liquid Examples thereof include polybutadiene, liquid polyisoprene, terminal-modified polyisoprene, hydrogenated terminal-modified polyisoprene, liquid thiochol, and hydrocarbon-based synthetic lubricating oil. 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,
Examples thereof include 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 with respect to 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.
As the vulcanization accelerator, specifically, N-cyclohexyl-2
-Benzothiazole sulfenamide (CBS), N-oxydiethylene-2-benzothiazole sulfenamide (OBS), Nt-butyl-2-benzothiazole sulfenamide (BBS), N, N-diisopropyl-2-benzo Sulfenamide compounds such as thiazole sulfenamide; 2-mercaptobenzothiazole (MBT), 2- (2,
4-dinitrophenyl) mercaptobenzothiazole, 2-
Thiazole compounds such as (4-morpholinothio) benzothiazole, 2- (2,6-diethyl-4-morpholinothio) benzothiazole and dibenzothiazyl disulfide; diphenylguanidine (DPG), triphenylguanidine,
Guanidine compounds such as diorsonitrile guanidine (DOTG), orthotolylbaiguanide, diphenylguanidine phthalate; acetaldehyde-aniline condensate, butyraldehyde-aniline condensate, hexamethylenetetramine (H), aldehyde amines such as acetaldehyde ammonia, or Aldehyde-ammonia-based compounds; 2-mercaptoimidazoline and other imidazoline-based compounds; thiocarbanilide, diethylthiourea (EU
R), dibutylthiourea, trimethylthiourea, diorsotolylthiourea and other thiourea compounds; tetramethylthiuram monosulfide (TMTM), tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide, tetrabutylthiuram disulfide, tetrakis (2-ethylhexyl) ) Thiuram-based compounds such as thiuram disulfide (TOT) and dipentamethylene thiuram tetrasulfide (TRA); zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, butylphenyldithiocarbamine. Zinc acid, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, dimethyldithiocarbamate Examples thereof include dithiocarbamate salts such as Lulu; xanthate salts such as zinc dibutylxanthate; and compounds such as zinc white (zinc oxide).

These vulcanization accelerators are usually used in a proportion of 0.1 to 20 parts by weight based on 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, and these anti-aging agents are used within a range that does not impair the object of the present invention. .

Examples of the amine anti-aging agent include diphenylamines and phenylenediamines. As the sulfur anti-aging agent, a sulfur anti-aging agent usually used for rubber is used. As the processing aid, it is possible to use a processing aid which is usually used for processing rubber. 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. As the foaming agent, specifically, an inorganic foaming agent such as sodium bicarbonate (baking soda), sodium carbonate, ammonium bicarbonate, ammonium carbonate, ammonium nitrite; N,
N'-Dimethyl-N, N'-dinitrosoterephthalamide, N, N '
-Nitroso compounds such as dinitrosopentamethylenetetramine (DPT); azodicarbonamide (ADCA),
Azo compounds such as azobisisobutyronitrile (AZBN), azobiscyclohexylnitrile, azodiaminobenzene, and barium azodicarboxylate; benzenesulfonyl hydrazide (BSH), toluenesulfonyl hydrazide (TSH), p, p'-oxybis ( Benzenesulfonyl hydrazide) (OBSH), diphenyl sulfone
Sulfonyl hydrazide compounds such as -3,3'-disulfonyl hydrazide; and azide compounds such as calcium azide, 4,4-diphenyldisulfonyl azide and p-toluenesulphonyl azide.

Further, other known rubber or resin may be blended and used in the vulcanized rubber component. Examples of such other rubber include natural rubber (NR), isoprene rubber such as isoprene rubber (IR), and butadiene rubber (B).
R), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR), and other conjugated diene rubbers.

Examples of other resins include polyethylene, polypropylene, 1,2-polybutadiene, polybutene and the like. [Preparation of Rubber Composition and Vulcanized Rubber Molded Product Thereof] The rubber composition used in the preparation of the vulcanized rubber molded product is an internal mixer (closed-type mixer) such as a Banbury mixer, a kneader or an intermix. After kneading various 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 20 minutes, Using sulfur as a roll such as an open roll or a kneader, sulfur is additionally mixed with a vulcanization accelerator, a vulcanization aid, a foaming agent, and a foaming aid, if necessary, and a roll temperature of 40
It can be prepared by kneading at -80 ° C for 5 to 30 minutes and then dispensing.

The rubber composition for extrusion molding prepared as described above is formed into an intended shape by an extrusion molding machine, and at the same time as molding, or by introducing the molding 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 (Powd
er Curing Medium or Powder Curing Method), U
A heating means such as HF (ultra-high frequency electromagnetic wave) or steam can be used.

Although the weather strip has been described as an example here, the first and second olefinic thermoplastic elastomers according to the present invention are of course applicable to the case where a fusion molded product is formed on a vulcanized rubber molded product. It can also be applied to a case where a skin portion such as a door trim is formed of a fusion skin layer.

[0091]

According to the present invention, the adhesive strength is sufficient for the vulcanized rubber (base material) without intervening the adhesive layer and the base material is broken at the time of peeling (that is, if the peeling occurs at the adhesive interface). A thermoplastic elastomer composition capable of forming a molded body) and a molded body obtained by welding the composition to a vulcanized rubber, and a molded body having sufficient hardness and rubber elasticity as a thermoplastic elastomer. It is possible to provide a thermoplastic elastomer composition which can be formed and is excellent in moldability and economy, a method for producing the same, and a molded article obtained by welding the composition to a vulcanized rubber.

[0092]

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 high-density polyethylene and polypropylene used in Examples 1-8 and Comparative Examples 1-3
m), the heat of fusion of the thermoplastic elastomer (TPE) compositions obtained in Examples 1-8 and Comparative Examples 1-3, melt flow rate (MFR), Examples 1-8 and Comparative Example 1
Measurement and evaluation of the tensile peel strength of the molded article made of the thermoplastic elastomer composition obtained in any one of 3 to 3 and the fracture mode at the time of peeling, hardness, tensile strength, elongation, compression set (CS), and moldability are as follows. It was performed according to the method of. Also,
Observation of the sea-island structure was performed according to the following method. (1) Melting point (Tm) of high-density polyethylene and polypropylene, melting calorific pellets of TPE composition were annealed at 230 ° C. for 10 minutes, and then 10 ° C. up to 30 ° C. using a differential scanning calorimeter (DSC).
After decreasing the temperature at a rate of / min, hold for 1 minute, raise the temperature at a rate of 10 ° C / min, and set the temperature with the maximum absorbed heat as the melting point (Tm), and melt from the area between the measurement curve and the baseline. The heat quantity (total heat of fusion) was determined. (2) The heat of fusion of 125 ° C. or less was determined from the temperature curve for measuring the heat of fusion at each temperature obtained by the heat of fusion of 125 ° C. or less (1) of the TPE composition. (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 Failure Mode at Peeling Vulcanized rubber press sheet obtained in Reference Example described later (length 1
2 cm x 14.7 cm wide x 2 mm thick flat plate) is cut as a material to be adhered with a cutter, and vertical 2.5 cm x 14.7
cm × thickness 2 mm, and the vulcanized rubber molded product obtained as the material to be adhered was adhered 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 cut surface of the vulcanized rubber molded product at the injection stage. did. The molded product melt-bonded in this way is punched out in a strip shape with a width of 2 cm to 200 m
A peeling test was performed at a pulling speed of m / min, and the tensile peeling strength (adhesive peeling strength) at that time was measured, and at the same time, the peeling state during the peeling test was visually determined. (5) Hardness For the hardness, Shore A hardness was measured according to JIS K6301. (Measurement conditions) A sheet was produced by a press molding machine, and a scale was read immediately after contact with a pressing needle using an A type measuring instrument. (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. (Test conditions) A sheet is produced by a press molding machine, and the JI
The No. S3 test piece was punched out at a tensile speed of 200 mm / min. (7) Compression set The compression set (CS) was measured under the following conditions according to JIS K6301. (Measurement conditions) A columnar molded product having a diameter of 29.0 mm and a thickness of 12.7 mm was manufactured by a vertical injection molding machine, and compressed in a 25% thickness direction by a spacer under a temperature condition of 70 ° C.
The compression set was calculated by measuring the thickness after release for 22 hours. (8) Observation of sea-island structure Ruthenium staining was performed so as to embed the pellet surface of the olefinic thermoplastic elastomer, frozen ultrathin sections were prepared, carbon deposition was performed, and a transmission electron microscope (T
EM) (JEM-2000FX, manufactured by JEOL Ltd.).

[0094]

[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%, 135
Intrinsic viscosity [η] measured in decalin at ℃ = 2.8dl /
g, iodine value = 12) 100 parts by weight and FEF grade carbon black [Asahi Carbon Co., Ltd., trade name Asahi # 60
G] 170 parts by weight, softener [made by Idemitsu Kosan Co., Ltd., trade name Diana Process Oil ^TM PS-430] 95 parts by weight, stearic acid 1 part by weight, zinc flower No. 1 5 parts by weight, and activator [Lion Co., Ltd., product name Arcade 2
HT-F] 1 part by weight was kneaded with a Banbury mixer [BB-2 type mixer manufactured by Kobe Steel, Ltd.] having a volume of 1.7 liters.

The kneading method was as follows. First, the raw material rubber was masticated for 1 minute, and 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, and a 14-inch open roll (manufactured by Nippon Roll Co., Ltd.) (surface temperature of front roll 60 ° C., surface temperature of rear roll 60 ° C., front roll) The rubber compound (I) was wrapped around a roll rotation speed of 16 rpm and a post-roll rotation speed of 18 rpm, and 5 parts by weight of sulfur, 2-mercaptobenzothiazole [manufactured by Sanshin Chemical Industry Co., Ltd., trade name Sunceller M] ]
15 parts by weight, dibenzothiazyl disulfide (manufactured by Sanshin Chemical Industry Co., Ltd., trade name Suncellar DM) 5 parts by weight, zinc dibutyldithiocarbamate [Sanshin Chemical Industry Co., Ltd.]
20 parts by weight of Sancella BZ], zinc dimethyldithiocarbamate [manufactured by Sanshin Chemical Industry Co., Ltd., 5 parts by weight of Suncellar PZ] ethylene thiourea [manufactured by Sanshin Chemical Industry Co., Ltd., product name of Suncellar 22C ] 10 parts by weight, dithiodimorpholine [manufactured by Sanshin Chemical Industry Co., Ltd., trade name Sanfer R] 5 parts by weight, and calcium oxide [Inoue Lime Industry Co., Ltd., trade name Vesta PP] 50 parts by weight are added. A 14-inch open roll (manufactured by Nippon Roll Co., Ltd., roll temperature 60 ° C.) was kneaded for 7 minutes 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.

[0098]

Example 1 High density polyethylene [Density (ASTM D 150
5): 0.956 g / cm ³ , MFR (ASTM D 1238, 190
℃, 2.16kg load): 6g / 10 minutes, melting point (Tm): 12
7 ° C .; hereinafter abbreviated as HDPE-1. ] 15 parts by weight and oil-extended ethylene / propylene / 5-ethylidene as a rubber component
-2-Norbornene copolymer rubber [ethylene content: 78 mol%, propylene content: 22 mol%, iodine value: 13,
Mooney viscosity [ML _{1 + 4} (100 ° C.)] 74, oil extension: 40 parts by weight of paraffinic process oil (trade name PW-380, manufactured by Idemitsu Kosan Co., Ltd.) per 100 parts by weight of rubber; Abbreviated as EPT. ] 47 parts by weight and propylene / ethylene / 1-butene terpolymer as polypropylene [MFR (ASTM D 1238, 230 ° C, 2.16 kg load):
7.0 g / 10 min, melting point (Tm): 136 ° C .;
Abbreviated as P-1. ) 38 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-based weathering stabilizer [Nippon Ciba-Geigy Co., Ltd.] as a weathering agent
0.1 parts by weight of TINUVIN 326, a product name, and a slip agent [Lion Co., Armoslip C, product name]
P] 0.3 part by weight, organic peroxide as a cross-linking agent [Nippon Yushi-Seiyaku Co., Ltd., trade name Perhexa 25B] 0.08 part by weight, and divinylbenzene (DVB) as a cross-linking aid
Mix well with 0.04 parts by weight with a Henschel mixer,
Extruder [Part number TEM-50, manufactured by Toshiba Machine Co., L /
D = 40, cylinder temperature: C1 to C2 120 ° C., C
3 to C4 140 ° C, C5 to C6 180 ° C, C7 to C8
200 ° C, C9 to C12 220 ° C, die temperature: 2
10 ° C, screw rotation speed: 200 rpm, extrusion rate: 4
Granulation was performed while injecting 20 parts by weight of paraffin-based process oil [trade name: PW-380, manufactured by Idemitsu Kosan Co., Ltd.] into a cylinder at 0 kg / h) to obtain pellets of a thermoplastic elastomer composition.

The thermoplastic elastomer composition obtained was
According to the transmission electron microscope (TEM), EPT phase and HD
It was observed that the PE-1 phase was an island and the PP-1 phase was the sea. The average particle size of the island phase was 2 μm or less, and the number of island phases having a ratio of major axis to minor axis of 2 or more was 0.5% with respect to the total number of island phases. In addition, this composition has a gel fraction of 7% by weight and has a heat quantity upon fusion (total heat of fusion) of 45 J.
/ G, and the ratio of the heat of fusion of 125 ° C. or less to the total heat of fusion was 58%.

The pellet-shaped thermoplastic elastomer composition was injection-molded, and the obtained molded body was evaluated according to the above-mentioned method. Then, this thermoplastic elastomer composition was molded on a cut surface of the vulcanized rubber press sheet by a 100 ton injection molding machine so as to be melt-bonded at the injection molding stage. The following molded product was subjected to the tensile peel test. <Tensile Peeling Test of Molded Product> 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 joined, for example, a weather strip. For a molded product having a large number of joints, grip the two places sandwiching the joints and pull at a pulling speed of 2
A tensile test was performed at 00 mm / min, and a cross section after the test was observed to confirm whether the base material was broken or the interface was peeled.

The results are shown in Table 1.

[0102]

Example 2 In Example 1, instead of HDPE-1, the density (ASTM D 1505) was 0.954 g / cm ³ , MF
R (ASTM D 1238, 190 ℃, 2.16kg load) is 0.8g / 1
Pellets of the thermoplastic elastomer composition were obtained in the same manner as in Example 1 except that high-density polyethylene (hereinafter abbreviated as HDPE-2) having a melting point (Tm) of 131 ° C. for 0 minutes was used.

The thermoplastic elastomer composition obtained was
It had a sea-island structure, the average particle size of the island phase was 2 μm or less, and the number of island phases having a ratio of major axis to minor axis of 2 or more was 1.3% with respect to the total number of island phases. In addition, this composition
The gel fraction is 8% by weight and the calorific value upon melting is 45 J / g
The ratio of the heat of fusion below 125 ° C. to the total heat of fusion was 57%.

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

[0105]

Example 3 In Example 1, instead of HDPE-1, the density (ASTM D 1505) was 0.965 g / cm ³ , MF
R (ASTM D 1238, 190 ℃, 2.16kg load) is 13g / 10
The pellets of the thermoplastic elastomer composition were obtained in the same manner as in Example 1 except that high density polyethylene (hereinafter abbreviated as HDPE-3) having a melting point (Tm) of 131 ° C. was used.

The thermoplastic elastomer composition obtained was
It had a sea-island structure, the average particle size of the island phase was 2 μm or less, and the number of island phases having a ratio of major axis to minor axis of 2 or more was 0.3% with respect to the total number of island phases. In addition, this composition
The gel fraction is 7% by weight and the calorific value upon melting is 45 J / g.
The ratio of the heat of fusion below 125 ° C. to the total heat of fusion was 58%.

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

[0108]

Example 4 In Example 1, instead of PP-1,
Propylene / Ethylene Binary Copolymer [MFR (ASTM D 1
238, 230 ℃, 2.16kg load): 21g / 10min, melting point (T
m): 145 ° C.] (hereinafter, abbreviated as PP-2), except that the thermoplastic elastomer composition pellets were obtained in the same manner as in Example 1.

The thermoplastic elastomer composition obtained was
It had a sea-island structure, the average particle size of the island phase was 2 μm or less, and the number of island phases having a ratio of major axis to minor axis of 2 or more was 0.6% with respect to the total number of island phases. In addition, this composition
The gel fraction is 9% by weight, and the heat when melting is 48 J / g.
The ratio of the heat of fusion of 125 ° C. or less to the total heat of fusion was 61%.

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.

[0111]

Example 5 In Example 1, instead of 47 parts by weight of EPT, 32 parts by weight of EPT and an ethylene / propylene copolymer rubber [MFR (ASTM D 1238, 190 ° C., 2.16 kg load): 0.7 g / 10 minutes, Ethylene content: 81 mol%;
Hereinafter, it is abbreviated as EPR-1. ] A thermoplastic elastomer composition pellet was obtained in the same manner as in Example 1 except that 15 parts by weight was used.

The thermoplastic elastomer composition obtained was
It had a sea-island structure, the average particle size of the island phase was 2 μm or less, and the number of island phases having a ratio of major axis to minor axis of 2 or more was 0.4% with respect to the total number of island phases. In addition, this composition
The gel fraction is 7% by weight and the calorific value upon melting is 46 J / g.
The ratio of the heat of fusion of 125 ° C. or less to the total heat of fusion was 59%.

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.

[0114]

Example 6 In Example 1, EPT and PP-1
Pellets of the thermoplastic elastomer composition were obtained in the same manner as in Example 1 except that the compounding amounts of the above were changed to 52 parts by weight and 33 parts by weight, respectively. The obtained thermoplastic elastomer composition has a sea-island structure, and the average particle size of the island phase is 2 μm.
The number of island phases having a ratio of major axis to minor axis of 2 or more was 1.5% or less with respect to the total number of island phases. Further, this composition had a gel fraction of 10% by weight, a calorific value upon melting of 42 J / g, and a ratio of the calorific value of melting of 125 ° C. or less to the total calorific value of melting was 63%.

The 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.

[0116]

Example 7 In Example 1, EPT and PP-1
Change the compounding amount of each to 27 parts by weight and 33 parts by weight,
Furthermore, ethylene / 1-octene copolymer rubber [MFR (AS
TM D1238, 190 ° C, 2.16 kg load): 1 g / 10 minutes, ethylene content: 87 mol%; hereinafter abbreviated as EOR. ] The pellets of the thermoplastic elastomer composition were obtained in the same manner as in Example 1 except that 25 parts by weight was used.

The thermoplastic elastomer composition obtained was
It had a sea-island structure, the average particle size of the island phase was 2 μm or less, and the number of island phases having a ratio of major axis to minor axis of 2 or more was 1.3% with respect to the total number of island phases. In addition, this composition
The gel fraction is 9% by weight and the calorific value upon melting is 42 J / g.
The ratio of the heat of fusion of 125 ° C. or less measured by DSC to the total heat of fusion was 65%.

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.

[0119]

[Embodiment 8] EPT, HDPE-1 in Embodiment 1
Pellets of the thermoplastic elastomer composition were obtained in the same manner as in Example 1 except that the amounts of PP and PP-1 were changed to 52 parts by weight, 20 parts by weight and 28 parts by weight, respectively.
The obtained thermoplastic elastomer composition has a sea-island structure, the average particle size of the island phase is 2 μm or less, and the number of island phases having a ratio of major axis to minor axis of 2 or more is based on the total number of island phases. Was 1.7%. This composition also has a gel fraction of 1
0% by weight, the amount of heat upon melting is 50 J / g, 1
The ratio of the heat of fusion below 25 ° C to the total heat of fusion is 71
%Met.

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.

[0121]

Example 9 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 extruded at an extruder head temperature of 80 ° C.
Extrusion molding was performed at a speed of 2.5 m / min using a modified nozzle having a cross-sectional shape of FIG. 1 of length 2 mm × width 25 mm, and a microwave vulcanization tank (UHF) and a hot air vulcanization tank (HAV) were connected in series. Vulcanization was carried out using a molding line connected to 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. The total residence time in both vulcanization tanks was 5 minutes. Then, using a 70 ton vertical injection molding machine, 20
It was cut at intervals of cm, and set in a mold such as reference numeral 4 in FIG. 1 so that the thermoplastic elastomer composition could be welded to the cut surface. Thereafter, the thermoplastic elastomer composition obtained in Example 1 was melt-bonded at an injection temperature of 230 ° C. and a mold temperature of 50 ° C. As a result of the peeling test, destruction of the base material was observed.

[0123]

Comparative Example 1 In Example 1, EPT and HDPE
Pellets of the thermoplastic elastomer composition were obtained in the same manner as in Example 1 except that the compounding amounts of -1 were changed to 62 parts by weight and 0 parts by weight, respectively. The obtained thermoplastic elastomer composition has a sea-island structure, and the average particle size of the island phase is 2
The number of island phases having a ratio of major axis to minor axis of 2 or more was 1.5% with respect to the total number of island phases. In addition, this composition had a gel fraction of 4% by weight, a calorific value upon melting of 18 J / g, and a ratio of the calorific value of melting of 125 ° C. or lower to the total calorific value of melting was 35%.

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.

[0125]

[Comparative Example 2] Example 2 except that the amounts of the cross-linking agent (trade name Perhexa 25B) and the cross-linking aid (divinylbenzene) were changed to 0.16 parts by weight and 0.08 parts by weight, respectively. In the same manner as in 1, pellets of the thermoplastic elastomer composition were obtained. The obtained thermoplastic elastomer composition has a sea-island structure, the average particle size of the island phase is 2 μm or less, and the number of island phases having a ratio of major axis to minor axis of 2 or more is based on the total number of island phases. Was 5%. In addition, this composition had a gel fraction of 37% by weight, a calorific value upon melting of 43 J / g, and a ratio of the calorific value of melting of 125 ° C. or less to the total calorific value of melting was 58%.

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.

[0127]

[Comparative Example 3] Example 3 except that the amounts of the cross-linking agent (trade name Perhexa 25B) and the cross-linking aid (divinylbenzene) were changed to 0.24 parts by weight and 0.12 parts by weight, respectively. In the same manner as in 1, pellets of the thermoplastic elastomer composition were obtained. The obtained thermoplastic elastomer composition has a sea-island structure, the average particle size of the island phase is 2 μm or less, and the number of island phases having a ratio of major axis to minor axis of 2 or more is based on the total number of island phases. Was 7%. Further, this composition had a gel fraction of 47% by weight, a calorific value upon melting of 42 J / g, and a ratio of the calorific value of melting of 125 ° C. or less to the total calorific value of melting was 58%.

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.

[0129]

Comparative Example 4 With respect to the sample of Comparative Example 1, a molded body was manufactured in the same manner as in Example 9 and a tensile peel test was conducted. As a result, no fracture of the base material was observed and interfacial peeling was observed. In addition,
Regarding components not described as composition components in Table 1, the amount of the slip agent in Examples 1 to 8 and Comparative Examples 1 to 3 was 0.3 parts by weight, and the amount of the antioxidant and the weather resistance stabilizer was 0.1 parts by weight, and the blending amount of the paraffinic process oil is 20 parts by weight.

(*) In Table 1: Ratio of major axis to minor axis is 2
Percentage obtained by dividing the number of island phases above by the total number of island phases.

[0131]

[Table 1]

[0132]

[Table 2]

[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 member is formed of the thermoplastic elastomer composition according to the present invention,
FIG. 1B is a schematic perspective view for explaining a method of forming the corner member of the weather strip.

[Explanation of symbols]

1, 2 ... Cut-out extrusion 3 ・ ・ Joint corner member 4 ... Injection mold

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) B29K 23:00 B29K 23:00 F term (reference) 4F071 AA15X AA16 AA20X AA21X AA82 AA87 AA88 AA89 AC08 AE04 AE05 AE11 AF15Y AF19Y AF21Y AF25Y AF26Y AH09 AH11 4F211 AA03 AA45 AD05 AG28 AH23 TA06 TC08 TC13 TD07 TN82 4J002 BB03W BB12Y BB15X EK026 EK036 EK046 EK056 EK086 GF00 GN00

Claims (10)

[Claims] 1. An olefinic thermoplastic elastomer having a sea-island structure morphology, wherein the island phase has an average particle size of 2 μm or less, a gel fraction of 0.5 to 15 wt%, and a differential An olefin-based thermoplastic elastomer characterized in that the heat of fusion at 125 ° C. or less measured by a scanning calorimeter (DSC) is 40% or more of the total heat of fusion. 2. The olefinic thermoplastic elastomer according to claim 1, wherein the calorific value at the time of melting measured by a differential scanning calorimeter (DSC) is 30 J / g or more. 3. The density (ASTM D 1505) is 0.940 g / c.
5-50 parts by weight of high-density polyethylene (A) having m ³ or more, and ethylene / α-olefin (/ non-conjugated polyene) consisting of ethylene, α-olefin having 3 to 20 carbon atoms, and optionally non-conjugated polyene. ) Copolymer rubber (B) 5
70 parts by weight, polypropylene (C) 5 to 50 parts by weight [component (A),
The total amount of (B) and (C) is 100 parts by weight], and the gel fraction is 0.5 to 15% by weight. Plastic elastomer. 4. The olefinic thermoplastic elastomer is an olefinic thermoplastic elastomer having a sea-island structure morphology, and the island phase has an average particle diameter of 2 μm.
The gel fraction is 0.5 to 15% by weight, and the heat of fusion at 125 ° C or lower measured by a differential scanning calorimeter (DSC) is 40% or more of the total heat of fusion. The olefinic thermoplastic elastomer according to claim 3, wherein 5. The thermoplastic elastomer has a calorific value at the time of melting of 30 J / as measured by a differential scanning calorimeter (DSC).
The olefin-based thermoplastic elastomer according to claim 4, which is g or more. 6. The density (ASTM D 1505) is 0.940 g / c.
5-50 parts by weight of high-density polyethylene (A) having m ³ or more, 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, polypropylene (C) 5 to 50 parts by weight [component (A),
The total amount of (B) and (C) is 100 parts by weight], and the blended product is melt-kneaded in the presence of the crosslinking agent (D) to give a gel fraction of 0.5 to 15% by weight. A method for producing an olefin-based thermoplastic elastomer, characterized in that the thermoplastic elastomer is obtained. 7. A molded body made of vulcanized rubber, and claims 1-5.
A molded body formed by joining the molded bodies made of the thermoplastic elastomer according to any one of 1. 8. The molded product according to claim 7, wherein the molded product is for an automobile interior / exterior material. 9. The molded article according to claim 8, wherein the automobile interior / exterior material is a weather strip material. 10. A weather strip material in which a straight portion and a joining corner member are joined, wherein the straight portion is made of a molded product of the vulcanized rubber, and the corner member is any one of claims 1 to 5. The molded article according to claim 9, which is formed from the thermoplastic elastomer according to claim 9.