JP2003003023A - Thermoplastic elastomer composition and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic elastomer composition excellent in moldability which has excellent weldability with an extruded article such as a weather strip made of a thermoplastic elastomer or made of a vulcanized rubber, is capable of forming a corner part having a moderate softness (stiffness) and exhibits such weldability that matrix fracture occurs when it is used as an extruded article and peeled off from a thermoplastic elastomer. SOLUTION: The thermoplastic elastomer composition contains (A) a propylene-based polymer containing at least one of copolymers (A1) composed of propylene and a 2C or 4-20C α-olefin having a melting point Tm of 145 deg.C or below and a heat of fusion of 90 J/g or below, (B) an ethylene-based rubber component and, optionally, a higher fatty acid amide and/or a polyorganosiloxane at a specified ratio. The composition is obtained by heat- treating dynamically the blend of the respective components in the (non-)presence of a crosslinking agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic elastomer composition and its use. More specifically, the present invention relates to a corner member used for fusion-molding a corner irregular connecting portion or an irregular terminal portion of a weather strip or door trim of an automobile. As, and a thermoplastic elastomer composition also suitable as a linear member on the side where the corner member is fused, and
The present invention relates to a thermoplastic elastomer molded article that exhibits excellent adhesiveness at a fusion-bonded portion between a corner member and a linear member by using such a thermoplastic elastomer composition.

[0002]

BACKGROUND OF THE INVENTION Various materials have been conventionally used for parts or parts that require rubber elasticity used in automobile parts, industrial machine parts, electric / electronic parts, building materials and the like. For example, a weather strip is an example of such an automobile part. The weather strip is a guide member provided between the window glass and the window frame, and facilitates the lifting and opening / closing operation of the window glass, and at the same time, tightly (liquid-tightly) between the window glass and the window frame. It is necessary to perform a tight sealing operation.

Conventional weather strips are made of ethylene-
A vulcanized rubber such as propylene-diene copolymer rubber is used as a base material, and a nylon film or the like for sliding on a window glass is attached to its surface with an adhesive. In addition, a method has been performed in which vulcanization adhesion is performed on a base material by injection molding and then steps such as deburring are performed.

Such a glass run channel made of vulcanized rubber has a problem that it has many steps and is complicated, and the vulcanized rubber cannot be recycled. Therefore, in recent years, the number of steps has been reduced, and a recyclable thermoplastic elastomer has been used, a vulcanized rubber or a thermoplastic elastomer has been used as a base material, and a thermoplastic elastomer has been used as a corner material. It was

Conventionally, as a method of manufacturing a weather strip made of a thermoplastic elastomer, a straight member of a weather strip (extruded product) made of a thermoplastic elastomer is cut and set in a mold from both sides to form a cavity. In addition, a method of injection molding a thermoplastic elastomer of the same kind as a corner member, for example, an olefinic thermoplastic elastomer is adopted.

However, in the above-mentioned conventional techniques, the welding strength between the weather strip (extruded product) and the corner portion is weak, and in particular, the welding between the lip portion and the corner portion of the weather strip is incomplete. When the weather strip is bent, there is a problem that the corner portion is peeled off from the lip portion of the weather strip.

Therefore, in the conventional olefinic thermoplastic elastomer, the cross-linking ethylene rubber component is reduced and the polypropylene component is increased to improve the heat-bonding strength and to separate the corner portion from the lip portion of the weather strip. Was prevented. However, the corner molded body obtained by this method has too high hardness,
It was unsuitable for use as a corner portion of a weather strip for automobiles. Regarding the welding of the base material and the corner material, in the case of vulcanized rubber, vulcanization adhesion is performed,
In the case of an olefinic thermoplastic elastomer, while it exhibits adhesiveness that indicates base material failure during the peeling test of the welded surface,
It has been found that there is a problem that only adhesiveness that exhibits interfacial peeling behavior can be obtained.

Therefore, as a weather strip, a thermoplastic material having excellent weldability between a straight line portion and a corner portion and excellent in moldability capable of forming a corner portion or a straight line portion having appropriate softness (hardness) The advent of elastomeric compositions is desired.

[0009]

SUMMARY OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, in which a thermoplastic elastomer weatherstrip, a vulcanized rubber weatherstrip, or the like is used as a linear member. In this case, a thermoplastic elastomer composition having excellent weldability and excellent moldability capable of forming a corner portion having appropriate softness (hardness), and the thermoplastic elastomer composition being linear With the object of providing a thermoplastic elastomer composition having good adhesiveness such that the base material is broken when the welded portion is peeled off when the thermoplastic elastomer of the corner member is welded There is.

[0010]

SUMMARY OF THE INVENTION The first thermoplastic elastomer composition according to the present invention is a copolymer (A1) of propylene and an α-olefin having 2 or 4 to 20 carbon atoms [differential scanning calorimeter (DSC)]. The melting point Tm measured by the method is 145 ° C. or less, and the heat quantity at the time of melting is 90 J / g or less. ] Propylene-based polymer (A) 5 containing at least one
To 95 parts by weight and 5 to 95 parts by weight of the ethylene rubber component (B) [the total amount of the component (A) and the component (B) is 100 parts by weight].

The first thermoplastic elastomer composition according to the present invention preferably has a calorific value of 25 J / g or less when melted as measured by DSC of the entire composition. In the above first thermoplastic elastomer composition, the copolymer (A1) is a crystalline propylene / ethylene copolymer (A
1-1) and / or crystalline propylene / ethylene / 1-
It is preferably a butene copolymer (A1-2).

The propylene-based polymer (A) is 100 weight% of the total amount of the crystalline propylene / ethylene copolymer (A1-1) and the crystalline propylene / ethylene / 1-butene copolymer (A1-2). Propylene rubber (A2)
It is desirable to contain 0.1 to 200 parts by weight.
The ethylene rubber component (B) is preferably an ethylene / propylene copolymer rubber (B1) and / or an ethylene / propylene / diene copolymer rubber (B2).

The first thermoplastic elastomer composition according to the present invention further comprises a higher fatty acid amide (C) relative to 100 parts by weight of the total amount of the propylene polymer (A) and the ethylene rubber component (B). ) 0.1 to 2.0 parts by weight and / or polyorganosiloxane (D) 0.1 to
It is desirable to contain 10 parts by weight. The second thermoplastic elastomer composition according to the present invention comprises the propylene polymer (A) and the ethylene rubber component (B) which constitute the above-mentioned first thermoplastic elastomer composition according to the present invention. It is characterized in that it is obtained by dynamically heat treating the formulation in the presence of a crosslinker (E).

In the second thermoplastic elastomer composition according to the present invention obtained by this heat treatment, the ethylene rubber component (B) is crosslinked. On the other hand, in the first thermoplastic elastomer composition according to the present invention, the ethylene rubber component (B) is not crosslinked. these,
The first and second thermoplastic elastomer compositions according to the present invention form a corner portion that is welded to a thermoplastic elastomer molding or a vulcanized rubber molding used as an interior / exterior material of a vehicle, for example, a corner portion of a weather strip for an automobile. It is preferably used for

As the first or second thermoplastic elastomer composition according to the present invention, when a molded body is prepared from the thermoplastic elastomer composition, the Shore A hardness (JIS K 6301) of the molded body is It is 85 or less, and the thermoplastic elastomer composition is injected onto the surface of the thermoplastic elastomer molded product or the vulcanized rubber molded product at an injection temperature of 190 ° C.
When melt-bonded by injection molding under the above condition, the adhesive peel strength of the melt-bonded portion is preferably 2.5 MPa or more.

The molded article according to the present invention is obtained by adding the thermoplastic elastomer composition (ii) to the molded article (I) of the thermoplastic elastomer composition (i) according to the first or second aspect of the present invention. It is characterized by being welded. In the molded article according to the present invention, it is desirable that the peeled form shows base material fracture when a peeling test is performed on the welded portion of the molded article (I) and the thermoplastic elastomer composition (ii).

The thermoplastic elastomer composition (ii) is preferably the thermoplastic elastomer composition according to the first or second aspect. The molded product according to the present invention is suitable for use as an automobile interior / exterior material. This car interior and exterior material,
It may be a portion including a corner of the weather strip. Here, the portion including the corner of the weather strip refers to the entire portion where the linear member and the corner portion are joined.

The molded article (I) comprising the first and second thermoplastic elastomer compositions (i) according to the present invention exhibits excellent adhesiveness to a corner material, and therefore the corner portion of a weather strip for automobiles. It is preferably used as a linear member of a portion including. The portion formed by the thermoplastic elastomer composition (ii) is preferably used as a corner member of the portion including the corner of the weather strip.

Here, the linear member is a linear portion of the weather strip, and the linear portion is joined by a corner member. The corner member is formed by joining the straight members of the weather strip.

[0020]

DETAILED DESCRIPTION OF THE INVENTION The thermoplastic elastomer composition according to the present invention and its use will be specifically described below. The thermoplastic elastomer composition according to the present invention contains a propylene polymer (A), an ethylene rubber component (B), and optionally a higher fatty acid amide (C) and a polyorganosiloxane (D). .

The thermoplastic elastomer composition according to the present invention is a non-crosslinking type thermoplastic resin obtained by dynamically heat-treating a composition comprising the above components in the absence of a crosslinking agent (E). It may be an elastomer composition, or a cross-linkable thermoplastic elastomer composition obtained by dynamically heat-treating a composition comprising the above components in the presence of a cross-linking agent (E). It may be.

The propylene polymer (A) is
It comprises at least one copolymer (A1) of propylene and an α-olefin having 2 or 4 to 20 carbon atoms.
First, the copolymer (A1) used in the thermoplastic elastomer composition according to the present invention will be described below. Copolymer (A1) The copolymer (A1) used in the present invention has a melting point Tm measured by a differential scanning calorimeter (DSC) of 145 ° C. or less,
Usually 115-145 ° C, preferably 115-135
C., more preferably in the range of 115 to 125.degree. C., and having a calorific value at the time of melting of 90 J / g or less, usually 30.
To 90 J / g, preferably 30 to 70 J / g, and more preferably 30 to 50 J / g.

The melt flow rate (MFR; ASTM D 1238, 230 ° C., 2.16 kg load) of the copolymer (A1) is
Usually, 0.1 to 1000 g / 10 minutes, preferably 1 to 1
The amount is 00 g / 10 minutes, more preferably 5 to 50 g / 10 minutes. When the copolymer (A1) within the above range is used,
Excellent weldability with extrusion molded products such as weather strips made of thermoplastic elastomer and weather strips made of vulcanized rubber, as well as excellent formability capable of forming corners with appropriate softness (hardness). A thermoplastic elastomer composition can be obtained.

Such a copolymer (A1) is a copolymer of propylene and an α-olefin having 2 or 4 to 20 carbon atoms. As the α-olefin having 2 or 4 to 20 carbon atoms, specifically, ethylene, 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-hexadecene, Examples thereof include 1-octadecene and 1-eicosene. Among them, ethylene and 1-butene are preferably used. These α-olefins may be used alone or in combination of two or more.

The method for producing the copolymer (A1) is not particularly limited, and it can be prepared by a conventionally known method for producing a propylene (co) polymer. Such a copolymer (A
As 1), specifically, crystalline propylene / ethylene copolymer (A1-1), crystalline propylene / ethylene / 1-
Butene copolymer (A1-2), crystalline propylene / 1-butene copolymer (A1-3), propylene / 1-octene copolymer (A1-4), propylene / 1-hexene copolymer (A1) -
5) and the like. Among them, crystalline propylene / ethylene copolymer (A1-1) and crystalline propylene / ethylene / 1-butene copolymer (A1-2) are preferable.

"Crystallinity" in the copolymer (A1) means that the content of a component derived from an α-olefin other than propylene (that is, an α-olefin having 2 or 4 to 20 carbon atoms) is 10% by weight. It means less than%.
Further, the copolymer (A1) is a random copolymer and /
Alternatively, it is composed of a block copolymer. The copolymer (A1) used in the present invention comprises one or more of these copolymers, and preferably the crystalline propylene / ethylene copolymer (A1-1) and the crystalline propylene / ethylene / 1- A polymer containing butene copolymer (A1-2) or a mixture thereof is desirable. When the copolymer (A1) contains the above mixture, the copolymer (A1-1) is more than 0% by weight and less than 100% by weight, and the copolymer (A1-2) is 0% by weight.
More than 100% by weight and less than 100% by weight.

Propylene-based rubber (A2) The propylene-based rubber (A2) used in the present invention is the propylene-based polymer (A) containing the copolymer (A1-1) and the copolymer (A1-2). , A mixture of the copolymer (A1-1) and a copolymer other than the copolymer (A1-2), and the copolymer (A1-2) and the copolymer (A1- In the case of containing one mixture selected from a mixture with a copolymer other than 1) and a propylene rubber (A2), this mixture 1
00 parts by weight [When the (A1-2) does not exist, the (A1-
The amount of 1) is 100 parts by weight, and when the (A1-1) is not present, the amount of the (A1-2) is 100 parts by weight. ], 0.1-200 parts by weight, preferably 1-100
It is desirable to contain the compound in an amount of, preferably 5 to 80 parts by weight, particularly preferably 10 to 50 parts by weight. When the propylene rubber (A2) is used in a ratio within the above range, it is possible to form a corner portion having more appropriate softness (hardness).

The propylene rubber (A2) is not particularly limited, but it is made of a copolymer of propylene and an α-olefin having 2 or 4 to 20 carbon atoms. As the α-olefin having 2 or 4 to 20 carbon atoms, specifically, ethylene, 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-hexadecene, 1-octadecene, 1-eicosene, and the like, among them, ethylene, 1- Butene is preferably used. These α-olefins may be used alone or in combination of two or more.

As such a propylene rubber (A2), specifically, a propylene / ethylene copolymer rubber,
Propylene / 1-butene copolymer rubber, propylene / ethylene / 1-butene copolymer rubber, propylene / 1-hexene copolymer rubber, propylene / 1-octene copolymer rubber and the like can be mentioned. Among these, propylene / ethylene copolymer rubber and propylene / 1-butene copolymer rubber are particularly preferable. The propylene-based rubber (A2) means a random copolymer in which the content of the component derived from propylene is 50% by weight or more and 90% by weight or less. These propylene-based rubbers (A2) may be used alone or in combination of 2
A combination of two or more species can be used.

Propylene-based Polymer (A) The propylene-based polymer (A) used in the present invention contains at least one of the above-mentioned copolymers (A1), and the copolymer (A1) is It is desirable to contain 10 to 100 parts by weight, preferably 30 to 90 parts by weight, more preferably 40 to 80 parts by weight, and particularly preferably 50 to 70 parts by weight, based on 100 parts by weight of the combined product (A).

As the propylene-based polymer (A) used in the present invention, a propylene homopolymer may be used in addition to the copolymer (A1) and the propylene-based rubber (A2). The propylene homopolymer is a copolymer (A
It is desirable that the total amount of 1) and the propylene-based rubber (A2) is 100 parts by weight or more, usually more than 0 parts by weight and 50 parts by weight or less, preferably more than 0 parts by weight and 20 parts by weight or less.

When the thermoplastic elastomer composition according to the present invention comprises a propylene polymer (A) and the following ethylene rubber component (B), the propylene polymer (A) is It is used in a proportion of 5 to 95 parts by weight, preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, based on 100 parts by weight of the total amount of A) and the rubber component (B).

When the propylene-based polymer (A) containing the copolymer (A1) in the ratio within the above range is used in the ratio within the above range, a weather strip made of a thermoplastic elastomer,
It has excellent weldability with extrusion molded products such as weather strips made of vulcanized rubber, and can form corners with appropriate softness (hardness), and also has weldability when used as a linear member. It is possible to obtain a thermoplastic elastomer composition which is excellent in moldability and has an appropriate softness (hardness).

Ethylene-based rubber component (B) The ethylene-based rubber component (B) used in the present invention is mixed with a peroxide and kneaded under heating to crosslink, resulting in a decrease in fluidity or no flow. It is a crosslinkable rubber, and specific examples thereof include ethylene / propylene copolymer rubber (B1) and ethylene / propylene / diene copolymer rubber (B2). These rubbers can be used alone or in combination of two or more.

The content of the component derived from ethylene in such a crosslinkable rubber exceeds 50% by weight. As a result, the content of the component derived from propylene is necessarily less than 50% by weight, and in this respect, the ethylene rubber component (B) is distinguished from the propylene rubber (A2). The ethylene-based rubber component (B) used in the present invention is a so-called oil-extended rubber containing a softening agent, preferably a mineral oil-based softening agent, in the production of the ethylene-based copolymer rubber as described above. May be. Examples of the mineral oil-based softening agent include conventionally known mineral oil-based softening agents such as paraffin-based process oil.

The Mooney viscosity [ML1 + 4 (100 ° C.)] of the ethylene rubber component (B) is usually 10 to 25.
It is 0, preferably 30 to 150. In the present invention, the ethylene rubber component (B) is 100 in total of the propylene polymer (A) and the ethylene rubber component (B).
5 to 95 parts by weight, preferably 10 parts by weight
To 90 parts by weight, more preferably 20 to 80 parts by weight. When the rubber component (B) is used in a ratio within the above range, it has excellent weldability to 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 which is capable of forming a corner portion having the above-mentioned properties, has excellent weldability even when used as a linear member, and has an appropriate softness (hardness) and excellent moldability.

In the present invention, the composition of the propylene polymer (A) and the ethylene rubber component (B) is ¹³ C.
-Determined by measurement by NMR. Higher fatty acid amide (C) Specific examples of the higher fatty acid amide (C) used in the present invention include oleic acid amide, erucic acid amide, stearic acid amide, and behenic acid amide. These higher fatty acid amides can be used alone or in combination of two or more.

The higher fatty acid amide (C) is used as a so-called slip agent, based on 100 parts by weight of the total amount of the propylene polymer (A) and the ethylene rubber component (B).
0.1 to 2.0 parts by weight, preferably 0.2 to 1 part by weight,
More preferably, it is used in a proportion of 0.3 to 0.5 parts by weight. When the higher fatty acid amide (C) is used in a ratio within the above range, the thermoplastic elastomer composition obtained can prevent stickiness of the surface of the molded article due to the propylene polymer (A) having a low melting point, and Since the slip of the surface of the molded product becomes good, it is suitable for forming a member of a weather strip for automobiles.

The higher fatty acid amide (C) can be used together with the polyorganosiloxane (D) described later. Polyorganosiloxane (D) The polyorganosiloxane (D) optionally used in the present invention is not particularly limited, and examples thereof include an organosiloxane (so-called silicone oil) conventionally used as a slip agent. To be Specifically, polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane, and these polysiloxanes are epoxy-modified, alkyl-modified, amino-modified, carboxyl-modified,
Examples thereof include alcohol-modified, fluorine-modified, alkyl aralkyl polyether-modified, epoxy polyether-modified or polyether-modified modified polysiloxane.
These polyorganosiloxanes (D) can be used alone or in combination of two or more.

The polyorganosiloxane (D) is 0.1 to 10 parts by weight, preferably 0.5 to 10 parts by weight based on 100 parts by weight of the total amount of the propylene polymer (A) and the ethylene rubber component (B). It is used in an amount of 5 parts by weight, more preferably 1 to 3 parts by weight. When the polyorganosiloxane (D) is used in a ratio within the above range, the thermoplastic elastomer composition obtained can prevent stickiness of the surface of the molded article due to the propylene-based polymer (A) having a low melting point, and Since the slip of the surface of the molded product becomes good, it is suitable for forming a member of a weather strip for automobiles.

The polyorganosiloxane (D) may be used in combination with the above-mentioned higher fatty acid amide (C),
In addition, they may not be used together. Crosslinking Agent (E) The thermoplastic elastomer composition according to the present invention can be prepared by dynamically heat treating in the presence or absence of the crosslinking agent (E).

Examples of the cross-linking agent (E) 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 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-dichloro Benzoyl peroxide, tert-butyl peroxybenzoate, te
rt-butyl perbenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide,
Examples thereof include lauroyl peroxide and tert-butyl cumyl peroxide.

Among them, in terms of odor and scorch stability,
2,5-Dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-Dimethyl-2,5-di (tert-butylperoxy) hexyne-3,1,3-bis (tert-butylperoxy) Isopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane and n-butyl-4,4-bis (tert-butylperoxy) valerate are preferable, and among them, 1,3-bis Most preferred is (tert-butylperoxyisopropyl) benzene.

The amount of the organic peroxide compounded is about 0.05 to 3% by weight based on 100% by weight of the total amount of the propylene polymer (A) and the ethylene rubber component (B).
Preferably it is chosen to be in the range of about 0.1 to 1% by weight, more preferably about 0.1 to 0.5% by weight.
By setting the blending amount within the above range, the thermoplastic elastomer composition in which the ethylene-based rubber component (B) is crosslinked has sufficient rubber properties and strength such as heat resistance, tensile properties, elastic recovery and impact resilience. It also has excellent moldability.

In the present invention, during the crosslinking treatment with the organic peroxide, sulfur, p-quinonedioxime, p,
p'-dibenzoylquinone dioxime, N-methyl-N, 4-dinitrosoaniline, nitrobenzene, diphenylguanidine, trimethylolpropane-N, N'-m-phenylene dimaleimide and other crosslinking aids, or divinylbenzene, Polyallyl methacrylate such as triallyl cyanurate, eletin glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate, etc., and polyfunctional vinyl monomer such as vinyl butyrate or vinyl stearate. Can be blended. 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 ethylene rubber component (B) and the propylene polymer (A), which are the main components of the object to be treated, and is organic. It is most preferable because it has a peroxide solubilizing effect and acts as a dispersion aid for peroxide, so that a composition having a uniform crosslinking effect by heat treatment and a well-balanced fluidity and physical properties can be obtained.

In the present invention, the compounding amount of such a crosslinking aid or polyfunctional vinyl monomer is 100% by weight based on 100% by weight of the total amount of the propylene polymer (A) and the ethylene rubber component (B). Generally, the range of 0.1 to 2% by weight, particularly 0.3 to 1% by weight is preferable, and by blending in this range, the fluidity is excellent, and the physical properties depend on the thermal history when processing and molding the composition. A composition is obtained that does not cause changes in

Other components In the thermoplastic elastomer composition according to the present invention, if necessary, a slip agent (for example, paraffin type process oil) other than the above, a filler, an antioxidant, a weathering stabilizer,
Additives such as colorants can be added within a range that does not impair the object of the present invention.

Examples of slip agents other than those mentioned above include 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.

Thermoplastic Elastomer Composition The thermoplastic elastomer composition according to the present invention comprises the above-mentioned propylene polymer (A), ethylene rubber component (B),
And, if necessary, higher fatty acid amide (C) and polyorganosiloxane (D) are contained. Examples of the embodiment of the thermoplastic elastomer composition according to the present invention include the following compositions. (1) A thermoplastic elastomer composition obtained by mixing a propylene polymer (A) and an ethylene rubber component (B). (2) A thermoplastic elastomer composition obtained by mixing the propylene polymer (A), the ethylene rubber component (B) and the higher fatty acid (C). (3) A thermoplastic elastomer composition obtained by mixing the propylene polymer (A), the ethylene rubber component (B) and the polyorganosiloxane (D). (4) A thermoplastic elastomer composition obtained by mixing a propylene polymer (A), an ethylene rubber component (B), a higher fatty acid (C) and a polyorganosiloxane (D). (5) A thermoplastic elastomer resin composition obtained by dynamically heat-treating a mixture of a propylene polymer (A) and an ethylene rubber component (B) in the presence of a crosslinking agent (E). (6) A thermoplastic elastomer obtained by dynamically heat-treating a mixture of a propylene polymer (A), an ethylene rubber component (B) and a higher fatty acid amide (C) in the presence of a crosslinking agent (E). Resin composition. (7) A mixture of a propylene polymer (A), an ethylene rubber component (B), and a polyorganosiloxane (D),
A thermoplastic elastomer resin composition obtained by dynamically heat-treating in the presence of a crosslinking agent (E). (8) A mixture of a propylene polymer (A), an ethylene rubber component (B), a higher fatty acid amide (C), and a polyorganosiloxane (D) is dynamically added in the presence of a crosslinking agent (E). A thermoplastic elastomer resin composition obtained by heat treatment.

The heat quantity of the thermoplastic elastomer composition according to the present invention at the time of melting measured by DSC is usually 25 J / g or less, preferably 22 J / g or less, more preferably 20 J / g or less. Melt flow rate (MFR; ASTM D 123) of the thermoplastic elastomer composition according to the present invention
When used as a corner member, it is usually 0.1 to 100 g / 10 minutes, preferably 0.5 to 70 g / 10 minutes, more preferably 10 to 50,
g / 10 minutes. The thermoplastic elastomer composition having a melt flow rate within the above range has excellent moldability. When used as a linear member, the melt flow rate (MFR; ASTM D 1238, 230 ° C, 10 kg load) is
Although not particularly limited, it is usually 0.01 to 700 g / 10
Min, preferably 0.05 to 500 g / 10 min, more preferably 0.1 to 300 g / 10 min.

Among the thermoplastic elastomer compositions according to the present invention, the thermoplastic elastomer compositions in which the ethylene rubber component (B) as in the above (1) to (4) are not crosslinked are the above (1) to (4). It can be prepared by mixing the respective components constituting the composition of (4) and then dynamically heat-treating in the absence of the crosslinking agent (E). Here, “dynamically heat-treating” means kneading in a molten state (hereinafter the same).

The dynamic heat treatment in the present invention is preferably carried out in a non-open type apparatus, and is preferably carried out in an atmosphere of an inert gas such as nitrogen or carbon dioxide. The kneading temperature is usually 150 to 280 ° C., preferably 170.
~ 240 ° C. The kneading time is usually 1 to 20 minutes, preferably 3 to 10 minutes. Further, the shear force applied is, 10～100,000Sec ^-1 as the shear rate is preferably 100~50,000sec ^-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, a thermoplastic elastomer composition in a state where the ethylene rubber component (B) is not crosslinked is obtained by the above-mentioned dynamic heat treatment.

Among the thermoplastic elastomer compositions according to the present invention, the thermoplastic elastomer composition in which the ethylene rubber component (B) such as the above (5) to (8) is crosslinked has the above (5). ) To (8), the components constituting the composition are mixed and then dynamically heat-treated in the presence of the crosslinking agent (E) to produce the composition. The dynamic heat treatment here is also preferably performed in a non-open type apparatus, and is also 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 . The kneading device is as described above, and 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 ethylene rubber component (B) is crosslinked. The preferred thermoplastic elastomer used in the present invention is one in which the ethylene rubber component (B) is partially crosslinked, and this "partially crosslinked" means that the gel content measured by the following method is 5 or less. The gel content is preferably in the range of 10 to 70%, and in the present invention, the gel content is preferably in the range of 10 to 70%.

[Measurement method of gel content] As a sample, about 100 mg of a pellet of the thermoplastic elastomer composition was weighed,
A sufficient amount for this pellet in a closed container 3
Immerse in 0 ml of cyclohexane at 23 ° C. for 48 hours. Next, this sample was taken out on a filter paper and kept at room temperature for 72 minutes.
Dry until constant weight over time. The gel content is represented by the following formula.

Gel content [%] = (dry weight after immersion in cyclohexane) / (weight before immersion in cyclohexane) × 10
When a molded product (corner molded product) is prepared from the thermoplastic elastomer composition according to the present invention, the Shore A hardness (JIS K 6301) of this molded product is 85 or less, preferably 80 or less, and When the thermoplastic elastomer composition is injection-molded on the surface of the thermoplastic elastomer molded product or the vulcanized rubber molded product at an injection temperature of 190 ° C. and melt-bonded, the adhesive peel strength of the melt-bonded portion is 2 It is desirable that the pressure is 0.5 MPa or more, preferably 3.0 MPa or more.

Further, these thermoplastic elastomer compositions according to the present invention exhibit excellent adhesiveness to the corner material, and are therefore suitably used for forming straight portions of weather strips for automobiles. As the thermoplastic elastomer composition according to the present invention, a molded body is prepared from the thermoplastic elastomer composition, and when melt-bonded with the thermoplastic elastomer, when the peeling test of the welded portion is performed, the peeling form is It is desirable to show matrix failure. In the peeling test, a molded product having a bonded portion such as a weather strip is subjected to a tensile test at a tensile speed of 200 mm / min by gripping two portions sandwiching the bonded portion. Normally, the corner material is an uncolored product, and the straight part (adhesive material) is a black colored product, and the cross section after the test is observed. Visually observe the cross section and check if there is any corner material remaining on the cross section of the adherend.
Alternatively, if the adhered material remains on the cross section of the corner material, the base material is destroyed, and if the adhered material or the corner material does not remain on both cross sections, the interface peels.

The thermoplastic elastomer composition according to the present invention is a thermoplastic elastomer molded product (preferably a polyolefin-based thermoplastic elastomer molded product) or a vulcanized rubber molded product (preferably a polyolefin-based molded product) used as an interior / exterior material for vehicles. It is preferably used for a corner portion welded to a (vulcanized rubber molded product), for example, a corner portion (corner material) of a weather strip for an automobile. Specifically, the extruded product of a polyolefin-based thermoplastic elastomer or a polyolefin-based vulcanized rubber is cut, and in the molding of a corner portion connecting the obtained cut extrudates from different directions, the heat according to the present invention described above is used. A weather strip can be obtained by injection-molding a thermoplastic elastomer composition at a temperature equal to or higher than the melting point and bringing it into contact with an extruded product of a thermoplastic elastomer or a vulcanized rubber to cause it to adhere.

The thermoplastic elastomer according to the present invention can also be used as a straight portion of the interior / exterior material of the vehicle. In that case, as a method for producing the thermoplastic elastomer molded article according to the present invention, an extruder is used to produce the molded article. The production temperature is usually 180 to 280 ° C, preferably 190 to 270 ° C, more preferably 200 to 25.
The temperature is 0 ° C, and the shape and size of the final product are determined according to the purpose of use. If necessary, a dice capable of stacking may be used to thinly stack a skin layer having excellent slipperiness on the surface of the base material layer. The thickness of the skin layer at this time is 0.1 μm to 1 mm, preferably 10 to 50.
It is desirable that the thickness is 0 μm, more preferably 50 to 100 μm.

Weather Strip for Automobiles The weather strip having the straight line portion and the corner portion, which is made of the thermoplastic elastomer composition 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. 1A, the weather strip connects the cut extruded products (linear members) 1 and 2 made of a thermoplastic elastomer and the cut extruded products 1 and 2 from different directions. And a corner portion (corner member) 3 formed at that time. The cut extrusion-molded products 1 and 2 are obtained by extruding a thermoplastic elastomer 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 "corner portion" referred to here is a portion formed when the cut extruded products made of the thermoplastic elastomer are connected from different directions, and the straight portion is the extruded product formed by the extruder. Say.

Such a weather strip 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, cutting extrusion molded products 1 and 2 made of a conventional thermoplastic elastomer are inserted into the mold 4. Then, although not shown, the thermoplastic elastomer composition according to the present invention, which is melted at a temperature equal to or higher than the melting point in a heating chamber (screw), is injected into a space formed between the cavity of the mold 4 and the core. , On the end faces of the cut and extruded products 1 and 2,
After welding the thermoplastic elastomer composition according to the present invention melted at a temperature equal to or higher than the melting point, the composition is cooled,
A weather strip having a corner portion 3 as shown in FIG. 1 (A) is obtained.

Although the weather strip has been described as an example here, the thermoplastic elastomer composition according to the present invention is not limited to the case where a fusion molded product is formed on a thermoplastic elastomer molded product, and the skin portion such as a door trim is formed. It can also be applied to the case where it is formed of a fusion-bonded skin layer.
Conventionally, a propylene homopolymer has been used as a propylene-based polymer in a thermoplastic elastomer from the viewpoint of excellent rubber elasticity, but a thermoplastic elastomer composition containing a propylene-based polymer having low crystallinity as in the present invention. By using as a weatherstrip material, a thermoplastic elastomer composition for a weatherstrip, which can realize an adhesive strength and a peeling form after adhesion, that is, a base material fracture, which has not been achieved hitherto, and which is excellent in rubber elasticity, fluidity and rubber elasticity, can be obtained. The present invention is characterized in that a product can be obtained.

[0066]

EFFECTS OF THE INVENTION According to the present invention, a corner having an excellent weldability with an extrusion molded article such as a weather strip made of a thermoplastic elastomer, a weather strip made of a vulcanized rubber, and having an appropriate softness (hardness). It is possible to provide a thermoplastic elastomer composition which is capable of forming a part and which has excellent moldability and exhibits weldability such that the base material is broken when peeled from the thermoplastic elastomer when used as an extrusion molded article. .

[0067]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. The melting point Tm and heat of fusion of the propylene-based polymer used in the examples and comparative examples, the melt flow rate (MFR) of the thermoplastic elastomer resin composition obtained in the examples and comparative examples, and the examples and comparative examples. The measurement or evaluation of the adhesive peel strength, hardness, tensile strength, compression set, and moldability of the molded article made of the obtained thermoplastic elastomer composition was carried out according to the following method. (1) Melting point Tm and heat of fusion After pellets of a propylene polymer and a thermoplastic elastomer composition are annealed at 230 ° C for 10 minutes, a differential scanning calorimeter (DSC) is used to increase the temperature to 10 ° C / 30 ° C.
After the temperature was decreased at a rate of minute, the temperature was maintained for 1 minute, the temperature was increased at a rate of 10 ° C./minute, and the heat of fusion was measured. For the propylene-based polymer, the temperature at which the amount of absorbed heat was the maximum was measured as the melting point Tm. (2) Melt Flow Rate (MFR) The melt flow rate is ASTM D 1238-65T.
The measurement was performed under the conditions of 230 ° C. and a load of 2.16 kg. (3) Adhesive peel strength When measuring the adhesive peel strength, MVSS (vertical 34.5c
A metal mold capable of molding a flat plate of m × width 10.0 cm × thickness 3 mm), a 200 Ton injection molding machine was used.

First, the material to be adhered [length 30 cm × width 10 cm
A flat plate (trade name: C750B (manufactured by Mitsui Chemicals, Inc., Shore A hardness 81)) having a thickness of 3 mm is prepared.Then, the thermoplastic elastomer compositions obtained in Examples and Comparative Examples are subjected to an MVSS mold. After molding, measure the flow length, cut the adherend with a cutter according to the flow length, attach it to the mold, and injection mold the thermoplastic elastomer composition using the mold with the adherent attached The bonded molded product is punched out into a strip shape with a width of 2 cm and the adhesive peel strength is measured at a pulling speed of 200 mm / min (4) Adhesive peel strength When measuring the adhesive peel strength , Flat plate (length 12 cm x width 1
A mold, capable of molding a flat plate of 4.7 cm × 2 mm in thickness), a 100 Ton injection molding machine was used.

First, the plastic elastomers obtained in Examples and Comparative Examples were used as materials to be adhered (straight members) by hot press molding at a press temperature of 190 ° C., a mold temperature of 20 ° C., a preheating time of 6 minutes, and a pressure melting time. 12 cm in height x 14.7 in width in 4 minutes
A flat plate having a size of cm × 2 mm is formed and prepared. Next, immediately before adhering to the corner material, the adhering material molded product is cut with a cutter so that the length is 4 cm, and the thermoplastic elastomer is cut against the cutting surface of the cutter at the injection molding stage in the injection molding process. Set so that the molten resin reaches the mold. Then, injection molding temperature 230 ° C, mold temperature 50
The corner material is melt-bonded to the adherend at ℃ to obtain a test piece for observing the peeling state.

The joint portion of the test piece obtained as described above was punched into a strip having a width of 2 cm, and the pulling speed was 200 mm.
The peeling test is performed at the speed of 1 / min, the adhesive strength is measured, and the peeled cross section is visually observed. If the corner material remains in the cross section of the adhered material or if the adhered material is present in the cross section of the corner material. If it remains, the base material is destroyed, and if there is no adherend material or corner material left on both cross sections, the interface peels. If the corner material remained on the cross section after the test, the base material was broken, and if it did not remain, the interface was peeled. (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 was produced by a press molding machine, a JIS No. 3 test piece was punched out, and a test was conducted under a condition of a tensile speed of 200 mm / min. (7) Compression set The compression set was measured under the following conditions according to JIS K6301. (Measurement conditions) A columnar molded product having a diameter of 29 mm and a thickness of 12.7 mm was manufactured by a vertical injection molding machine, and the thickness when compressed in the thickness direction by 25% with a spacer at a temperature condition of 70 ° C. It was measured and the compression set was calculated. (8) Moldability A vertical injection molding machine has a diameter of 29.0 mm and a thickness of 12.7 m.
When manufacturing a cylindrical molded product of m, the moldability was evaluated according to the following criteria. <Evaluation Criteria> ◎: Adhesion of the sprue to the movable part of the mold is not observed at all ○: Adhesion is observed in some samples ×: When all samples adhere

[0071]

Example 1 As a propylene-based polymer, propylene
Ethylene copolymer [MFR = 6.7 g / 10 min, melting point T
m = 140 ° C., heat quantity upon melting = 78 J / g; hereinafter PE-
Abbreviated as 1. ] 28 parts by weight and homopolypropylene [M
FR = 1.5 g / 10 minutes, melting point Tm = 160 ° C., heat quantity at melting = 106 J / g; hereinafter abbreviated as PP-11. ] 13 parts by weight of the blended product 41 parts by weight, and as an ethylene-based rubber component, an oil-extended ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber [ethylene content = 78 mol%,
Propylene content = 22 mol%, iodine value = 13, Mooney viscosity [ML1 + 4 (100 ° C.)] = 74, oil extension = 100 parts by weight of rubber, paraffin-based process oil (trade name, manufactured by Idemitsu Kosan Co., Ltd.) 40 parts by weight of PW-1380); hereinafter abbreviated as EPT-11. ] 59 parts by weight, and as an antioxidant, a phenolic antioxidant [trade name: IRGANOX1010, manufactured by Nippon Ciba-Geigy Co., Ltd.]
05 parts by weight, and as a weather resistance agent, a diazo weather resistance stabilizer [manufactured by Nippon Ciba Geigy Co., Ltd., trade name TINUVIN32
6] 0.1 part by weight, and as a cross-linking agent, an organic peroxide [Nippon Yushi-Seiyaku Co., Ltd., trade name Perhexa 25B] 0.32
Parts by weight and 0.24 of divinylbenzene as a crosslinking aid
After thoroughly mixing parts by weight with a Henschel mixer, extruder [Part No. TEM150, manufactured by Toshiba Machine Co., Ltd., L / D =
40, cylinder temperature: C1 to C2 120 ° C, C3 to
C4 140 ° C, C5-C6 180 ° C, C7-C8
200 ° C, C9 to C12 220 ° C, die temperature: 210
° C, screw rotation speed: 200 rpm, extrusion rate: 40 k
g / h), as a slip agent, a paraffinic process oil [made by Idemitsu Kosan Co., Ltd., trade name PW-380] 2
Granulation was performed while pouring 8 parts by weight into a cylinder to obtain pellets of the thermoplastic elastomer composition. This pellet-shaped thermoplastic elastomer composition was injection-molded to obtain a molded body.

The thermoplastic elastomer composition and the molded article thus obtained were measured for the above physical properties and evaluated for the moldability according to the methods described above. The results are shown in Table 1.

[0073]

Example 2 A thermoplastic elastomer composition was prepared in the same manner as in Example 1 except that the amounts of the cross-linking agent and the cross-linking aid were changed to 0.64 parts by weight and 0.48 parts by weight, respectively. The pellets of the product were prepared, and the molded body was further prepared. The obtained thermoplastic elastomer composition and molded body were subjected to the above-mentioned measurement of physical properties and evaluation of moldability according to the methods described above.

The results are shown in Table 1.

[0075]

Example 3 In Example 1, as a propylene-based polymer, 13 parts by weight of PP-1 and 28 parts by weight of a propylene / ethylene / 1-butene terpolymer [MFR: 7.1
g / 10 minutes, melting point Tm = 136 ° C., heat quantity upon melting = 70 J
/ G; hereinafter abbreviated as PEB-1. ] Blended with 41
Pellets of the thermoplastic elastomer composition were prepared in the same manner as in Example 1 except that the parts by weight were used, and the molded product thereof was prepared.

The thermoplastic elastomer composition and the molded product thus obtained were subjected to the above-mentioned measurement of physical properties and evaluation of moldability according to the methods described above. The results are shown in Table 1.

[0077]

Example 4 The amount of EPT-1 compounded in Example 1 was changed to 54 parts by weight, and 28 parts by weight of PE-1 as a propylene-based polymer and 5 parts by weight of propylene-ethylene copolymer were used. Rubber [Mitsui Chemicals, Inc., trade name S40
20; hereinafter abbreviated as PE-12. ], And 13 parts by weight of PP
Pellets of the thermoplastic elastomer composition were prepared in the same manner as in Example 1 except that 46 parts by weight of the blended product with -1 was used, and further a molded product thereof was prepared.

The thermoplastic elastomer composition and the molded body thus obtained were subjected to the above-mentioned measurement of physical properties and evaluation of moldability according to the above-mentioned methods. The results are shown in Table 1.

[0079]

Example 5 The amount of EPT-1 mixed in Example 1 was changed to 49 parts by weight to obtain a propylene-based polymer of 28 parts by weight.
Thermoplastic elastomer composition in the same manner as in Example 1 except that 51 parts by weight of a blend of 1 part by weight of PE-1, 10 parts by weight of PE-2, and 13 parts by weight of PP-11 were used. Pellets were prepared, and the molded body was further prepared.

The thermoplastic elastomer composition and the molded body thus obtained were subjected to the above-mentioned measurement of physical properties and evaluation of moldability according to the methods described above. The results are shown in Table 1.

[0081]

Example 6 In Example 5, as a slip agent, higher fatty acid amide [trade name Armoslip CP,
Lion Co., Ltd.] Pellets of the thermoplastic elastomer composition were prepared in the same manner as in Example 5 except that 0.3 part by weight was added, and further a molded body thereof was prepared.

The thermoplastic elastomer composition and the molded article thus obtained were measured for the above physical properties and evaluated for the moldability according to the methods described above. The results are shown in Table 1.

[0083]

Example 7 In Example 5, as a slip agent, a higher fatty acid amide [trade name Armoslip CP,
Lion Co., Ltd.] 0.3 parts by weight, polyorganosiloxane masterbatch BY27-001 [trade name;
Toray Dow Silicone Co., Ltd.] Pellet of the thermoplastic elastomer composition was prepared in the same manner as in Example 5 except that 1 part by weight was added, and a molded product thereof was prepared.

The thermoplastic elastomer composition and the molded body thus obtained were measured for the above physical properties and evaluated for the moldability according to the methods described above. The results are shown in Table 1.

[0085]

Example 8 In Example 5, instead of PE-2 which is one component of the propylene polymer, a propylene / ethylene copolymer [manufactured by Mitsui Chemicals, Inc., trade name S4030;
Hereinafter, it is abbreviated as PE 13. ] 10 parts by weight, 0.3 parts by weight of higher fatty acid amide [trade name Armoslip CP, manufactured by Lion Corporation] as a slip agent, BY27-0 which is a polyorganosiloxane masterbatch
Pellets of the thermoplastic elastomer composition were prepared in the same manner as in Example 5, except that 1 part by weight of 01 [trade name; manufactured by Toray Dow Silicone Co., Ltd.] was added, and further a molded body thereof was prepared.

The thermoplastic elastomer composition and the molded article thus obtained were measured for the above physical properties and evaluated for the moldability according to the methods described above. The results are shown in Table 1.

[0087]

Example 9 In Example 5, as the propylene polymer, 28 parts by weight of PE-11 and 10 parts by weight of PE-13 were used.
And 51 parts by weight of a blend of 13 parts by weight of PP-1 were used, and the blending amounts of the cross-linking agent and the cross-linking aid were changed to 0.64 parts by weight and 0.48 parts by weight, respectively, as a slip agent. , 0.3 part by weight of higher fatty acid amide [trade name Armoslip CP, manufactured by Lion Corporation], BY27-00 which is a polyorganosiloxane masterbatch.
Pellets of the thermoplastic elastomer composition were prepared in the same manner as in Example 5 except that 1 part by weight of 1 (trade name; manufactured by Toray Dow Silicone Co., Ltd.) was added, and a molded product thereof was prepared.

The thermoplastic elastomer composition and the molded body thus obtained were subjected to the above-mentioned measurement of physical properties and evaluation of moldability according to the above-mentioned methods. The results are shown in Table 1.

[0089]

[Example 10] In Example 1, 54 parts by weight of EPT-1, 13 parts by weight of PP-1, 23 parts by weight of PE-1,
Propylene butene-1 rubber [trade name: XR-110T,
Manufactured by Mitsui Chemicals, Inc., hereinafter abbreviated as PBR], 15 parts by weight,
As a slip agent, higher fatty acid amide [Product name
Pellets of the thermoplastic elastomer composition were prepared in the same manner as in Example 1 except that 0.3 part by weight of Armoslip CP, manufactured by Lion Co., Ltd. was used, and a molded product thereof was prepared.

The thermoplastic elastomer composition and the molded body thus obtained were subjected to the above-mentioned measurement of physical properties and evaluation of moldability according to the above-mentioned methods. The results are shown in Table 1.

[0091]

Comparative Example 1 A thermoplastic resin was prepared in the same manner as in Example 1 except that 41 parts by weight of PP-1 alone was used as the propylene-based polymer and no cross-linking agent and no cross-linking aid were used. Preparing a pellet of the elastomer composition,
Further, the molded body was prepared.

The thermoplastic elastomer composition and the molded article thus obtained were measured for the above physical properties and evaluated for the moldability according to the methods described above. The results are shown in Table 1.

[0093]

Comparative Example 2 In Example 1, the amount of EPT-1 was changed to 75 parts by weight, and PP-1 was used as a propylene resin.
Pellets of the thermoplastic elastomer composition were prepared in the same manner as in Example 1 except that 25 parts by weight of each of them was not used, and the crosslinking agent and the crosslinking auxiliary agent were not used.

The thermoplastic elastomer composition and the molded article thus obtained were measured for the above physical properties and evaluated for the moldability according to the above methods. The results are shown in Table 1.

[0095]

[Example 11] Since the thermoplastic elastomer composition pellets used in Example 1 are used as an adherend, a hot press molding machine presses at 190 ° C, cools at 20 ° C, preheats for 6 minutes, and melts under pressure. 12 cm in length in 4 minutes
A flat plate molded product having a width of 14.7 cm and a thickness of 2 mm was obtained.

A molding was injection-molded using the thermoplastic elastomer composition used in Example 1 as a corner material to obtain a molding. The obtained molded body was measured and evaluated by the method described in (4) Adhesive peel strength. as a result,
The adhesive strength was 4.6 MPa, and the peeling form was destruction of the base material.

[0097]

Example 12 The procedure of Example 11 was repeated, except that the thermoplastic elastomer composition used in Example 2 was used as the adherend. The obtained molded body is measured by the method described in (4) Adhesive peel strength
evaluated. As a result, the adhesive strength was 4.7 MPa,
The peeling morphology was base material fracture.

[0098]

Example 13 The procedure of Example 11 was repeated, except that the thermoplastic elastomer composition used in Example 3 was used as the adherend. The obtained molded body is measured by the method described in (4) Adhesive peel strength
evaluated. As a result, the adhesive strength was 4.9 MPa,
The peeling morphology was base material fracture.

[0099]

Example 14 The procedure of Example 11 was repeated, except that the thermoplastic elastomer composition used in Example 6 was used as the adherend. The obtained molded body is measured by the method described in (4) Adhesive peel strength
evaluated. As a result, the adhesive strength was 5.1 MPa,
The peeling morphology was base material fracture.

[0100]

Example 15 The procedure of Example 11 was repeated, except that the thermoplastic elastomer composition used in Example 10 was used as the adherend. The obtained molded body was measured and evaluated by the method described in (4) Adhesive peel strength. As a result, the adhesive strength was 5.4 MPa, and the peeling form was destruction of the base material.

[0101]

Comparative Example 3 The procedure of Example 11 was repeated, except that the thermoplastic elastomer composition used in Comparative Example 1 was used as the adherend. The obtained molded body was measured and evaluated by the method described in (4) Adhesive peel strength. As a result, the adhesive strength was 4.9 MPa and the peeling form was interfacial peeling.

[0102]

Comparative Example 4 Example 11 was repeated except that the thermoplastic elastomer composition used in Comparative Example 2 was used as the adherend. The obtained molded body was measured and evaluated by the method described in (4) Adhesive peel strength. As a result, the adhesive strength was 3.9 MPa and the peeling form was interfacial peeling.

[0103]

[Table 1]

[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 molding (straight member) 3 ・ ・ ・ Corner part (corner member) 4 ... Injection mold

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08J 5/00 CES C08L 23/16 C08K 5/20 83/04 C08L 23/16 B29K 19:00 83/04 23:00 // B29K 19:00 105: 20 23:00 B29L 31:58 105: 20 B60J 1/16 A B29L 31:58 5/00 501J (72) Inventor Akira Uchiyama 3 Chikusaigan, Ichihara, Chiba Prefecture Mitsui Chemicals Co., Ltd. In-house F-term (reference) 3D201 AA37 CA19 DA06 DA31 EA01 FA04 4F071 AA14 AA20 AA67 AC12 AF19 AF25 AF58 AH11 BB05 BC03 BC04 BC06 4F206 AA11E AA45 AH23 AH26 JA06 JB12 4J002 BB10X CP176W BB176X CP176W

Claims (17)

[Claims] 1. A copolymer of propylene and an α-olefin having 2 or 4 to 20 carbon atoms (A1) [having a melting point Tm measured by a differential scanning calorimeter (DSC) of 145 ° C. or lower, and The amount of heat upon melting is 90 J / g or less. ] Propylene-based polymer (A) 5 containing at least one
~ 95 parts by weight, and ethylene rubber component (B) 5 to 95 parts by weight [component (A)
And the total amount of component (B) is 100 parts by weight]. 2. The total D of the thermoplastic elastomer composition.
The thermoplastic elastomer composition according to claim 1, wherein the amount of heat at melting measured by SC is 25 J / g or less. 3. The copolymer (A1) is a crystalline propylene / ethylene copolymer (A1-1) and / or a crystalline propylene / ethylene / 1-butene copolymer (A1-2). The thermoplastic elastomer composition according to claim 1 or 2. 4. The total amount of the propylene-based polymer (A), which is a crystalline propylene / ethylene copolymer (A1-1) and a crystalline propylene / ethylene / 1-butene copolymer (A1-2). 100 parts by weight of propylene rubber (A2)
0.1 to 200 parts by weight are contained, The thermoplastic elastomer composition of Claim 1 or 2 characterized by the above-mentioned. 5. The ethylene rubber component (B) is an ethylene / propylene copolymer rubber (B1) and / or an ethylene / propylene / diene copolymer rubber (B2). Or the thermoplastic elastomer composition described in 2. 6. A higher fatty acid amide (C) in an amount of 0.1 to 2.0 parts by weight and / or a total amount of 100 parts by weight of the propylene polymer (A) and the ethylene rubber component (B). Polyorganosiloxane (D) 0.1-10
The thermoplastic elastomer composition according to any one of claims 1 to 5, wherein the thermoplastic elastomer composition contains a part by weight. 7. A blend of the propylene polymer (A) and the ethylene rubber component (B), which constitutes the thermoplastic elastomer composition according to any one of claims 1 to 6, is added with a crosslinking agent (E ) The thermoplastic elastomer composition obtained by dynamic heat treatment in the presence of 8. The heat according to claim 1, which is for forming a corner portion to be welded to a thermoplastic elastomer molded product or a vulcanized rubber molded product used as an interior / exterior material of a vehicle. Plastic elastomer composition. 9. The thermoplastic elastomer composition according to claim 8, wherein the corner portion is a corner portion of a weather strip for automobiles. 10. When a molded product is prepared from the thermoplastic elastomer composition according to any one of claims 1 to 7, the Shore A hardness (JIS K 6301) of the molded product is 85 or less, and When the thermoplastic elastomer composition is injection-molded and melt-bonded on the surface of the thermoplastic elastomer molded product or the vulcanized rubber molded product under the condition of an injection temperature of 190 ° C., the adhesive peel strength of the melt-bonded portion is 2 The thermoplastic elastomer composition according to claim 8 or 9, wherein the thermoplastic elastomer composition has a pressure of 0.5 MPa or more. 11. A thermoplastic elastomer composition (ii) according to any one of claims 1 to 7, wherein the thermoplastic elastomer composition (ii) is welded to the molded article (I). Molded body. 12. The thermoplastic elastomer composition (ii)
Is the thermoplastic elastomer composition according to any one of claims 1 to 7, and the molded article according to claim 11. 13. A peeled form shows a base material fracture when a peeling test is performed on a welded portion of the molded body (I) and the thermoplastic elastomer composition (ii). Or the molded article according to item 12. 14. The molded product according to claim 11, wherein the molded product is for an automobile interior / exterior material. 15. The molded product according to claim 14, wherein the automobile interior / exterior material is a portion including a corner of a weather strip. 16. The thermoplastic elastomer composition (i)
(I) is a linear member of a portion including a corner of a weather strip, and a portion formed by the thermoplastic elastomer composition (ii) is a corner member of a portion including a corner of the weather strip. The molded article according to claim 15. 17. The molded product according to claim 11, which is obtained by insert molding.