JP2014193969A - Thermoplastic elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition having an excellent adhesiveness to a vulcanized rubber molding, unaccompanied by a tackiness-related problem within a high-temperature region, having an excellent injection molding appearance, having a moderate hardness, and capable of abbreviating the molding cycle.SOLUTION: The provided thermoplastic elastomer composition is manufactured from a raw ingredient composition including at least (A) an ethylene-α-olefin-non-conjugated polyene copolymer, (B) an α-olefin thermoplastic resin having a melting point of 140°C or above and a melting caloric value of 75 J/g or above as it is measured in compliance with JIS K 7122, (C) an α-olefin resin having a melting caloric value of 15 J/g or below as it is measured in compliance with JIS K 7122, and (D) a crosslinking agent and has a sea-island structure obtained by dispersing an island phase including at least the ethylene-α-olefin-non-conjugated polyene copolymer (A) within a sea phase including at least the α-olefin thermoplastic resin (B).

Description

  The present invention relates to a thermoplastic elastomer composition. More specifically, the present invention relates to an olefinic thermoplastic elastomer that can be suitably used for industrial products such as automobile weather strips.

Automotive weather strips such as exterior moldings, wind seal gaskets, door seal gaskets, trunk seal gaskets, etc. use composite members in which olefin vulcanized rubber molded bodies and olefin thermoplastic elastomers are joined. Yes. The composite molded body is produced by injecting a thermoplastic elastomer into the remaining cavity in a state where a pre-manufactured olefin vulcanized rubber molded body is set in a split mold of an injection molding machine, and then performing the vulcanization. It is common to use a method in which an injection molded product of a thermoplastic elastomer is fused to a rubber molded body. However, the composite member manufactured by such a method using a conventionally known material does not have sufficient adhesive strength between the vulcanized rubber molded body and the thermoplastic elastomer.
For this reason, various thermoplastic elastomer compositions have been proposed that advocate high adhesiveness to vulcanized rubber moldings. For example, in Patent Document 1, an ethylene / α-olefin-based amorphous copolymer and a propylene / α-olefin-based low crystalline copolymer having 4 or more carbon atoms are mainly components, and these are partially crosslinked. An improved thermoplastic elastomer composition has been proposed. In Patent Document 2, an ethylene / α-olefin copolymer rubber having a predetermined intrinsic viscosity, a mineral oil softener, an α-olefin amorphous polymer having a predetermined crystallinity and melt viscosity, There has been proposed a thermoplastic elastomer composition which is contained in a predetermined ratio and in which at least one part thereof is crosslinked.

JP-A-60-173032 International Publication No. WO01 / 81462 Pamphlet US Pat. No. 3,287,440 US Pat. No. 3,709,840 JP 2007-2111184 A

However, the thermoplastic elastomer composition described in Patent Document 1 has not only sufficient adhesion to the vulcanized rubber molded article, but also in a high temperature range of the weather strip operating temperature range (70 to 80 ° C.). There is a problem that inadequate tackiness develops. This is considered to be due to bleeding out of the low crystalline copolymer.
On the other hand, the thermoplastic elastomer composition described in Patent Document 2 has not only sufficient adhesion to a vulcanized rubber molded product, but also excellent fluidity at the time of melting, and further the composition itself (and its molded product). ) Is an excellent material having moderate flexibility and rubber elasticity. However, this composition also leaves room for improvement in terms of developing tackiness in the high temperature region.
Furthermore, in order to reduce the manufacturing cost of weatherstrip products, a material that can shorten the molding cycle is required. The molding cycle time in the injection molding can be shortened by increasing the crystallinity of the polymer contained in the thermoplastic elastomer composition. However, according to this method, the product becomes inconveniently hard or has a poor appearance. May occur. Accordingly, there is a need for a material that can have a moderate hardness and a good injection-molded appearance while shortening the molding cycle.
The present invention has been made to solve the above-described problems in the prior art.
The purpose of the present invention is excellent in adhesion to a vulcanized rubber molded article, does not cause the problem of stickiness in a high temperature region, has excellent appearance of injection molding, has an appropriate hardness, and shortens the molding cycle. Is to provide a thermoplastic elastomer composition capable of

According to the present invention, the above objects and advantages of the present invention are:
at least,
Ethylene / α-olefin / non-conjugated polyene copolymer (A),
An α-olefin-based thermoplastic resin (B) having a melting point of 140 ° C. or higher and a heat of fusion measured in accordance with JIS K 7122 of 75 J / g or more;
Α-olefin resin (C) having a heat of fusion of 15 J / g or less measured in accordance with JIS K 7122, and crosslinking agent (D)
A raw material composition containing, and
In the sea phase containing at least the α-olefin-based thermoplastic resin (B),
It is achieved by a thermoplastic elastomer composition characterized in that it has a sea-island structure in which island phases containing at least the ethylene / α-olefin / non-conjugated polyolefin copolymer (A) are dispersed.

  The thermoplastic elastomer composition of the present invention is excellent in adhesiveness with a vulcanized rubber molded article and does not cause a problem of tackiness in a high temperature region. Since the elastomer composition of the present invention can be taken out from the split mold in a short time after injection molding, the molding cycle can be shortened, and a flow mark is generated in the obtained injection molded article. Excellent appearance. Furthermore, since the elastomer composition of the present invention and the molded product thereof have an appropriate hardness, they can be suitably used for industrial product applications such as automobile weather strips.

2 is a TEM image of the thermoplastic elastomer composition obtained in Example 1. FIG.

Hereinafter, the form for implementing the thermoplastic elastomer composition of this invention is demonstrated concretely. However, the present invention includes all embodiments provided with the invention-specific matters described in the claims, and is not limited to the following embodiments. In the present specification, the “repeating unit derived from the monomer X” may be simply referred to as “X unit”.
The thermoplastic elastomer composition of the present invention is produced from a raw material composition containing a copolymer (A), a thermoplastic resin (B), a thermoplastic resin (C), and a crosslinking agent (D). The raw material composition preferably further contains an extender oil (E) and may contain other components that are optionally used.

[1] Component of raw material composition [1-A] Copolymer (A)
The copolymer (A) is a component used mainly for the purpose of imparting flexibility to the thermoplastic elastomer composition of the present invention.
The copolymer (A) preferably has an intrinsic viscosity [η] measured at 135 ° C. in a decalin solvent of 3.5 to 9.0 dl / g, and 4.0 to 8.0 dl / g. More preferably, it is 4.3 to 7.5 dl / g. From the viewpoint of maintaining the rubber elasticity of the obtained thermoplastic elastomer composition, it is preferably 3.5 or more. On the other hand, from the viewpoint of maintaining workability during molding, it is preferably 9.0 or less. This intrinsic viscosity [η] is adjusted appropriately for the polymerization conditions (for example, the type of monomer used, the amount of catalyst, the amount of molecular weight regulator (for example, hydrogen), etc.) in producing the copolymer (A). Thus, it is possible to adjust to the preferable range.
The copolymer (A) is a copolymer having a repeating unit derived from at least ethylene, α-olefin, and non-conjugated polyene.
As said alpha olefin, a C3-C10 alpha olefin is preferable. It is preferable to use an α-olefin having 10 or less carbon atoms because the copolymerizability between the α-olefin and another monomer becomes good. Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene and 1-decene. . Of these, propylene, 1-butene, 1-hexene and 1-octene are preferred, and propylene and 1-butene are more preferred. The copolymer (A) may contain a repeating unit derived from only one α-olefin among these α-olefins, or a repeating unit derived from two or more α-olefins. It may be included.

Examples of the non-conjugated polyene include linear acyclic dienes, branched acyclic dienes, and alicyclic dienes. Specific examples thereof include linear acyclic dienes such as 1,4-hexadiene, 1,5-hexadiene, 1,6-hexadiene and the like;
Examples of the branched acyclic dienes include 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, 5,7-dimethylocta-1,6-diene, and 3,7-dimethyl. -1,7-octadiene, 7-methylocta-1,6-diene, dihydromyrcene and the like;
Examples of the alicyclic dienes include tetrahydroindene, methyltetrahydroindene, dicyclopentadiene, bicyclo [2.2.1] -hepta-2,5-diene, 5-methylene-2-norbornene, and 5-ethylidene-2- Examples thereof include norbornene, 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene, and the like. Of these, 1,4-hexadiene, dicyclopentadiene and 5-ethylidene-2-norbornene are preferred. The copolymer (A) may contain a repeating unit derived from only one kind of nonconjugated polyene among these nonconjugated polyenes, or may contain a repeating unit derived from two or more kinds of nonconjugated polyenes. It may be included.
The content of ethylene units in the copolymer (A) is preferably 50 to 90 mol% when the total of ethylene units and α-olefin units constituting the copolymer (A) is 100 mol%. From the viewpoint of preventing the mechanical strength of the thermoplastic elastomer composition obtained due to insufficient crosslinking efficiency when the copolymer (A) is crosslinked together with other components in the raw material composition from the viewpoint of copolymerization. The ethylene unit content in the polymer (A) is preferably 50 mol% or more;
On the other hand, from the viewpoint of maintaining the flexibility of the obtained thermoplastic elastomer composition, this value is preferably 90 mol% or less.

The content of the α-olefin unit in the copolymer (A) is 5 to 50 mol% when the total of the ethylene units and α-olefin units constituting the copolymer (A) is 100 mol%. It is preferably 10 to 45 mol%, more preferably 15 to 40 mol%. From the viewpoint of ensuring rubber elasticity required for the thermoplastic elastomer composition to be obtained, the content of α-olefin units in the copolymer (A) is preferably 5 mol% or more, while the thermoplasticity obtained is From the viewpoint of maintaining the durability of the elastomer composition, this value is preferably 50 mol% or less.
The content of the non-conjugated polyene unit in the copolymer (A) is preferably 3 to 10 mol% when the total of all repeating units constituting the copolymer (A) is 100 mol%. More preferably, it is -8 mol%.
The copolymer (A) polymerizes ethylene, α-olefin and non-conjugated polyene in the presence of, for example, a Ziegler-Natta catalyst, a catalyst comprising a soluble vanadium compound and an organoaluminum compound, preferably in an appropriate solvent. Can be obtained. At this time, polymerization may be carried out while supplying hydrogen as a molecular weight regulator, if necessary. The polymerization can be carried out by either a gas phase method (fluidized bed or stirred bed) and a liquid phase method (slurry method or solution method).

As said catalyst, it is preferable to use the catalyst which consists of a soluble vanadium compound and an organoaluminum compound.
As the soluble vanadium compound, a reaction product of at least one selected from the group consisting of VOCl ₃ and VCl ₄ and an alcohol is preferably used. Examples of the alcohol in this case include methanol, ethanol, n-propanol, i-propanol, n-butanol, sec-butanol, t-butanol, n-hexanol, n-octanol, 2-ethylhexanol, n-decanol, n -Dodecanol etc. can be mentioned. Among these, it is preferable to use C3-C8 alcohol.
Examples of the organoaluminum compound include triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum dichloride, butylaluminum dichloride; Examples thereof include methylaluminoxane, which is a reaction product of trimethylaluminum and water. Among these, it is preferable to use ethylaluminum sesquichloride, butylaluminum sesquichloride; a mixture of ethylaluminum sesquichloride and triisobutylaluminum; or a mixture of triisobutylaluminum and butylaluminum sesquichloride.
As the solvent, it is preferable to use a hydrocarbon solvent, and it is particularly preferable to use n-pentane, n-hexane, n-heptane, n-octane, i-octane, cyclohexane and the like. These solvents can be used alone or in admixture of two or more.

The copolymer (A) may be a substituted copolymer or graft copolymer having the ethylene / α-olefin / non-conjugated polyene copolymer obtained as described above as a basic skeleton. Examples of the substituted copolymer include a halogenated copolymer in which a part of hydrogen atoms of the copolymer is substituted with a halogen atom such as a chlorine atom or a bromine atom. Examples of the graft copolymer include a graft copolymer obtained by graft-polymerizing an unsaturated monomer to the polymer. Examples of the unsaturated monomer include vinyl chloride, vinyl acetate, (meth) acrylic acid, maleic acid, methyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, maleic anhydride, maleimide, dimethyl maleate, Conventionally known unsaturated monomers such as butadiene, isoprene and chloroprene can be used.
The copolymer (A) may be a copolymer consisting of only one type of copolymer described above, or a copolymer consisting of a mixture of two or more types of copolymers. It may be a coalescence.
As an aspect of a copolymer (A), aspects, such as a bale, a crumb, a pellet, powder (a bale ground product is included), etc. are mentioned, for example, Any of these may be used.
The raw material composition for producing the thermoplastic elastomer composition of the present invention has a copolymer weight when the total of the copolymer (A), the thermoplastic resin (B) and the thermoplastic resin (C) is 100% by mass. The content (A) is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and particularly preferably 30 to 85% by mass. From the viewpoint of ensuring the flexibility of the resulting thermoplastic elastomer composition, the content of the copolymer (A) is preferably 10% by mass or more. On the other hand, from the viewpoint of ensuring the adhesiveness and thermoplasticity of the obtained molded body (composite member), the content of the copolymer (A) is preferably 95% by mass or less.
Advantages when the copolymer (A) is used as an oil-extended product will be described later.

[1-B] Thermoplastic resin (B)
The thermoplastic resin (B) is a component used mainly for the purpose of imparting mechanical strength and heat resistance to the thermoplastic elastomer composition of the present invention, has a melting point of 140 ° C. or higher, and conforms to JIS K 7122. It is an α-olefin thermoplastic resin having a heat of fusion measured in accordance with 75 J / g or more.
The thermoplastic resin (B) has a melting point of 140 ° C. or higher. When the melting point is 140 ° C. or higher, the heat resistance of the obtained thermoplastic elastomer composition is improved, and the molding cycle can be shortened because it quickly solidifies in the mold during injection molding. The melting point of the thermoplastic resin (B) is more preferably 145 ° C. or more, and particularly preferably 145 to 175 ° C. In this specification, the “melting point” means the maximum peak temperature (Tm) measured by the differential scanning calorimetry.
The thermoplastic resin (B) has crystallinity. Specifically, the heat of fusion measured in accordance with JIS K 7122 for the thermoplastic resin (B) is 75 J / g or more. The amount of heat of fusion is preferably 80 J / g or more, and more preferably 95 J / g or more. Further, the thermoplastic resin (B) has a crystallinity measured by an X-ray diffraction method of preferably 50% or more, more preferably 53% or more, and particularly preferably 55% or more. The crystallinity as described above is required from the viewpoint of obtaining the mechanical strength and heat resistance of the resulting thermoplastic elastomer composition.
The density of the thermoplastic resin (B) is preferably 0.89 to 0.94 g / cm ³ , and preferably in the range of 0.90 to 0.94 g / cm ³ . The density has a strong correlation with the crystallinity. From the viewpoint of ensuring the mechanical strength and heat resistance of the obtained thermoplastic elastomer composition, the density of the thermoplastic resin (B) is preferably 0.89 g / cm ³ or more. On the other hand, from the viewpoint of ensuring rubber elasticity of the obtained thermoplastic elastomer composition, the density of the thermoplastic resin (B) is preferably 0.94 g / cm ³ or less. Incidentally, the density of the α-type crystal (monoclinic crystal) of polypropylene is 0.936 g / cm ³ , the density of the smectic crystal (pseudo hexagonal crystal) is 0.886 g / cm ³ , and the density of the amorphous (atactic) component is 0. 850 g / cm ³ . On the other hand, the isotactic crystal of poly-1-butene has a density of 0.91 g / cm ³ and the amorphous (atactic) component has a density of 0.87 g / cm ³ .

Furthermore, the thermoplastic resin (B) preferably has a melt flow rate (MFR) of 0.1 to 100 g / 10 min, more preferably 0.5 to 80 g / 10 min, and particularly 1 to 50 g. / 10 minutes is preferable. From the viewpoint of imparting sufficient kneadability or mixing processability and extrusion processability to the resulting thermoplastic elastomer composition, the MFR of the thermoplastic resin (B) is preferably 0.1 g / 10 min or more. . On the other hand, from the viewpoint of ensuring the mechanical strength of the resulting thermoplastic elastomer composition, the density of the thermoplastic resin (B) is preferably 100 g / 10 min or less. The “melt flow rate (MFR)” here means a melt flow rate measured under conditions of a temperature of 230 ° C. and a load of 21.2 N.
The thermoplastic resin (B) is preferably a resin composed of a polymer having an α-olefin unit as a main component. Specifically, when the total polymer is 100 mol%, the resin is preferably a resin composed of a polymer containing 80 mol% or more of α-olefin units, and is a resin composed of a polymer containing 90 mol% or more. Is more preferable.
Here, the “α-olefin” is a concept including ethylene. As the α-olefin for deriving the α-olefin unit in the thermoplastic resin (B), ethylene and an α-olefin having 3 to 12 carbon atoms are preferable, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, Examples thereof include 3-methyl-1-pentene, 4-methyl-1-pentene, 3-ethyl-1-pentene, 1-octene, 1-decene, 1-undecene and the like. Among these, as at least a part of the α-olefin, use of one or more selected from the group consisting of propylene and 1-butene of an organic peroxide decay type maintains the workability at the time of molding. To preferred.
The thermoplastic resin (B) may be a homopolymer of one α-olefin among the α-olefins described above, or may be a copolymer of two or more α-olefins. The α-olefin copolymer may be a block copolymer or a random copolymer.

Accordingly, examples of the thermoplastic resin (B) include propylene homopolymer, propylene / ethylene copolymer, propylene / 1-butene copolymer, propylene / 1-pentene copolymer, propylene / 3-methyl-1- Butene copolymer, propylene / 1-hexene copolymer, propylene / 3-methyl-1-pentene copolymer, propylene / 4-methyl-1-pentene copolymer, propylene / 3-ethyl-1-pentene copolymer Examples thereof include a polymer, a propylene / 1-octene copolymer, a propylene / 1-decene copolymer, and a propylene / 1-undecene copolymer. Of these, propylene homopolymer and propylene / ethylene copolymer are preferred.
When the thermoplastic resin (B) is an ethylene / α-olefin copolymer, the content of the ethylene unit is preferably less than 40 mol% when the entire copolymer is 100 mol%, More preferably, it is less than%. From the viewpoint of maintaining the crystallinity of the thermoplastic resin (B) within an appropriate range and obtaining an appropriate melting point, the ethylene unit content is preferably less than 40 mol%.
The thermoplastic resin (B) may be a copolymer of the α-olefin and a monomer other than the α-olefin. Examples of monomers other than α-olefin include acrylic acid, methacrylic acid, and vinyl acetate. When the thermoplastic resin (B) is a copolymer of α-olefin and a monomer other than α-olefin, if the total content of α-olefin units (including ethylene units) is low, the thermoplastic resin The crystallinity of (B) may be insufficient and the melting point may be lowered. This tendency is particularly remarkable in the case of a random copolymer. Specifically, the total content of α-olefin units (including ethylene units) when the total of all the repeating units of the copolymer constituting the thermoplastic resin (B) is 100 mol%,
In the case of a block copolymer, it is preferably 60 mol% or more, more preferably 80 mol% or more;
In the case of a random copolymer, it is preferably 85 mol% or more, more preferably 90 mol% or more.

When the thermoplastic resin (B) is a random copolymer, the same method as the copolymer (A) is used;
When this is a block copolymer, it can be obtained, for example, by anionic polymerization of α-olefin or the like in the presence of a Ziegler-Natta catalyst.
As the thermoplastic resin (B) in the present invention, only one of the above polymers may be used alone, or two or more polymers may be mixed and used.
The raw material composition for producing the thermoplastic elastomer composition of the present invention is thermoplastic when the total of the copolymer (A), the thermoplastic resin (B) and the thermoplastic resin (C) is 100% by mass. The resin (B) is preferably contained in an amount of 3 to 65% by mass, more preferably 5 to 55% by mass, and particularly preferably 10 to 45% by mass. From the viewpoint of ensuring the mechanical strength of the resulting thermoplastic elastomer composition, the thermoplastic resin (B) is preferably 3% by mass or more;
From the viewpoint of ensuring sufficient rubber elasticity of the obtained thermoplastic elastomer composition, it is preferable that the thermoplastic resin (B) is 65% by mass or less.

[1-C] Thermoplastic resin (C)
The thermoplastic resin (C) lowers the melt viscosity of the resulting thermoplastic elastomer composition, imparts fluidity to the composition, and prevents the composition from solidifying during the flow process in the mold. It is a component added for the main purpose.
The thermoplastic resin (C) in the present invention is an α-olefin resin having a heat of fusion of 15 J / g or less measured according to JIS K7122. The heat of fusion is preferably 10 J / g or less.
The thermoplastic resin (C) has a crystallinity measured by an X-ray diffraction method of 0% or more and 50% from the viewpoints of preventing solidification in the above flow process and securing adhesion to vulcanized rubber. Less than 30%, more preferably 30% or less, and particularly preferably 20% or less.
The thermoplastic resin (C) preferably has a density in the range of 0.85 to 0.89 g / cm ³ , and preferably in the range of 0.85 to 0.88 g / cm ³ . As described above, the density of the polymer has a strong correlation with the crystallinity. From the viewpoint of ensuring the mechanical strength of the obtained thermoplastic elastomer composition, the density of the thermoplastic resin (C) is preferably 0.85 g / cm ³ or more. On the other hand, the density of the thermoplastic resin (C) is preferably 0.89 g / cm ³ or less from the viewpoint of securing the adhesive strength of the resulting thermoplastic elastomer composition to the vulcanized rubber.
The number average molecular weight (Mn) of the thermoplastic resin (C) is preferably in the range of 1,000 to 20,000, and more preferably in the range of 1,500 to 15,000. From the viewpoint of ensuring the heat resistance of the resulting thermoplastic elastomer composition, the Mn of the thermoplastic resin (C) is preferably 1,000 or more. On the other hand, the Mn of the thermoplastic resin (C) is preferably 20,000 or less from the viewpoint of ensuring the fluidity of the resulting thermoplastic elastomer composition and the adhesion to the vulcanized rubber. Here, the “number average molecular weight (Mn)” is a value in terms of polystyrene measured using gel permeation chromatography.
The thermoplastic resin (C) preferably has a melt viscosity of 50,000 MPa · s or less, more preferably in the range of 100 to 30,000 MPa · s, particularly 200 to 20,000 MPa · s. It is preferable to be within the range. With respect to the thermoplastic elastomer composition obtained, the melt viscosity of the thermoplastic resin (C) is preferably 50,000 MPa · s or less from the viewpoint of ensuring adhesion to the vulcanized rubber. The “melt viscosity” referred to here is a melt viscosity at 190 ° C. measured in accordance with the method described in ASTM-D3236.

The α-olefin resin as the thermoplastic resin (C) in the present invention is an α-olefin homopolymer or a copolymer of two or more α-olefins, or an α-olefin and an α-olefin. It can be a copolymer of unsaturated monomers other than olefins.
Examples of the α-olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and the like;
Examples of unsaturated monomers other than α-olefins include acrylic acid, methacrylic acid, and vinyl acetate.
When the thermoplastic resin (C) is a copolymer of an α-olefin and an unsaturated monomer other than the α-olefin, the content of the α-olefin unit in the copolymer is the copolymer. When the total amount is 100% by mass, it is preferably 50% by mass or more, and more preferably 60% by mass or more.
By using the polymer as described above, the solidification preventing effect in the flow process is effectively expressed and a molded article having a good appearance is obtained, and the effect of improving the adhesion to vulcanized rubber is exhibited. The

The thermoplastic resin (C) is preferably an α-olefin homopolymer or a copolymer of two or more α-olefins. Specifically, for example, atactic polypropylene, atactic poly 1-butene. Homopolymers such as
Consists of more than 50 mol% of propylene units and other α-olefin (for example, ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, etc.) units. Copolymer;
It consists of more than 50 mol% of 1-butene units and other α-olefin (eg, ethylene, propylene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, etc.) units. A copolymer etc. are mentioned. Of these, atactic polypropylene;
Preference is given to terpolymers comprising more than 50 mol% of propylene units, 1-butene units and ethylene units; or terpolymers comprising more than 50 mol% of 1-butene units, propylene units and ethylene units. . Particularly preferred as the thermoplastic resin (C) is a terpolymer comprising 50 to 75 mol% of 1-butene units, 15 to 30 mol% of propylene units and 10 to 20 mol% of ethylene units.
When the thermoplastic resin (C) is a copolymer, the copolymer may be a random copolymer or a block copolymer. However, when the block copolymer has a propylene homopolymer block, the propylene units must be bonded in an atactic structure.

When the thermoplastic resin (C) is a random copolymer, the same method as the copolymer (A) is used;
When this is a block copolymer, it can be obtained, for example, by anionic polymerization of α-olefin or the like in the presence of a Ziegler-Natta catalyst.
As the thermoplastic resin (C) in the present invention, only one of the above polymers may be used alone, or two or more polymers may be mixed and used.
The raw material composition for producing the thermoplastic elastomer composition of the present invention is obtained when the total of the copolymer (A), the thermoplastic resin (B) and the thermoplastic resin (C) is 100% by mass. The content of the plastic resin (C) is preferably 0.1 to 10% by mass, and more preferably 1 to 10% by mass. From the viewpoint of ensuring adhesion of the resulting thermoplastic elastomer composition to the vulcanized rubber, the content of the thermoplastic resin (C) is preferably 0.1% by mass or more. On the other hand, the content of the thermoplastic resin (C) is ensured from the viewpoint of ensuring the mechanical strength of the obtained thermoplastic elastomer composition and ensuring that no stickiness is produced in a high temperature region of about 70 to 80 ° C. Is preferably 10% by mass or less.

[1-D] Crosslinking agent (D)
The crosslinking agent (D) crosslinks at least a part of the copolymer (A), the thermoplastic resin (B), and the thermoplastic resin (C) between the same or different components by heat treatment. It has a function.
Examples of such crosslinking agents (D) include phenolic crosslinking agents, organic peroxides, sulfur, sulfur compounds, p-quinones, p-quinone dioxime derivatives, bismaleimide compounds, epoxy compounds, silane compounds, amino acids. Resins, polyol cross-linking agents, polyamines, triazine compounds, metal soaps and the like can be mentioned. Of these, it is preferable to use a phenol-based crosslinking agent or an organic peroxide. When using a phenol type crosslinking agent as a crosslinking agent (D), it is preferable to use a crosslinking accelerator together. When using an organic peroxide as the crosslinking agent (D), it is preferable to use a crosslinking aid in combination.
Examples of the phenol-based crosslinking agent include o-substituted phenol / aldehyde condensates, m-substituted phenol / aldehyde condensates, brominated alkylphenol / aldehyde condensates, compounds represented by the following general formula (1), and the like. it can. Of these, compounds represented by the following general formula (1) are preferred.

(In the formula (1), a plurality of Rs are each independently a saturated hydrocarbon group having 1 to 15 carbon atoms, m is an integer of 0 to 10, and X and Y are each independently a hydroxyl group. Or a halogen atom.)
The compound represented by the general formula (1) is used for rubber as described in, for example, Patent Document 3 (US Pat. No. 3,287,440) and Patent Document 4 (US Pat. No. 3,709,840). It is a compound generally used as a crosslinking agent. This compound can be produced by polycondensation of a substituted phenol and an aldehyde in the presence of an alkali catalyst.

When using a phenol-based crosslinking agent as the crosslinking agent (D), the raw material composition has a total of 100 parts by mass of the copolymer (A), the thermoplastic resin (B), and the thermoplastic resin (C). It is preferable to contain 0.2-10 mass parts of this phenol type crosslinking agent, and it is more preferable to contain 0.5-5 mass parts. From the viewpoint of providing a sufficient degree of crosslinking and ensuring the rubber elasticity and mechanical strength of the resulting thermoplastic elastomer composition, the content of the phenolic crosslinking agent is preferably 0.2 parts by mass or more. On the other hand, from the viewpoint of suppressing the tendency that the degree of crosslinking becomes excessively high and as a result, the molding processability deteriorates or the mechanical properties of the resulting molded article are impaired, the content of the phenolic crosslinking agent is 10 masses. It is preferable to keep it below the part.
Although the phenolic crosslinking agent may be used alone, it is preferable to use a crosslinking accelerator in combination in order to adjust the crosslinking rate. Examples of the crosslinking accelerator include metal halides such as stannous chloride and ferric chloride; organic halides such as chlorinated polypropylene, butyl bromide rubber, and chloroprene rubber. In addition to the crosslinking accelerator, it is more preferable to further use a metal oxide such as zinc oxide or a dispersant such as stearic acid.
The usage rate of the crosslinking accelerator should be 10 parts by mass or less with respect to 100 parts by mass in total of the copolymer (A), the thermoplastic resin (B), the thermoplastic resin (C), and the extender oil (E). Is preferable and it is more preferable to set it as 0.2-5 mass parts.
The usage rate of the dispersant may be 10 parts by mass or less with respect to 100 parts by mass in total of the copolymer (A), the thermoplastic resin (B), the thermoplastic resin (C), and the extender oil (E). Preferably, it is more preferable to set it as 0.2-5 mass parts.

  Examples of the organic peroxide include 1,3-bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, 2,5- Dimethyl-2,5-bis (t-butylperoxy) hexene-3, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, 2,2'-bis (t-butylperoxy) ) -P-isopropylbenzene, dicumyl peroxide, di-t-butyl peroxide, t-butyl peroxide, p-menthane peroxide, 1,1-bis (t-butylperoxy) -3,3,5 -Trimethylcyclohexane, dilauroyl peroxide, diacetyl peroxide, t-butyl peroxybenzoate, 2,4-dichlorobenzoyl peroxide, p-chloro Nzoyl peroxide, benzoyl peroxide, di (t-butylperoxy) perbenzoate, n-butyl-4,4-bis (t-butylperoxy) valerate, t-butylperoxyisopropyl carbonate, etc. it can. It is preferable to use an organic peroxide having a relatively high decomposition temperature from the viewpoint that the decomposition reaction proceeds gently, and therefore the crosslinking reaction proceeds after the polymer components are uniformly mixed. For example, an organic peroxide having a 1 minute half-life temperature of 150 ° C. or higher can be suitably used. Specific examples of such organic peroxides include, for example, 1,3-bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3. 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and the like. These organic peroxides may be used alone or in combination of two or more.

  When an organic peroxide is used as the crosslinking agent (D), the raw material composition has a total of 100 parts by mass of the copolymer (A), the thermoplastic resin (B), and the thermoplastic resin (C). It is preferable to contain 0.05-10 mass parts of this organic peroxide, and it is more preferable to contain 0.1-5 mass parts. The content of the crosslinking agent (D) is 0.05 mass from the viewpoint of maintaining the degree of crosslinking and ensuring the rubber elasticity and mechanical strength of the resulting thermoplastic elastomer composition. Part or more. On the other hand, the content of the crosslinking agent (D) is 10 parts by mass or less from the viewpoint of maintaining the degree of crosslinking within an appropriate range, ensuring good molding processability and ensuring the mechanical properties of the molded article. Is preferred.

The organic peroxide may be used alone, but it is preferable to use a crosslinking aid in combination so that the crosslinking reaction proceeds gently to form uniform crosslinking. Examples of crosslinking aids include sulfur;
Sulfur compounds such as powdered sulfur, colloidal sulfur, precipitated sulfur, insoluble sulfur, surface treated sulfur, dipentamethylene thiuram tetrasulfide;
oxime compounds such as p-quinone oxime and p, p′-dibenzoylquinone oxime;
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Diallyl phthalate, tetraallyloxyethane, triallyl cyanurate, N, N′-m-phenylene bismaleimide, N, N′-toluylene bismaleimide, maleic anhydride, divinylbenzene, zinc di (meth) acrylate, etc. A polyfunctional monomer etc. can be mentioned. Among these, it is preferable to use p, p′-dibenzoylquinone oxime, N, N′-m-phenylene bismaleimide or divinylbenzene. N, N′-m-phenylenebismaleimide is a compound that functions as a crosslinking aid and also functions as a crosslinking agent.
One of these crosslinking aids may be used alone, or two or more thereof may be used in combination.
When the crosslinking aid is used, when the total of the copolymer (A), the thermoplastic resin (B) and the thermoplastic resin (C) is 100 parts by mass, the usage rate of the crosslinking aid is 10 parts by mass. It is preferable to set it as follows, and it is more preferable to set it as 0.2-5 mass parts. From the viewpoints of maintaining an appropriate degree of crosslinking, ensuring good molding processability, and ensuring the mechanical properties of the molded article, the usage rate of the crosslinking aid is preferably 10 parts by mass or less.

[1-E] Extension oil (E)
The raw material composition for producing the thermoplastic elastomer composition of the present invention may optionally contain an extending oil (E). This extender oil (E) is used mainly for the purpose of imparting fluidity to the resulting thermoplastic elastomer composition.
Examples of the extending oil (E) include mineral oil-based hydrocarbons and low molecular weight hydrocarbons.
The mineral oil-based hydrocarbon preferably has a weight average molecular weight Mw of 300 to 2,000, more preferably 500 to 1,500. From the viewpoint of securing the moldability of the resulting thermoplastic elastomer composition, it is preferable that Mw is 300 or more. On the other hand, from the viewpoint of preventing the mineral oil-based hydrocarbon from bleeding out from the thermoplastic elastomer composition, Mw is preferably 2,000 or less.
The mineral oil-based hydrocarbon preferably has a kinematic viscosity (40 ° C.) of 20 to 800 cSt, and more preferably 50 to 600 cSt. From the viewpoint of preventing bleeding out from the thermoplastic elastomer composition, it is preferable to use a mineral oil-based hydrocarbon having a kinematic viscosity (40 ° C.) of 20 cSt or more. On the other hand, the kinematic viscosity (40 ° C.) of the mineral oil-based hydrocarbon is preferably 800 cSt or less from the viewpoint of easy handling and ensuring the molding processability of the resulting thermoplastic elastomer composition.

The mineral oil-based hydrocarbons are often classified as follows.
Paraffinic mineral oil: A mixture of aromatic rings, naphthene rings and paraffin chains, where the carbon number of the paraffin chains occupies 50% or more of the total number of carbons Naphthenic mineral oil: A mixture of aromatic rings, naphthene rings and paraffin chains The naphthene ring occupies 30 to 45% of the total carbon number. Aromatic mineral oil: A mixture of aromatic ring, naphthene ring and paraffin chain, and the aromatic ring carbon number is the total carbon number. Of the above, the extending oil (E) in the present invention is preferably a paraffinic mineral oil of the above, and particularly a hydrogenated paraffinic mineral oil (hydrogenated paraffinic mineral oil). It is more preferable to use
Examples of such commercial products of mineral oil softeners include Diana Process Oil PW90, PW100, PW380 (above, manufactured by Idemitsu Kosan Co., Ltd.) and the like under the trade name.
Examples of the low molecular weight hydrocarbon include low molecular weight polybutene and low molecular weight polybutadiene.

The extending oil (E) in the present invention is preferably a mineral oil-based hydrocarbon.
The content of the extender oil (E) in the raw material composition for producing the thermoplastic elastomer composition of the present invention may be 300 parts by mass or less when the copolymer (A) is 100 parts by mass. Preferably, the amount is 20 to 250 parts by mass, and more preferably 30 to 200 parts by mass. From the viewpoint of preventing the extending oil (E) from bleeding out from the thermoplastic elastomer composition, the content is preferably 300 parts by mass or less.
The extended oil (E) uses at least one of the copolymer (A), the thermoplastic resin (B), and the thermoplastic resin (C) as an oil-extended product, and is a raw material contained in the oil-extended product. May be added to the composition; the copolymer (A), the thermoplastic resin (B), and the thermoplastic resin (C) may be added to the raw material composition in a separated form; or Both may be sufficient. Most preferably, the copolymer (A) is used as an oil-extended product, and a part of the extender oil (E) is added in a form contained in the oil-extended product; The coalescence (A), the thermoplastic resin (B) and the thermoplastic resin (C) are post-added to the raw material composition in a separated form. In this case, the extension oil (E) contained in the oil-extended product and the extension oil (E) added later may be the same type or different types.
When the copolymer (A) is used as an oil-extended product, the extension oil (E) may be added to the polymerization reaction system during the polymerization of the copolymer (A), or the polymerization of the copolymer (A). It may be mixed later.
When the copolymer (A) is used as an oil-extended product, the ratio of the extending oil (E) contained in the oil-extended product is preferably 30 to 60% by mass, more preferably 40 to 55% by mass. . From the viewpoint of preventing the processability of the resulting thermoplastic elastomer composition from deteriorating, the content of the extender oil (E) is preferably 30% by mass or more. On the other hand, from the viewpoint of preventing bleeding out from the thermoplastic elastomer composition, the content of the extending oil (E) is preferably 60% by mass or less.

[1-F] Other components The raw material composition for producing the elastomer composition of the present invention may further contain other components in addition to the above components.
Examples of the other components include polymer compounds, oligomers, antibacterial / antifungal agents, plasticizers, crystal nucleating agents, flame retardants, tackifiers, foaming aids, antioxidants, antistatic agents, blocking agents, Sealability improvers, lubricants, stabilizers (eg anti-aging agents, heat stabilizers, weathering agents, metal deactivators, UV absorbers, light stabilizers, copper damage inhibitors, etc.), colorants / pigments (eg titanium oxide) Carbon black, etc.), metal powder (eg ferrite), inorganic fiber (eg glass fiber, metal fiber etc.), organic fiber (eg carbon fiber, aramid fiber etc.), composite fiber, inorganic whisker (eg potassium titanate whisker etc.) ), Fillers (eg glass beads, glass balloons, glass flakes, asbestos, mica, calcium carbonate, talc, wet silica, dry silica, alumina, alumina Mosquito, calcium silicate, hydrotalcite, kaolin, diatomaceous earth, graphite, pumice, evo powder, cotton flock, cork powder, barium sulfate, fluororesin, polymer beads, polyolefin wax, cellulose powder, rubber powder, wood powder, etc. And the like.
The thermoplastic elastomer composition of the present invention may further contain a polymer compound as long as the effects of the present invention are not impaired.
Examples of such a polymer compound include ionomer, aminoacrylamide polymer, polyisobutylene, polyethylene oxide, polystyrene, ABS resin, ACS resin, AS resin, AES resin, ASA resin, MBS resin, acrylic resin, methacrylic resin, and chloride. Vinyl resin, vinylidene chloride resin, polyamide resin, polycarbonate, acrylic resin, methacrylic resin, vinyl chloride resin, vinylidene chloride resin, vinyl alcohol resin, vinyl acetal resin, methyl methacrylate resin, fluorine resin, polyether resin, polyethylene terephthalate, poly Acrylic acid ester, styrene / butadiene rubber, butadiene rubber, polyisobutylene / isopreneprene copolymer, isoprene rubber, styrene / isoprene rubber, nitrile rubber Acrylic rubber, silicone rubber, fluoro rubber, butyl rubber, natural rubber, syndiotactic-1,2-polybutadiene, styrene / butadiene block copolymer, styrene / isoprene conjugated diene block copolymer, implant type olefin thermoplastic elastomer , Polyurethane-based thermoplastic elastomers, polyester-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, fluorine-based thermoplastic elastomers, and the like; and hydrogenated products thereof, maleic anhydride graft polymers, and the like. These high molecular compounds may be used individually by 1 type, and may use 2 or more types together.
The usage rate of these polymer compounds is 50 parts by mass when the total of the copolymer (A), the thermoplastic resin (B), the thermoplastic resin (C) and the extender oil (E) is 100 parts by mass. The content is preferably 10 parts by mass or less, more preferably 5 parts by mass or less. From the viewpoint of maintaining the good injection molding appearance, moderate hardness, molding cycle characteristics, and tackiness of the molded body, and at the same time ensuring the adhesion between the thermoplastic elastomer molded body and the vulcanized rubber molded body in the composite member. The usage rate of the polymer compound is preferably 300 parts by mass or less.

[2] Method for Producing Raw Material Composition The raw material composition for producing the thermoplastic elastomer composition of the present invention can be prepared by kneading and mixing at least one of the above components. it can.
The raw material composition may be kneaded / mixed in advance for all the components, or only a part of the components may be kneaded / mixed in advance, and the remainder of the raw material composition during the production of the thermoplastic elastomer composition of the present invention. It is good also as adding a component.
The kneading | mixing of a raw material composition can be performed with a kneader, a Banbury mixer, a roll, etc., for example. The kneading of the raw material composition can be performed using, for example, a Henschel mixer, a drum tumbler, or the like.

[3] Thermoplastic elastomer composition The thermoplastic elastomer composition of the present invention is produced from the raw material composition as described above, and
In the sea phase containing at least the thermoplastic resin (B),
It has a sea-island structure in which island phases containing at least the copolymer (A) are dispersed. By adopting such a phase structure, a thermoplastic elastomer composition having good hardness, injection molding appearance and vulcanized rubber adhesiveness can be obtained while the molding cycle can be shortened. The state in which the thermoplastic resin (C) is present in the composition is not yet clear, but the inventors have studied that the formation of the phase structure as described above is the subject of the present invention. It is clear that this is a necessary condition for realizing the expected effect.
In contrast, for example, a composition having a sea-island structure in which an island phase containing a thermoplastic resin (B) is dispersed in a sea phase containing a copolymer (A) has rubber elasticity and flexibility. Although good, the appearance and non-adhesiveness of the injection molding, and the adhesion between the thermoplastic elastomer molded body and the vulcanized rubber molded body in the composite member are insufficient. In addition, the composition having a structure in which the phase containing the copolymer (A) and the phase containing the thermoplastic resin (B) each form a continuous phase has rubber elasticity, flexibility and non-adhesiveness. And the adhesiveness between the thermoplastic elastomer molded body and the vulcanized rubber molded body in the composite member are insufficient.
The shape of the island phase in the thermoplastic elastomer composition of the present invention can be a sphere, an oval sphere, a rod, a polyhedron, an indefinite shape, or the like. As for the size of the island phase, the number average value of the maximum diameter is preferably 0.1 to 10 μm, and more preferably 0.5 to 5 μm.
The phase structure of the thermoplastic elastomer composition and the shape and size of the island phase can each be known by electron microscope observation.
The elastomer composition of the present invention is preferably at least one of a copolymer (A), a thermoplastic resin (B) and a thermoplastic resin (C) (and a polymer compound as another component if present). Some are cross-linked. The degree of this crosslinking can be estimated from the cyclohexane insoluble content of the composition.
The cyclohexane insoluble content of the thermoplastic elastomer composition of the present invention is preferably 80% by mass or more, more preferably 85% by mass or more, and still more preferably 90% by mass or more. This value may be 100% by mass.

[3-1] Method for Producing Thermoplastic Elastomer Composition The thermoplastic elastomer composition of the present invention as described above can be obtained by subjecting the raw material composition as described above to heat treatment under shear. Can do. This heat treatment under shearing is a technique known as “dynamic crosslinking” in the art and can be performed using an appropriate kneading apparatus (described later). Also in this specification, the term “dynamic crosslinking” is used hereinafter to mean a heat treatment under shear.
The shear force applied during the dynamic crosslinking is preferably 100 to 20,000 / second, more preferably 150 to 15,000 / second, and 200 to 10,000 / second as the shear rate. More preferably. By performing dynamic crosslinking at such a shear rate, a thermoplastic elastomer composition having high mechanical strength can be obtained.
The heating temperature at the time of dynamic crosslinking is preferably a temperature equal to or higher than the melting point (Tm, unit ° C.) of the thermoplastic resin (B). The heating temperature is preferably (Tm + 5) to (Tm + 100) ° C., and more preferably (Tm + 10) Tm to (Tm + 80) ° C. If this temperature is lower than Tm ° C., the thermoplastic resin (B) is mixed in the composition in a state where it is not melted, and as a result, the dispersibility during dynamic cross-linking deteriorates, resulting in insufficient vaporization strength. . On the other hand, when this temperature exceeds (Tm + 100) ° C., the mechanical strength of the resulting thermoplastic elastomer composition may be impaired.
The time for performing the dynamic crosslinking is preferably 0.5 to 25 minutes, more preferably 1 to 10 minutes.

As a kneading apparatus for performing dynamic crosslinking as described above, among the appropriate apparatuses known in the art, an apparatus that can generate the preferred shearing force and that can include a heating facility. Can be preferably used. As a kneading apparatus for performing dynamic crosslinking, for example, a Henschel mixer, a kneader, a drum tumbler or the like has insufficient shearing force. As a kneading apparatus for performing dynamic crosslinking, for example, a twin screw extruder can be exemplified. As the twin screw extruder, either a different direction rotating twin screw extruder or a same direction rotating twin screw extruder may be used. As a commercial product of a twin screw extruder, for example, a high-speed twin screw continuous mixer “CIM” (trade name, manufactured by Nippon Steel Works), “Mixtron FCM / NCM / LCM / ACM” can be used. "(Trade name, manufactured by Kobe Steel, Ltd.), etc .;
For example, “GT / PCM series” (trade name, manufactured by Ikegai Co., Ltd.), “KTX” (trade name, manufactured by Kobe Steel, Ltd.), “TEX” (trade name, (Manufactured by Nippon Steel), "TEM" manufactured by Toshiba Machine Co., Ltd. (trade name, manufactured by Toshiba Machine Co., Ltd.), "ZSK" (trade name, manufactured by Warner & Friedler, Germany), etc. Each can be mentioned.

In order to produce the thermoplastic elastomer composition of the present invention, a series of devices connected in series with the above-mentioned different direction rotating twin screw extruder as the upstream side and the same direction rotating twin screw extruder as the downstream side are connected. Most preferably, dynamic cross-linking is used. Specifically, for example, it can be performed in accordance with the conditions described in Patent Document 5 (Japanese Unexamined Patent Application Publication No. 2007-2111184). The outline of preferable dynamic crosslinking conditions is listed as follows. “Tm” in the following means the melting point of the thermoplastic resin (B).
<Upstream different direction rotating twin screw extruder>
Cylinder temperature: Tm (° C) or less Specific energy: 0.01 to 2.0 kW / hr · kg
Screw rotation speed: 150-850rpm
Kneaded product outlet temperature: Tm (° C.) or more and [Tm + 200] (° C.) or less <Downstream side co-rotating twin screw extruder>
Cylinder temperature: [Tm-30] (° C) or more, [Tm + 200] (° C) or less Specific energy: 0.1 to 10 kW / hr · kg
Screw rotation speed: 100-850rpm
Kneaded product outlet temperature: [Tm + 10] (° C.) or more and [Tm + 200] (° C.) or less During kneading, the temperature of the kneaded product increases due to frictional heat of the material. Therefore, it will be obvious to those skilled in the art that the preferable cylinder temperature and the like do not necessarily coincide with the temperature of the kneaded product.

[3-2] Other components The elastomer composition of the present invention obtained as described above may be used as it is or may optionally contain other components.
As said other component, the same thing as what was illustrated above can be mentioned as another component which the raw material composition of the elastomer composition of this invention can contain.
However, it is preferable that the elastomer composition of the present invention does not contain these other components. However, the other components already contained at the time of the raw material composition do not impair the effects of the present invention even if the elastomer composition of the present invention contains them as they are.

[4] Composite Member Using the thermoplastic elastomer composition of the present invention as described above, a composite member in which a thermoplastic elastomer molded body and a vulcanized rubber are joined can be produced.
Examples of the vulcanized rubber used here include a vulcanized rubber obtained from EPMD.
The composite member can be manufactured by injection molding. Specifically, for example, the vulcanized rubber as described above is previously placed in an injection mold, the thermoplastic elastomer composition of the present invention is injected into the mold by injection molding, and then cooled. Can be manufactured by a method.
In this injection molding, for example, a cylinder temperature of 200 to 270 ° C., an injection rate of 10 to 100 cc / sec, and a mold cooling temperature of 30 to 60 ° C. are used as the thermoplastic elastomer molded body and the vulcanized rubber molded body in the composite member. From the viewpoint of adhesiveness.

[5] Use of composite member The composite member obtained as described above can be used in various applications such as automobile bumpers; exterior moldings; wind seal gaskets; door seal gaskets; trunk seal gaskets; Emblems; Inner and outer skin materials such as inner panels, door trims, console boxes, etc .; Weather strips; Leather sheets that require scratch resistance; Aircraft and marine sealing materials and inner and outer skin materials; Civil and architectural sealing materials , Interior / exterior skin materials, waterproof sheet materials, etc .; seal materials for general machinery / equipment, etc .; weak electrical parts / water supply packing; seal materials, skin materials, housings, etc. in fuel cell stacks; railway track pads; Roll; Cleaning blade; Film for electronic parts; Semiconductor and flat panel display (FPD) Protective film in manufacturing process; Image protective film such as photographs; Medical equipment parts; Electric wire; Daily miscellaneous goods; General processed products such as sports equipment can be widely applied.

  Hereinafter, the thermoplastic elastomer composition of the present invention will be described more specifically with reference to examples. However, these examples merely show some embodiments of the present invention. Accordingly, the present invention should not be construed as being limited to these examples.

Examples 1-4 and Comparative Examples 1-10
<I> Production of Thermoplastic Elastomer Composition A thermoplastic elastomer composition was produced using an apparatus in which the following two devices were connected in series via a conveyance pipe.
Upstream equipment: Continuous different direction rotating twin screw kneader, model name “Mixtron LCM50”, manufactured by Kobe Steel, Ltd., different direction meshing type 2 rotor, L / D = 10, screw diameter 49 mm, cylinder inner diameter 54 mm, Motor driving force 37kw
Downstream equipment: Co-rotating twin screw extruder, model name “TEX44αII”, manufactured by Nippon Steel Co., Ltd., Co-directional non-meshing screw, L / D = 52.5, screw diameter 46 mm, cylinder inner diameter 47 mm, motor Driving force 132kw
The types and amounts of copolymers (A) (oil-extended products), thermoplastic resins (B) and thermoplastic resins (C) shown in Table 1, and the types of crosslinking agents (D) listed below and crosslinking assistants The amounts (parts by mass) shown in Table 1 of the agent, black content, anti-aging agent, weathering agent, oleic acid amide, polydimethylsiloxane (1) and polydimethylsiloxane (2) were put into a Henschel mixer, The raw material composition was obtained by mixing for 30 seconds.
Next, the above raw material composition was charged from the raw material inlet of the above upstream equipment at a discharge rate of 40 kg / h using two weight type feeders (model name “KF-C88” manufactured by Kubota Corporation). ,
The amount shown in Table 1 of the following types of extender oil (added after) is press-fitted from the cylinder of the first kneading rotor part of the upstream equipment,
The thermoplastic resin (B) and the thermoplastic resin (C) are melted at a set temperature of the upstream device cylinder of 80 ° C., a screw rotation speed of 500 rpm, and a specific energy E1 set value of 0.925 kW · hr / kg. The kneading operation was performed in the state.
The kneaded material discharged from the upstream equipment is introduced into the downstream equipment through the transfer pipe,
By setting the setting temperature of the cylinder of the downstream equipment to 210 ° C, the screw rotation speed to 400 rpm and the setting value of specific energy E2 to 3.3 kW · hr / kg, and performing a crosslinking reaction by dynamic heat treatment, pelletized thermoplasticity An elastomer composition was obtained.

<II> Evaluation of thermoplastic elastomer composition (1) Evaluation of molding cycle Using the thermoplastic elastomer composition obtained in <I> above as a raw material, an injection molding machine (model name “SE50DU”, Sumitomo Heavy Industries, Ltd.) )), The conditions of injection temperature 250 ° C. and mold cooling temperature 50 ° C. are fixed, and the mold cooling time is changed from 0 seconds to 30 seconds in 1 second increments. A tube-shaped molded product having a thickness of 2 mm was produced. At this time, when the tubular molded product was taken out from the mold, the shortest mold cooling time at which the molded product was not deformed was evaluated as a molding cycle. A shorter mold cooling time indicates a faster molding cycle, which is preferable. Under the conditions in this example, it can be said that the molding cycle is sufficiently fast when the mold cooling time is 20 seconds or less.
(2) Measurement of melt flow rate The fluidity of the thermoplastic elastomer composition was evaluated based on the value of the melt flow rate (MFR). The measurement was performed under the conditions of a temperature of 210 ° C. and a load of 21.18 N in accordance with the method described in ISO1133.

(3) Evaluation of adhesion of vulcanized rubber (3-1) Production of vulcanized rubber adherend Ethylene / propylene / 5-ethylidene-2-norbornene terpolymer (trade name “EP 103AF”, JSR Corporation ), Ethylene unit content 59% by mass, propylene unit content 36.5% by mass, Mooney viscosity 91,) 100 parts by mass, carbon black (trade name “Seast 116”, manufactured by Tokai Carbon Co., Ltd.) 145 parts by mass, paraffin System process oil (trade name “PW380”, manufactured by Idemitsu Kosan Co., Ltd.) 85 parts by mass, activated zinc white (manufactured by Sakai Chemical Industry Co., Ltd.), 5 parts by mass, stearic acid (produced by ADEKA Co., Ltd.) 1 part by mass , 1 part by weight of processing aid (trade name “Hitanol 1501”, manufactured by Hitachi Chemical Co., Ltd.), mold release agent (trade name “Stractol WB212”, Germany Schill + Seilache GmbH Ltd.) 2 parts by mass and a plasticizer (polyethylene glycol) 1 part by weight, 50 ° C. using a Banbury mixer, 70 rpm, the mixture was obtained by mixing 2.5 minutes.
To 100 parts by mass (total amount) of the obtained mixture, 10 parts by mass of a dehydrating agent (trade name “VESTA PP”, manufactured by Inoue Lime Industry Co., Ltd.), 1 part by mass of trade name “M” as a vulcanization accelerator, 1 part by mass of the product name “PX”, 0.5 part by mass of the product name “TT” and 1 part by mass of the product name “D” (all of which are manufactured by Ouchi Shinsei Chemical Co., Ltd.) After kneading at 50 ° C. using an open roll, vulcanization was performed at 170 ° C. for 10 minutes to obtain a vulcanized rubber sheet of 120 mm × 120 mm × 2 mm (length × width × thickness). This sheet was punched out into a length of 60 mm and a width of 50 mm using a dumbbell cutter to obtain an olefin-based vulcanized rubber adherend.
(3-2) Evaluation of vulcanized rubber adhesion First, it was obtained as described above in a split mold of an injection molding machine (trade name “J-110AD”, manufactured by Nippon Steel Works) with a clamping force of 110 tons. An olefin-based vulcanized rubber adherend was pasted in advance.
Next, the thermoplastic elastomer composition obtained in the above <1> is injection-molded in the split mold so as to be accommodated in the notch (in the split mold to which the olefin-based vulcanized rubber adherend is attached). A flat plate (120 mm × 120 mm × 2 mm (length × width × thickness)) obtained by injection-sealing the thermoplastic elastomer composition and the olefin-based vulcanized rubber adherend was obtained.
Next, this flat plate was punched out with a JIS-3 dumbbell cutter to obtain a test piece (dumbbell-shaped test piece) for evaluating vulcanized rubber adhesion. At this time, the flat plate has an injection-fused surface (surface on which the thermoplastic elastomer composition and the olefin-based vulcanized rubber adherend are injection-fused) located between the marked lines and with respect to the tensile direction. Punched out to be vertical.
Next, using a tensile tester (model name “AG-2000”, manufactured by Shimadzu Corporation), the test piece was pulled at a load speed of 200 mm / min, and vulcanized with a value (unit MPa) of breaking strength. It was used as an index of rubber adhesion.
It can be judged that the one where the value of this adhesive strength is large is excellent in adhesiveness. However, the adhesiveness also depends on the hardness of the thermoplastic elastomer. Examples of the value of the adhesive strength that is judged to have sufficiently high adhesiveness for each hardness are as follows.
Hardness (durometer A hardness, hereinafter the same) 75 or more: Adhesive strength 3.0 MPa or more Hardness 65 or more and less than 75: Adhesive strength 2.5 MPa or more Hardness 55 or more and less than 65: Adhesive strength 2.0 MPa or more Hardness 45 or more 55 Less than: Adhesive strength 1.5 MPa or more

<III> Manufacture and Evaluation of Thermoplastic Elastomer Molded Body (1) Manufacture of Test Piece of Thermoplastic Elastomer Molded Body The thermoplastic elastomer composition obtained in the above <I> was molded into an injection molding machine (model name “J-110AD”). ”, Manufactured by Nippon Steel Co., Ltd.) was used to obtain a 120 × 120 × 2 mm test piece made of a thermoplastic elastomer molded body.
(2) Evaluation of appearance of injection molding The test piece obtained in (1) above was visually observed to check for the presence of a flow mark. The case where the flow mark was not seen was evaluated as good injection molding appearance (◯), and the case where the flow mark was seen was evaluated as poor injection molding appearance (×).
(3) Measurement of hardness Durometer A hardness was measured according to the method described in ISO868 for the test piece obtained in (1) above. It can be evaluated that a molded object is so flexible that this value is low. It can be said that the molded body having this value in the range of 20 to 90 has moderate flexibility.
(4) Evaluation of adhesiveness From the test piece obtained in the above (1), three rectangular test pieces having a length of 40 mm and a width of 30 mm were punched out, and each was left in a constant temperature bath under the following conditions.
60 ° C, 95% humidity
70 ° C, humidity 95%
80 ° C, humidity 95%
The surface of the test piece after standing for 500 hours after touching with each of the above conditions was touched with a finger to examine the presence or absence of tackiness, and evaluated as having no tackiness (O) or having tackiness (X).
(5) Evaluation of phase structure About the test piece obtained by said (1), the thin film piece was produced by cut | disconnecting in a thickness direction using a microtome. This thin film slice was stained with RuO ₄ and a transmission electron micrograph (TEM image) was taken to examine the phase structure. The phase structure was evaluated according to the following criteria.
A: Sea-island structure in which the island phase containing the copolymer (A) is dispersed in the sea phase containing the thermoplastic resin (B) B: In the sea phase containing the copolymer (A), Sea-island structure in which the island phase containing the thermoplastic resin (B) is dispersed C: The phase containing the copolymer (A) and the phase containing the thermoplastic resin (B) each form a continuous phase Structure of TEM The TEM image obtained in Example 1 is shown in FIG. The portion that appears black in FIG. 1 (portion stained with RuO ₄ ) is an island phase containing the copolymer (A).
All the above evaluation results are shown in Table 1.

Example 5
<I> Production of thermoplastic elastomer composition Copolymer (A) (oil-extended product), thermoplastic resin (B) and thermoplastic resin (C) of the types and amounts shown in Table 1, and listed below The amount (parts by mass) shown in Table 1 of each type of extender oil (post-added), anti-aging agent, weathering agent, oleic acid amide and polydimethylsiloxane (2) was added to a Henschel mixer, and the thermoplastic The resin (B) was kneaded at 40 rpm (shearing speed 200 / sec) for 15 minutes until the resin (B) melted and each component was uniformly dispersed. The obtained kneaded material in a molten state was pelletized by a feeder ruder (manufactured by Moriyama Co., Ltd.).
Next, the total amount of the above pellets, the types of crosslinking agents listed below (D), crosslinking assistants and black pigments were added in amounts (parts by mass) shown in Table 1 to a Henschel mixer and mixed for 30 seconds. Using a co-rotating twin screw extruder (manufactured by Nippon Steel Works, model name “TEX44αII”), the set temperature of the cylinder is 210 ° C., the screw rotation speed is 400 rpm, and the specific energy E2 is set to 3.3 kW · hr. A pellet-shaped thermoplastic elastomer composition was obtained by performing a crosslinking reaction by dynamic heat treatment.

<II> Evaluation Various evaluations were performed in the same manner as in Examples 1 to 4 and Comparative Examples 1 to 10 except that the thermoplastic elastomer composition produced in <I> was used.
The evaluation results are shown in Table 1.
Abbreviations of each component in Table 1 have the following meanings.
[Copolymer (A)]
A-1: Ethylene / propylene / 5-ethylidene-2-norbornene terpolymer (ethylene unit content 66 mass%, 5-ethylidene-2-norbornene unit content 4.5 mass%, intrinsic viscosity 4.6) 50 Oil exhibition product consisting of 50% by mass and paraffinic mineral oil content of 50% by mass. In Table 1, the copolymer (A) (denoted as “EPDM” in the table) and the paraffinic mineral oil (denoted as “extension oil” in the table) are listed separately.
[Thermoplastic resin (B)]
B-1: Propylene homopolymer, trade name “Novatech PP MA2”, manufactured by Nippon Polypro Co., Ltd., melting point 160 ° C., density 0.90 g / cm ³ , melt flow rate (230 ° C., load 21.2 N) 16 g / 10 Min, heat of fusion 103J / g
B-2: Propylene / ethylene / 1-butene random copolymer, trade name “Novatech PP FL02A”, manufactured by Nippon Polypro Co., Ltd., melting point 139 ° C., density 0.90 g / cm ³ , melt flow rate (230 ° C., (Load 21.2N) 20 g / 10 min, heat of fusion 74 J / g

[Thermoplastic resin (C)]
C-1: Ethylene / propylene / 1-butene copolymer, trade name “VESTOPLAST508”, manufactured by Evonik Degussa GmbH, Germany, ethylene unit content 16 mol%, propylene unit content 24 mol%, melt viscosity (190 ° C., ASTM-D3236) 8,000 MPa · s, density 0.87 g / cm ³ , heat of fusion 8.5 J / g
C-2: Propylene / 1-butene copolymer, trade name “REXTac RT2780”, US HUNTSMAN POLYMERS Corp. Manufactured, propylene unit content 62 mol%, melt viscosity (190 ° C., ASTM-D3236) 8,000 MPa · s, density 0.87 g / cm ³ , heat of fusion 17 J / g
C-3: Ethylene / propylene copolymer, trade name “REXTac RT2280”, US HUNTSMAN POLYMERS Corp. Manufactured, ethylene unit content 3.5 mol%, melt viscosity (190 ° C., ASTM-D3236) 8,000 MPa · s, density 0.87 g / cm ³ , heat of fusion 16 J / g
The detail of each component below the crosslinking agent (D) used above is as follows.
Crosslinking agent (D): 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, trade name “Perhexa 25B-40”, manufactured by NOF Corporation Crosslinking aid: N, N′— m-Phenylene bismaleimide, trade name “Barnock PM”, manufactured by Ouchi Shinsei Chemical Co., Ltd.)
Black content: a mixture of crystalline thermoplastic resin and carbon black (carbon black content 40% by mass)
Anti-aging agent: Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], trade name “Irganox 1010”, European BASF SE company Weathering agent: Tetrakis (1,2 , 2,6,6-pentamethyl-4-piperidyl) = 1,2,3,4-butanetetracarboxylate, trade name “ADK STAB LA-52” (manufactured by ADEKA)
Oleic acid amide: Trade name “Armoslip CP Powder”, manufactured by Lion Akzo Co., Ltd. Polydimethylsiloxane (1): Polydimethylsiloxane with kinematic viscosity 100 mm ² / s, Trade name “Silicone Oil SH200”, Toray Dow Corning (Made by Co., Ltd.)
Polydimethylsiloxane (2): Polydimethylsiloxane having a kinematic viscosity of 1,000 mm ² / s, trade name “Silicone Oil SH200”, manufactured by Toray Dow Corning Co., Ltd.)
Extension oil (post-added): hydrogenated paraffinic mineral oil, trade name “Diana Process Oil PW90”, manufactured by Idemitsu Kosan Co., Ltd., pour point -15 ° C., kinematic viscosity (40 ° C.) 95.54 cSt
The number of each component in Table 1 is the blended amount (parts by mass). The “extension oil (E) total” column is the total amount of the extension oil in the copolymer (A) oil-extended product and the post-added extension oil.

From the results shown in Table 1, the following is clear.
The thermoplastic elastomer composition of Example 1 has an excellent molding cycle and a good appearance of injection molding as compared with Comparative Examples 1 to 7, and exhibits adhesiveness even in a high temperature region of about 70 to 80 ° C. There wasn't.
As for Examples 2 to 4 which are different in hardness from Example 1, Example 2 and Comparative Example 8, Example 3 and Comparative Example 9, and Examples 4 and 10 are compared, respectively. It can be seen that the plastic elastomer composition is also excellent in the molding cycle.
On the other hand, the thermoplastic elastomer composition of Comparative Example 1 had a poor appearance of injection molding. This result is considered to be due to the poor fluidity because the composition of Comparative Example 1 does not contain the thermoplastic resin (B). In each of the thermoplastic elastomer compositions of Comparative Examples 2 and 3, an α-olefin resin whose heat of fusion does not satisfy the provisions of the present invention is used in place of the α-olefin resin (C). In these comparative examples, the adhesiveness was developed in a high temperature range of about 70 to 80 ° C. In Comparative Examples 4 to 10, an α-olefin resin whose heat of fusion does not satisfy the provisions of the present invention is used instead of the thermoplastic resin (B). In each of these comparative examples, the molding cycle became longer. It should be noted that since the molding cycle time greatly depends on the composition of the thermoplastic elastomer composition, the evaluation of the molding cycle time should be performed with respect to a similar composition.
Similar to Example 1, the thermoplastic elastomer composition of Example 5 was excellent in the molding cycle, had a good appearance of injection molding, and did not exhibit tackiness even in a high temperature region of about 70 to 80 ° C.

Claims (7)

at least,
Ethylene / α-olefin / non-conjugated polyene copolymer (A),
An α-olefin-based thermoplastic resin (B) having a melting point of 140 ° C. or higher and a heat of fusion measured in accordance with JIS K 7122 of 75 J / g or more;
Α-olefin resin (C) having a heat of fusion of 15 J / g or less measured in accordance with JIS K 7122, and crosslinking agent (D)
A raw material composition containing, and
In the sea phase containing at least the α-olefin-based thermoplastic resin (B),
A thermoplastic elastomer composition having a sea-island structure in which an island phase containing at least the ethylene / α-olefin / non-conjugated polyolefin copolymer (A) is dispersed.   The thermoplastic elastomer composition according to claim 1, wherein the raw material composition further contains an extender oil (E).   The thermoplastic elastomer composition according to claim 1 or 2, which is produced by subjecting the raw material composition to a heat treatment under shear. In the raw material composition, when the total of the copolymer (A), the thermoplastic resin (B) and the resin (C) is 100 parts by mass,
The content of the copolymer (A) is 35 to 95 parts by mass,
The content rate of the said thermoplastic resin (B) is 3-50 mass parts, and the content rate of the said resin (C) is 0.1-10 mass parts, It is as described in any one of Claims 1-3. Thermoplastic elastomer composition.   The thermoplastic elastomer composition according to claim 2, wherein the content of the extending oil (E) in the raw material composition is 20 to 300 parts by mass with respect to 100 parts by mass of the copolymer (A).   A composite member obtained by bonding a thermoplastic elastomer molded article obtained by molding the thermoplastic elastomer composition according to any one of claims 1 to 5 and vulcanized rubber. A method for producing the thermoplastic elastomer according to claim 1, comprising:
at least,
Ethylene / α-olefin / non-conjugated polyene copolymer (A),
An α-olefin-based thermoplastic resin (B) having a melting point of 140 ° C. or higher and a heat of fusion measured in accordance with JIS K 7122 of 75 J / g or more;
Α-olefin resin (C) having a heat of fusion of 15 J / g or less measured in accordance with JIS K 7122, and crosslinking agent (D)
The said method characterized by performing heat processing under a shear with respect to the raw material composition containing this.