WO2017073695A1

WO2017073695A1 - Thermoplastic elastomer composition, member, weather seal, and corner member for weather seal

Info

Publication number: WO2017073695A1
Application number: PCT/JP2016/081960
Authority: WO
Inventors: 小西　大輔; 佐々木　啓光; 陽介上原
Original assignee: 株式会社クラレ
Priority date: 2015-10-30
Filing date: 2016-10-27
Publication date: 2017-05-04
Also published as: TW201728733A; JP6867034B2; JPWO2017073695A1

Abstract

Provided is a thermoplastic elastomer composition which has high adhesion to vulcanized rubber and dynamically crosslinked thermoplastic elastomers (TPVs), and has excellent flexibility, weather resistance and moldability. Further provided are a member having a portion made of the thermoplastic elastomer composition, a weather seal comprising the member and a corner member for a weather seal having a portion made of the thermoplastic elastomer composition. The thermoplastic elastomer composition is, specifically, a thermoplastic elastomer composition comprising an olefin-based rubber (I), a hydrogenated block copolymer (II) described below, a polyolefin-based resin (III), and a softening agent (IV). The content ratio of the olefin-based rubber (I) and hydrogenated block copolymer (II) [(I)/(II)] is 90/10 to 10/90 (mass ratio). With respect to a total of 100 parts by mass of the olefin-based rubber (I) and the hydrogenated block copolymer (II), the content of the polyolefin-based resin (III) is 10 to 200 parts by mass, and the content of the softening agent (IV) is 15 to 300 parts by mass. The hydrogenated block copolymer (II) comprises: a polymer block (A), primarily comprising structural units derived from an aromatic vinyl compound; and a polymer block (B) primarily comprising structural units derived from at least one substance selected from the group consisting of isoprene and butadiene, in which the total content of 3,4-bond units and 1,2-bond units is 45% or more. The peak top molecular weight of the hydrogenated block copolymer (II) is 50,000 to 200,000, and 70 mol% or more of the carbon-carbon double bonds in the polymer block (B) are hydrogenated.

Description

Thermoplastic elastomer composition, member, weather seal, corner member for weather seal

The present invention relates to a thermoplastic elastomer composition, a member, a weather seal, and a weather seal corner member.

In addition to vulcanized rubber that has been used for automotive parts, dynamic crosslinked thermoplastic elastomers (TPV) are also attracting attention, and are currently widely used in automotive applications and the like.
One of the parts for automobiles is a weather seal. As a material for the weather seal, vulcanized rubber having a small compression set and excellent flexibility has been used so far. However, with recent regulations for reducing carbon dioxide emissions, there is a tendency to replace TPV with better molding processability and light specific gravity (see Non-Patent Document 1).
A weather seal for an automobile usually has a straight portion and a corner portion. Industrially, the straight part is manufactured by extrusion molding, but the corner part is manufactured by injection molding. Therefore, it is necessary to select a material capable of injection molding as the material of the corner part. However, even a TPV having better moldability than vulcanized rubber cannot be said to have sufficient moldability, and there is room for further improvement. For this reason, vulcanized rubber or TPV is used as the material for the straight portion of the weather seal, but it is desirable to use another material that is excellent in molding processability while maintaining various characteristics as the material for the corner portion. .

Damping members; building materials such as packing; automotive interior / exterior components such as bumper parts and airbag covers; molding processability, flexibility, vibration damping, strain recovery at high temperatures, and softening A thermoplastic elastomer composition having excellent agent retention is known (Patent Document 1).
The thermoplastic elastomer composition described in Patent Document 1 is derived from olefin rubber (I), a polymer block (A) composed of structural units derived from an aromatic vinyl compound, and isoprene or a mixture of isoprene and butadiene. A hydrogenated block copolymer having a structural unit and a polymer block (B) having a total content of 3,4-bond units and 1,2-bond units of 45% or more, A hydrogenated block copolymer (II) having a peak top molecular weight (Mp) of 250,000 to 500,000 determined by gel permeation chromatography in terms of standard polystyrene, a polyolefin resin other than the above (I) (III ) And a softening agent (IV) comprising a olefinic rubber (I) and a hydrogenated block co-polymer The blend (II) is contained in a ratio of olefinic rubber (I): hydrogenated block copolymer (II) = 90: 10 to 10:90 (mass ratio), and the olefinic rubber (I) and hydrogenated block Thermoplastic elastomer composition containing 10 to 200 parts by mass of polyolefin resin (III) and 10 to 300 parts by mass of softener (IV) with respect to 100 parts by mass of copolymer (II) It is.

JP 2014-080488 A

As a result of studies by the present inventors, it has been found that the thermoplastic elastomer composition described in Patent Document 1 has room for further improvement in molding processability, and as a material for the corner portion of the weather seal, a better material has been developed. It has been demanded. Furthermore, when the material of the straight part of the weather seal is TPV, if the thermoplastic elastomer composition described in Patent Document 1 is used as the material of the corner part, there is room for further improvement in the adhesion with the straight part. It has been found.
Accordingly, an object of the present invention is to provide a thermoplastic elastomer having high adhesive strength to vulcanized rubber and dynamically cross-linked thermoplastic elastomer (TPV), and being excellent in moldability as well as flexibility and weather resistance. It is to provide a composition. Furthermore, it is providing the member which has a site | part which consists of this thermoplastic elastomer composition, the weather seal containing this member, and the corner member for weather seals which has a site | part which consists of the said thermoplastic elastomer composition.

The inventors of the present invention made extensive studies to solve the above-mentioned problems. As a result, the olefin rubber (I), the specific hydrogenated block copolymer (II), the polyolefin resin (III), and the softener ( IV) a thermoplastic elastomer composition comprising the olefin rubber (I) and the hydrogenated block copolymer (II) in a specific range, and a polyolefin resin (III). It has been found that the above-mentioned problems can be solved if the thermoplastic elastomer composition has a content of the softening agent (IV) within a specific range, and the present invention has been achieved.

The present invention relates to the following [1] to [18].
[1] Olefin rubber (I),
The following hydrogenated block copolymer (II),
Polyolefin resin (III) and softener (IV)
A thermoplastic elastomer composition comprising:
The content ratio [(I) / (II)] of the olefin rubber (I) and the hydrogenated block copolymer (II) is 90/10 to 10/90 by mass ratio,
The content of polyolefin resin (III) is 10 to 200 parts by mass and the content of softener (IV) is 100 parts by mass in total of olefin rubber (I) and hydrogenated block copolymer (II). A thermoplastic elastomer composition having a content of 15 to 300 parts by mass.
Hydrogenated block copolymer (II): mainly from a polymer block (A) mainly composed of a structural unit derived from an aromatic vinyl compound and a structural unit derived from at least one selected from the group consisting of isoprene and butadiene. And a hydrogenated product of a block copolymer having a polymer block (B) having a total content of 3,4-bond units and 1,2-bond units of 45% or more, Water having a peak top molecular weight of 50,000 to 200,000 determined by standard polystyrene conversion by an association chromatography and hydrogenated 70 mol% or more of the carbon-carbon double bonds in the polymer block (B). A block copolymer.
[2] The thermoplastic elastomer composition according to the above [1], wherein the hydrogenated block copolymer (II) has a glass transition temperature of −45 to 0 ° C.
[3] The thermoplastic elastomer composition according to the above [1] or [2], wherein the content of the polymer block (A) in the hydrogenated block copolymer (II) is 5 to 40% by mass.
[4] The thermoplastic elastomer composition according to any one of the above [1] to [3], wherein the content of the polymer block (A) in the hydrogenated block copolymer (II) is 5 to 18% by mass.
[5] Two polymer blocks (A1) in which the polymer block (A) in the hydrogenated block copolymer (II) has the same or different peak top molecular weight determined in terms of standard polystyrene by gel permeation chromatography And (A2), and the hydrogenated block copolymer (II) is composed of the polymer block (A1), the polymer block (B), and the polymer block (A2). The thermoplastic elastomer composition according to any one of the above [1] to [4], which is a hydrogenated product of the triblock copolymer [A1-B-A2].
[6] In the hydrogenated block copolymer (II),
The polymer block (A1) in which the polymer block (A) is mainly composed of a structural unit derived from an aromatic vinyl compound and has a peak top molecular weight of Mp (A1) determined in terms of standard polystyrene by gel permeation chromatography. And a polymer block (A2) having a peak top molecular weight of Mp (A2), which is mainly composed of a structural unit derived from an aromatic vinyl compound, and calculated in terms of standard polystyrene by gel permeation chromatography,
The thermoplastic elastomer composition according to the above [5], wherein the ratio [Mp (A1) / Mp (A2)] of the Mp (A1) to the Mp (A2) satisfies 1/10 to 8/10.
[7] The thermoplastic elastomer according to any one of [1] to [6] above, wherein the olefin rubber (I) and the polymer block (B) of the hydrogenated block copolymer (II) are crosslinked. Composition.
[8] The olefin rubber (I) is a copolymer rubber of (I-1) ethylene and one or more α-olefins having 3 to 20 carbon atoms, or a crosslinked product thereof, and (I-2) ethylene. And at least one selected from the group consisting of a copolymer rubber of at least one α-olefin having 3 to 20 carbon atoms and at least one non-conjugated polyene or a crosslinked product thereof [1] The thermoplastic elastomer composition according to any of [7].
[9] The polyolefin resin (III) is at least one selected from the group consisting of polyethylene resin, polypropylene resin, poly (1-butene) and poly (4-methyl-1-pentene). The thermoplastic elastomer composition according to any one of the above [1] to [8].
[10] A member having a portion (X1) made of the thermoplastic elastomer composition according to any one of [1] to [9].
[11] The member according to the above [10], which has a portion (Y1) made of a material different from the thermoplastic elastomer composition according to any one of the above [1] to [9] in addition to the portion (X1).
[12] The member according to [11] above, wherein the material of the part (Y1) is vulcanized rubber or a dynamically crosslinked olefin-based thermoplastic elastomer (TPV).
[13] In addition to the part (X1), the thermoplastic elastomer composition according to any one of the above [1] to [9] (provided that the thermoplastic elastomer composition is the same as the thermoplastic elastomer composition forming the part (X1)). The member according to [10] above, which has a portion (X2) consisting of the same.
[14] The member according to any one of [10] to [13], wherein the part (X1) is a part obtained by injection molding.
[15] A weather seal containing the member according to any one of [10] to [14].
[16] It has a portion (X1) made of the thermoplastic elastomer composition according to any one of [1] to [9], and
In addition to the part (X1), it has a part (Y1) made of a material different from the thermoplastic elastomer composition of any one of the above [1] to [9], or in addition to the part (X1) A part comprising the thermoplastic elastomer composition according to any one of the above [1] to [9] (however, it may be the same as or different from the thermoplastic elastomer composition forming the part (X1)). A weather seal containing a member having (X2),
A weather seal having a corner portion made of the portion (X1) and a straight portion made of the portion (X2) or (Y1).
[17] The weather seal according to [15] or [16], which is for automobiles, ships, or aircraft.
[18] A weather seal corner member having a portion (X1) made of the thermoplastic elastomer composition according to any one of [1] to [9].

According to the present invention, there is provided a thermoplastic elastomer composition having high adhesive strength to vulcanized rubber and dynamically cross-linked thermoplastic elastomer (TPV), and having excellent flexibility and weather resistance as well as excellent moldability. can do. Furthermore, the member which has a site | part which consists of this thermoplastic elastomer composition can be provided.
Further, since the thermoplastic elastomer composition of the present invention is suitable for weather seals, particularly for corner portions of weather seals, a weather seal containing a member having a portion made of the thermoplastic elastomer composition of the present invention, the present A corner member for a weather seal having a portion made of the thermoplastic elastomer composition of the invention can also be provided.

[Thermoplastic elastomer composition]
The thermoplastic elastomer composition of the present invention comprises:
Olefin rubber (I),
The following hydrogenated block copolymer (II),
Polyolefin resin (III) and softener (IV)
A thermoplastic elastomer composition comprising:
The content ratio [(I) / (II)] of the olefin rubber (I) and the hydrogenated block copolymer (II) is 90/10 to 10/90 by mass ratio,
The content of polyolefin resin (III) is 10 to 200 parts by mass and the content of softener (IV) is 100 parts by mass in total of olefin rubber (I) and hydrogenated block copolymer (II). 15 to 300 parts by mass of a thermoplastic elastomer composition.
Hydrogenated block copolymer (II): mainly from a polymer block (A) mainly composed of a structural unit derived from an aromatic vinyl compound and a structural unit derived from at least one selected from the group consisting of isoprene and butadiene. And a hydrogenated product of a block copolymer having a polymer block (B) having a total content of 3,4-bond units and 1,2-bond units of 45% or more, Water having a peak top molecular weight of 50,000 to 200,000 determined by standard polystyrene conversion by an association chromatography and hydrogenated 70 mol% or more of the carbon-carbon double bonds in the polymer block (B). A block copolymer.
Hereinafter, each component will be described in detail in order.

(Olefin rubber (I))
As the olefin rubber (I),
(I-1) a copolymer rubber of ethylene and one or more α-olefins having 3 to 20 carbon atoms (hereinafter sometimes referred to as “ethylene / α-olefin copolymer rubber”) or a cross-linked product thereof;
(I-2) Copolymer rubber of ethylene, one or more α-olefins having 3 to 20 carbon atoms and one or more non-conjugated polyenes (hereinafter referred to as “ethylene / α-olefin / non-conjugated polyene copolymer”) Rubber ”) or cross-linked products thereof.
Etc. Olefin rubber (I) may be used individually by 1 type, and may use 2 or more types together.
When two or more kinds are used in combination, it is preferable to use a cross-linked product of the ethylene / α-olefin copolymer rubber and a cross-linked product of the ethylene / α-olefin / non-conjugated polyene copolymer rubber together.
Among them, the olefin rubber (I) is preferably an ethylene / α-olefin / non-conjugated polyene copolymer rubber or a cross-linked product thereof from the viewpoint of better strain recovery at high temperatures. An α-olefin / non-conjugated polyene copolymer rubber or a cross-linked product of ethylene / α-olefin / non-conjugated polyene copolymer rubber may be used.

Examples of the α-olefin having 3 to 20 carbon atoms constituting the copolymer rubber or a crosslinked product thereof include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-octene, and the like. Examples include decene. These α-olefins may be used alone or in combination of two or more. Among these, at least one selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene is preferable, and at least one selected from the group consisting of propylene and 1-butene is preferable. More preferably, it is propylene.

In ethylene / α-olefin copolymer rubber, the molar ratio of ethylene to α-olefin having 3 to 20 carbon atoms (ethylene / α-olefin having 3 to 20 carbon atoms) is high in mechanical strength and strain recovery at high temperature. From the viewpoint that the properties are maintained in a well-balanced manner, 40/60 to 93/7 is preferable, 50/50 to 85/15 is more preferable, and 60/40 to 80/20 is more preferable.

Examples of the non-conjugated polyene constituting the ethylene / α-olefin / non-conjugated polyene copolymer rubber include, for example, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-propylidene-2-norbornene, 5-vinyl- Cyclic polyenes such as 2-norbornene, 2,5-norbornadiene, 1,4-cyclohexadiene, 1,4-cyclooctadiene, 1,5-cyclooctadiene; 1,4-hexadiene, 4-methyl-1,4 -Hexadiene, 5-methyl-1,4-hexadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6 -Octadiene, 5,7-dimethyl-1,6-octadiene, 7-methyl-1,7-nonadiene, 8-methyl-1,7- Nadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 4-ethylidene-1,6-octadiene, 7-methyl-4-ethylidene-1,6-octadiene, 7-methyl- 4-ethylidene-1,6-nonadiene, 7-ethyl-4-ethylidene-1,6-nonadiene, 6,7-dimethyl-4-ethylidene-1,6-octadiene, 6,7-dimethyl-4-ethylidene- C6-C15 chain polyene having an internal unsaturated bond, such as 1,6-nonadiene; 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1, Examples include α, ω-dienes such as 9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, and the like.
Among these, cyclic polyenes and chain polyenes having 6 to 15 carbon atoms having an internal unsaturated bond are preferable. 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methyl-1,4 -At least one selected from the group consisting of hexadiene and 7-methyl-1,6-octadiene is more preferable, and 5-ethylidene-2-norbornene, dicyclopentadiene and More preferred is at least one selected from the group consisting of 5-vinyl-2-norbornene.

In the ethylene / α-olefin / non-conjugated polyene copolymer rubber, the molar ratio of ethylene to the α-olefin having 3 to 20 carbon atoms and the non-conjugated polyene [ethylene / (α-olefin having 3 to 20 carbon atoms and The conjugated polyene) is preferably 90/10 to 40/60, particularly 80/20 to 50/50 from the viewpoint of flexibility and rubber elasticity.

The iodine value (iodine value before crosslinking) of the ethylene / α-olefin / non-conjugated polyene copolymer rubber is preferably 3 to 40, more preferably 5 to 25, from the viewpoint of mechanical strength and rubber elasticity. More preferably, it is 5-15. If the iodine value is 3 or more, the mechanical strength of the molded product obtained from the thermoplastic elastomer composition tends to be good, and if the iodine value is 40 or less, the rubber elasticity of the thermoplastic elastomer composition is impaired. It tends to be difficult. As used herein, “iodine value” refers to the iodine value measured by the method described in JIS K1525 (2005).

The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the olefin rubber (I) is preferably 25 to 350, more preferably 40 to 300, and more preferably 60 to 150 from the viewpoint of moldability and mechanical strength. Further preferred.
In this specification, “Mooney viscosity (ML _{1 + 4} , 100 ° C.)” refers to a viscosity measured by the method described in JIS K6300-1 (2013).

The olefin rubber (I) may be pre-crosslinked, and the degree of crosslinking is not particularly limited, but when the crosslinked olefin rubber (I) is subjected to Soxhlet extraction treatment with cyclohexane for 10 hours. The degree of crosslinking is such that the mass ratio (gel fraction) of the gel remaining without being dissolved in cyclohexane is 80% or more, particularly 95% or more with respect to the mass of the olefin rubber after crosslinking before the extraction treatment. Is preferable from the viewpoint of strain recovery at high temperatures.
In addition, the crosslinking agent and crosslinking adjuvant which can be used for the said crosslinking reaction can use the same thing as the crosslinking agent and crosslinking adjuvant which are mentioned later.

(Hydrogenated block copolymer (II))
The thermoplastic elastomer composition of the present invention needs to contain a hydrogenated block copolymer (II). When it does not contain the hydrogenated block copolymer (II), it has high adhesion to vulcanized rubber and dynamically cross-linked thermoplastic elastomer (TPV), and is molded with flexibility and weather resistance. It becomes impossible to solve at least one of the problems of excellent performance. In particular, the influence of molding processability and adhesive strength on TPV and vulcanized rubber is great.
The hydrogenated block copolymer (II) includes a polymer block (A) mainly composed of a structural unit derived from an aromatic vinyl compound, and a structural unit derived from at least one selected from the group consisting of isoprene and butadiene. A hydrogenated product of a block copolymer having a polymer block (B) mainly comprising a 3,4-bond unit and a 1,2-bond unit content of 45% or more, comprising a gel The peak top molecular weight determined by standard polystyrene conversion by permeation chromatography is 50,000 to 200,000, and 70 mol% or more of the carbon-carbon double bonds in the polymer block (B) are hydrogenated. It is a hydrogenated block copolymer.
In this specification, 3,4-bond units and 1,2-bond units in structural units derived from isoprene and 1,2-bond units in structural units derived from butadiene are collectively referred to as “vinyl bond units”. The total amount may be referred to as “vinyl bond content”.

The polymer block (A) of the hydrogenated block copolymer (II) mainly comprises a structural unit derived from an aromatic vinyl compound (hereinafter sometimes abbreviated as an aromatic vinyl compound unit). Here, “mainly” means that the aromatic vinyl compound unit is preferably 90% by mass or more, more preferably 95% by mass or more, and further preferably 100% by mass based on the mass of the polymer block (A). Means that.

Examples of the aromatic vinyl compound constituting the polymer block (A) include styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, Examples include 2,4-dimethylstyrene, 2,4,6-trimethylstyrene, monofluorostyrene, difluorostyrene, monochlorostyrene, dichlorostyrene, methoxystyrene, vinylnaphthalene, and vinylanthracene. The polymer block (A) may contain only a structural unit derived from one kind of the above-described aromatic vinyl compound, or may contain a structural unit derived from two or more kinds. Especially, it is preferable that a polymer block (A) mainly consists of the structural unit derived from styrene.

The polymer block (A) may contain a small amount of a structural unit derived from another copolymerizable monomer together with a structural unit derived from an aromatic vinyl compound. At this time, the proportion of the structural unit derived from the other copolymerizable monomer is preferably 10% by mass or less based on the mass of the polymer block (A), and more preferably 5% by mass or less. preferable. Examples of such other copolymerizable monomers include copolymerizable monomers capable of ion polymerization such as 1-butene, pentene, hexene, butadiene, isoprene, and methyl vinyl ether. When a structural unit derived from another copolymerizable monomer is contained together with a structural unit derived from an aromatic vinyl compound, the bonding form thereof may be random or tapered.

In the hydrogenated block copolymer (II), the content of the polymer block (A) is preferably 5 to 40% by mass, more preferably 5 to 30% by mass with respect to the hydrogenated block copolymer (II). 5 to 20% by mass is more preferable, and 5 to 18% by mass is particularly preferable. If the content of the polymer block (A) is 5% by mass or more, mechanical properties and flexibility tend to be good, and good strain recovery at high temperatures is obtained, and heat resistance is also good. It tends to be excellent. If the content of the polymer block (A) is 40% by mass or less, the melt viscosity of the hydrogenated block copolymer (II) does not become too high and melt mixing with other components tends to be easy. Furthermore, flexibility and adhesion to TPV and vulcanized rubber tend to be excellent. In addition, content of the polymer block (A) in hydrogenated block copolymer (II) is the value calculated | required by the method described in the Example.

The polymer block (B) contained in the hydrogenated block copolymer (II) mainly comprises structural units derived from at least one selected from the group consisting of isoprene and butadiene. The term “mainly” as used herein means that the structural unit derived from at least one selected from the group consisting of isoprene and butadiene based on the mass of the polymer block (B) is preferably 70% by mass or more, more preferably It means 90% by mass or more.
The polymer block (B) preferably mainly comprises a structural unit derived from isoprene or a structural unit derived from a mixture of isoprene and butadiene.

When the polymer block (B) is composed only of a structural unit derived from isoprene, the structural unit is a 2-methyl-2-butene-1,4-diyl group [—CH ₂ —C (CH ₃ ) ═CH— CH _2- ; 1,4-bonding unit], isopropenylethylene group [-CH (C (CH ₃ ) = CH ₂ ) -CH _2- ; 3,4-bonding unit] and 1-methyl-1-vinylethylene It consists of a group [—C (CH ₃ ) (CH═CH ₂ ) —CH ₂ —; 1,2-bond units], and in the present invention, the vinyl bond content is 45% (mol%) or more. The vinyl bond content is more preferably 47% or more, and further preferably 50% or more. Although there is no restriction | limiting in particular in the upper limit of vinyl bond content, Usually, it is preferably 95% or less, More preferably, it is 90% or less, More preferably, it is 80% or less.

When the polymer block (B) is composed of a structural unit derived from a mixture of isoprene and butadiene, the structural unit is a 2-methyl-2-butene-1,4-diyl group, isopropenyl derived from isoprene. Ethylene group and 1-methyl-1-vinylethylene group, and 2-butene-1,4-diyl group derived from butadiene [—CH ₂ —CH═CH—CH ₂ —; 1,4-bond unit] and vinyl It consists of an ethylene group [—CH (CH═CH) —CH ₂ —; 1,2-bond unit] and has a vinyl bond content of 45% (mol%) or more. The vinyl bond content is more preferably 47% or more, and further preferably 50% or more. Although there is no restriction | limiting in particular in the upper limit of vinyl bond content, Usually, it is preferably 95% or less, More preferably, it is 90% or less, More preferably, it is 80% or less.
In the copolymer block, the bonding form of the structural unit derived from isoprene and the structural unit derived from butadiene may be random, block, or tapered.

When the polymer block (B) is composed of a structural unit derived from a mixture of isoprene and butadiene, the structural unit derived from isoprene / the structural unit derived from butadiene (molar ratio) is 10 from the viewpoint of adhesive strength and flexibility. / 90 to 99/1 is preferable, 30/70 to 99/1 is more preferable, 40/60 to 99/1 is further preferable, and 40/60 to 70/30 is preferable. Is particularly preferred, with 40/60 to 55/45 being most preferred.

The polymer block (B) may have a small amount of structural units derived from other copolymerizable monomers together with structural units derived from isoprene or structural units derived from isoprene and butadiene. At this time, the proportion of the structural unit derived from the other copolymerizable monomer is preferably 30% by mass or less based on the mass of the polymer block (B), and more preferably 10% by mass or less. Preferably, it is 5 mass% or less.
Examples of such other copolymerizable monomers include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, diphenylethylene, 1-vinylnaphthalene, Copolymerizable monomers capable of anion polymerization such as aromatic vinyl compounds such as 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene Is mentioned. These other copolymerizable monomers may be used individually by 1 type, and may use 2 or more types together. In the case where the polymer block (B) has a structural unit derived from other copolymerizable monomer as described above in addition to a structural unit derived from isoprene or a structural unit derived from a mixture of isoprene and butadiene, the bonding form thereof May be either random or tapered.

The hydrogenated block copolymer (II) has one or more functional groups such as a carboxyl group, a hydroxyl group, an acid anhydride group, an amino group, and an epoxy group in the molecular chain and / or at the molecular end. It may be.

In the hydrogenated block copolymer (II), particularly from the viewpoint of heat resistance and weather resistance, 70 mol% or more of unsaturated double bonds (carbon-carbon double bonds) in the polymer block (B) are hydrogenated. Need to be. From the same viewpoint, 80 mol% or more is more preferably hydrogenated, and 85 mol% or more is more preferably hydrogenated.
The hydrogenation rate of the carbon-carbon double bond in the polymer block (B) is determined by the content of the carbon-carbon double bond in the polymer block (B) before and after the hydrogenation. It can be determined from the iodine value measurement described in the examples.

The hydrogenated block copolymer (II) is a hydrogenated product of a block copolymer containing at least one polymer block (A) and each polymer block (B). Preferably, the hydrogenated block copolymer (II) is a hydrogenated product of a block copolymer containing two or more polymer blocks (A) and one or more polymer blocks (B). The bonding form of the polymer block (A) and the polymer block (B) is not particularly limited, and may be linear, branched, radial, or a combination of two or more of these. In addition, a linearly bonded form is preferable. In particular, when the polymer block (A) is represented by 'A' and the polymer block (B) is represented by 'B', (AB) 1, A- (BA) m, B- (A- B) n (wherein l, m and n each independently represents an integer of 1 or more) is preferably a bonded form, and from the viewpoint of rubber elasticity, mechanical strength and ease of handling, (A -B) A bond form represented by 1 or A- (BA) m is more preferred, and a diblock structure represented by AB or a triblock structure represented by ABA The bonding form is more preferable, and the bonding form of the triblock structure represented by ABA is particularly preferable.
When the hydrogenated block copolymer (II) has two or more polymer blocks (A) or two or more polymer blocks (B), each polymer block (A) and each polymer block (A) The combined block (B) may be a block having the same configuration or a block having a different configuration. For example, the two polymer blocks (A) in the triblock structure represented by [ABA] may have the same or different types of aromatic vinyl compounds constituting them. Good.

In the hydrogenated block copolymer (II), the peak top molecular weight (Mp) of the polymer block (A) is preferably 2,000 to 60,000, more preferably 2,500 to 30,000, still more preferably. 3,000 to 20,000. The peak top molecular weight of the polymer block (B) is preferably 130,000 to 190,000, more preferably 50,000 to 180,000 in the state before hydrogenation.

The polymer block (A) in the hydrogenated block copolymer (II) has two polymer blocks (A1) and (A2) having the same or different peak top molecular weights determined in terms of standard polystyrene by gel permeation chromatography. And the hydrogenated block copolymer (II) is composed of the polymer block (A1), the polymer block (B), and the polymer block (A2). A hydrogenated product of the polymer [A1-B-A2] is preferable.
In this case, the hydrogenated block copolymer (II) is a peak obtained by converting the polymer block (A) mainly from a structural unit derived from an aromatic vinyl compound, and in terms of standard polystyrene by gel permeation chromatography. A peak top molecular weight mainly composed of a polymer block (A1) having a top molecular weight of Mp (A1) and a structural unit derived from an aromatic vinyl compound and determined in terms of standard polystyrene by gel permeation chromatography is Mp (A2 And the ratio of Mp (A1) to Mp (A2) [Mp (A1) / Mp (A2)] satisfies 1/10 to 8/10. However, it is preferable from the viewpoint of moldability. The ratio [Mp (A1) / Mp (A2)] indicates that Mp (A1) is smaller than Mp (A2). From the same viewpoint, it is more preferably 3/10 to 7/10. The hydrogenated product of the triblock copolymer [A1-B-A2] is an apparently asymmetric triblock copolymer because Mp (A1) and Mp (A2) are different as described above. It can be said.
A hydrogenated block copolymer (II) in which Mp (A1) and Mp (A2) are substantially equal is also preferable. Here, “substantially equal” means that [Mp (A1) / Mp (A2)] is approximately 1/1 or close to 1/1, and more specifically, 9/10 to 11 / It means being in the range of 10.
Mp (A1) and Mp (A2) are each preferably 1,000 to 30,000, more preferably 2,000 to 20,000, and still more preferably 2,000 to 15,000. Among the numerical ranges, Mp (A1) is particularly preferably 3,000 to 10,000, and Mp (A2) is particularly preferably 4,000 to 14,000.

The total peak top molecular weight (Mp) of the hydrogenated block copolymer (II) is 50,000 to 200,000, preferably 70,000 to 200,000, after hydrogenation. Preferably, it is 100,000 to 200,000. If the peak top molecular weight (Mp) of the hydrogenated block copolymer (II) is within the above range, the powdered hydrogenated block copolymer (II) having a bulk density of 0.10 to 0.40 g / ml is obtained. It tends to be easily obtained, and tends to be excellent in moldability, flexibility and strain recovery at high temperatures.
In addition, this peak top molecular weight (Mp) is the value calculated | required by the method as described in an Example.

The glass transition temperature (Tg) of the hydrogenated block copolymer (II) is preferably −45 to 0 ° C., more preferably −45 to −5 ° C., and further preferably −45 to −− from the viewpoint of vibration damping properties. It is 10 ° C., particularly preferably −40 to −10 ° C.

<Method for producing hydrogenated block copolymer (II)>
Examples of the method for producing the hydrogenated block copolymer (II) include ionic polymerization methods such as anionic polymerization and cation polymerization, polymerization methods such as single site polymerization method and radical polymerization method. In the case of the anionic polymerization method, for example, an alkyl lithium compound or the like is used as a polymerization initiator and is selected from the group consisting of an aromatic vinyl compound, isoprene and butadiene in an inert organic solvent such as n-hexane or cyclohexane. The block copolymer is produced by sequentially polymerizing at least one of the above to produce a block copolymer having a desired molecular structure and molecular weight, and then adding an active hydrogen compound such as alcohols, carboxylic acids and water to stop the polymerization. Copolymers can be produced. The hydrogenated block copolymer (II) can be obtained by conducting a hydrogenation reaction in the presence of a hydrogenation catalyst in an inert organic solvent without preferably isolating the obtained block copolymer. it can.

Examples of the alkyl lithium compound include alkyl lithium compounds having 1 to 10 carbon atoms in the alkyl residue, and methyl lithium, ethyl lithium, butyl lithium, and pentyl lithium are particularly preferable. The amount of the initiator such as an alkyl lithium compound is appropriately determined depending on the peak top molecular weight (Mp) of the hydrogenated block copolymer (II). On the other hand, 0.01 to 0.2 parts by mass are preferably used. The polymerization is usually preferably carried out at 0 to 80 ° C., preferably 0.5 to 50 hours.

In the polymer block (B) of the hydrogenated block copolymer (II), the structural unit derived from at least one selected from the group consisting of isoprene and butadiene has a vinyl bond content of 45% or more. Uses a Lewis base as a cocatalyst during the polymerization. Examples of the Lewis base include ethers such as dimethyl ether, diethyl ether, and tetrahydrofuran; glycol ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; triethylamine, N, N, N ′, N′-tetramethylenediamine, and N-methylmorpholine. And amine compounds such as The amount of the Lewis base used is preferably 0.1 to 1000 moles per 1 mole of lithium atoms in the alkyllithium compound used as the initiator.

In the hydrogenation reaction, an unhydrogenated block copolymer is dissolved in an inert organic solvent such as n-hexane or cyclohexane which is inert to the reaction and the hydrogenation catalyst in the presence of a hydrogenation catalyst. Thus, a method of reacting molecular hydrogen is preferably used. In addition, it is also possible to subject the reaction liquid obtained by sequentially copolymerizing an aromatic vinyl compound and at least one selected from the group consisting of isoprene and butadiene to a hydrogenation reaction as it is.
Examples of hydrogenation catalysts include Raney nickel; heterogeneous catalysts such as Pt, Pd, Ru, Rh, Ni and other metals supported on carbon, alumina, diatomaceous earth, etc .; transition metal compounds and alkylaluminum compounds, alkyllithiums A Ziegler-based catalyst composed of a combination of compounds is used.
The reaction is usually carried out under conditions of a hydrogen pressure of preferably 0.1 to 20 MPa, a reaction temperature of preferably 20 ° C. to 250 ° C., and a reaction time of preferably 0.1 to 100 hours.

For example, the hydrogenated block copolymer (II) in the form of powder having a bulk density of 0.10 to 0.40 g / ml can be produced by the following method. The bulk density referred to in this specification is a value calculated by putting a weighed powdered hydrogenated block polymer (II) into a graduated cylinder and measuring its volume, and dividing the mass of the polymer by the volume. is there.
The reaction solution from which the hydrogenation catalyst has been removed by filtration after the above hydrogenation reaction is heated to 40 to 150 ° C., preferably 60 to 150 ° C., and a surfactant such as a fatty acid salt or a polyoxyalkylene derivative is mixed as necessary. In this state, it is fed into hot water at 80 to 130 ° C. at a rate of 100 parts by mass / hour. At the same time, steam of 1 MPa is supplied at a rate of 40 to 60 parts by mass / hour, and when the boiling point of an inert organic solvent such as a saturated hydrocarbon or the inert organic solvent and water azeotrope, the azeotropic temperature is exceeded. After steam stripping at a temperature of 150 ° C. or less, the water content is dehydrated to 55% by mass / WB (wet base, the same applies hereinafter), preferably 45% by mass / WB or less, using a compressed water squeezer. Next, a desired moisture content of 0.1% by mass / WB or less is obtained by drying at 60 to 100 ° C. using a screw extruder type dryer, an expander dryer, a conduction heat transfer type dryer, a hot air dryer or the like. A powdered hydrogenated block copolymer (II) can be produced.

(Content ratio of olefin rubber (I) and hydrogenated block copolymer (II))
In the thermoplastic elastomer composition of the present invention, the content ratio [(I) / (II)] of the olefin rubber (I) and the hydrogenated block copolymer (II) is 90/10 to 10 by mass ratio. / 90, preferably 90/10 to 50/50, more preferably 80/20 to 20/80, and still more preferably 80/20 to 60/40. Within this range, the moldability, flexibility and strain recovery at high temperatures are excellent.

(Polyolefin resin (III))
Examples of the polyolefin resin (III) used in the present invention include polyethylene resin, polypropylene resin, poly (1-butene), poly (4-methyl-1-pentene) and the like. Polyolefin resin (III) may be used individually by 1 type, and may use 2 or more types together. Among these, from the viewpoint of moldability, at least one selected from the group consisting of polyethylene resins and polypropylene resins is preferable, and polypropylene resins are more preferable.
Here, the polyethylene-based resin refers to a polymer having a content of structural units derived from ethylene (hereinafter sometimes abbreviated as ethylene content) of 60 mol% or more, and the ethylene content is Preferably it is 70 mol% or more, More preferably, it is 80 mol% or more. The polypropylene resin refers to a polymer in which the content of structural units derived from propylene (hereinafter sometimes abbreviated as propylene content) is 60 mol% or more, and the propylene content is preferably Is 70 mol% or more, more preferably 80 mol% or more, and particularly preferably 90 mol% or more.
Needless to say, the polyolefin resin (III) is distinguished from the olefin rubber (I) which is “rubber”.

Examples of polyethylene resins include ethylene homopolymers such as high density polyethylene, medium density polyethylene, and low density polyethylene; ethylene / butene-1 copolymer, ethylene / hexene copolymer, ethylene / heptene copolymer, Ethylene / octene copolymer, ethylene / 4-methylpentene-1 copolymer, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / acrylic acid ester copolymer, ethylene / methacrylic acid copolymer And ethylene-based copolymers such as ethylene / methacrylic acid ester copolymers. Among these, at least one selected from the group consisting of high density polyethylene, medium density polyethylene, and low density polyethylene is preferable.

Examples of polypropylene resins include propylene homopolymer, ethylene / propylene random copolymer, ethylene / propylene block copolymer, propylene / butene-1 copolymer, propylene / ethylene / butene-1 copolymer, propylene / 4-methylpentene-1 copolymer and the like. Among these, from the viewpoint of moldability, at least one selected from the group consisting of a propylene homopolymer, an ethylene / propylene random copolymer, and an ethylene / propylene block copolymer is preferable.

The melt flow rate (MFR) measured under the conditions of 230 ° C. and 2.16 kg of the polyolefin resin (III) is preferably 0.1 g / 10 min or more from the viewpoint of moldability. It is more preferably 1 to 50 g / 10 minutes, further preferably 1 to 40 g / 10 minutes, and particularly preferably 5 to 40 g / 10 minutes. The MFR is a value measured according to JIS K7210-1 (2014).

The content of the polyolefin resin (III) is 10 to 200 parts by weight, preferably 10 to 100 parts by weight, based on a total of 100 parts by weight of the olefin rubber (I) and the hydrogenated block copolymer (II). 15 to 100 parts by mass is more preferable, 20 to 80 parts by mass is more preferable, and 30 to 70 parts by mass is still more preferable. If it is less than 10 parts by mass with respect to 100 parts by mass in total of the olefin rubber (I) and the hydrogenated block copolymer (II), molding processability is poor, whereas if it exceeds 200 parts by mass, flexibility and rubber Elasticity decreases.
In the thermoplastic elastomer composition of the present invention, the polyolefin resin (III) forms a continuous phase in the thermoplastic elastomer composition by adjusting the content of the polyolefin resin (III) in the above range. In addition, the olefin rubber (I) and the hydrogenated block copolymer (II) have a dispersed morphology in the form of fine particles, and this is an adhesive force, flexibility, and flexibility to the vulcanized rubber and the dynamically crosslinked thermoplastic elastomer (TPV). It is presumed to have a good influence on the weather resistance and molding processability.

(Softener (IV))
Examples of the softener (IV) include petroleum-based process oils such as paraffinic process oil and naphthenic process oil; aromatic process oils; phthalic acid derivatives such as dioctyl phthalate and dibutyl phthalate; white oil; mineral oil; Vegetable oil-based softeners such as oil and rosin; liquid paraffin; liquid co-oligomer of ethylene and α-olefin, liquid polybutene, liquid polybutadiene, liquid polyisoprene, liquid polyisoprene / butadiene copolymer, liquid styrene / butadiene copolymer And synthetic softeners such as liquid styrene / isoprene copolymer.
As the softener (IV), the kinematic viscosity at 40 ° C. is 20 to 800 mm ² / s (preferably 40 to 600 mm ² / s, more preferably 60 to 400 mm ² / s, and further preferably 60 to 200 mm ² / s. Particularly preferred is a softening agent of 70 to 120 mm ² / s). The kinematic viscosity is a value measured according to JIS K2283 (2000).
The pour point of the softening agent (IV) is preferably −40 to 0 ° C., more preferably −30 to 0 ° C. The flash point (COC method) of the softening agent (IV) is preferably 200 to 400 ° C., more preferably 250 to 350 ° C.

As the softening agent (IV), petroleum process oil, liquid co-oligomer of ethylene and α-olefin, and liquid paraffin are preferable, petroleum process oil is more preferable, and paraffin process oil is more preferable.
The softener (IV) may be used alone or in combination of two or more.
Examples of commercially available softeners (IV) include paraffinic process oil and naphthenic process oil (preferably paraffinic process oil) in the “Diana Process Oil” series marketed by Idemitsu Kosan Co., Ltd. it can.

The content of the softening agent (IV) is 15 to 300 parts by weight, preferably 15 to 150 parts by weight, based on 100 parts by weight in total of the olefin rubber (I) and the hydrogenated block copolymer (II). It is more preferably 20 to 120 parts by mass, and further preferably 20 to 100 parts by mass. When the total amount of the olefin rubber (I) and the hydrogenated block copolymer (II) exceeds 100 parts by mass, the mechanical properties are deteriorated and the molded product obtained from the thermoplastic elastomer composition is used. The softening agent (IV) tends to bleed out and the mechanical strength is lowered. On the other hand, if it is less than 15 parts by mass, the flexibility and moldability of the thermoplastic elastomer composition will be insufficient.
In addition, the thermoplastic elastomer composition of the present invention has the advantage of having sufficient flexibility and moldability even if the content of the softening agent (IV) is reduced. For example, compared with the thermoplastic elastomer composition described in JP-A-2014-080488 (Patent Document 1), the content of the softening agent (IV) for imparting the same or higher flexibility and molding processability is small. . Therefore, in the thermoplastic elastomer composition of the present invention, the upper limit of the content of the softening agent (IV) may be 60 parts by mass or 50 parts by mass in any of the above numerical ranges. It may be 40 parts by mass or 30 parts by mass.

When the olefin rubber (I) and the polymer block (B) of the hydrogenated block copolymer (II) are crosslinked, a crosslinking agent (V), a crosslinking aid (VI) and a crosslinking accelerator (described later) VII) can be included as required. That is, the thermoplastic elastomer composition of the present invention may be obtained by crosslinking the olefin rubber (I) and the polymer block (B) of the hydrogenated block copolymer (II). By crosslinking in this way, the morphology tends to be easily formed.

(Crosslinking agent (V))
Examples of the crosslinking agent (V) include radical generators, sulfur and sulfur compounds.
Examples of the radical generator include dialkyl monoperoxides such as dicumyl peroxide, di-t-butyl peroxide, and t-butylcumyl peroxide; 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, , 5-Dimethyl-2,5-di (t-butylperoxy) hexyne-3, 1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy) -3,3 Diperoxides such as 5-trimethylcyclohexane and n-butyl-4,4-bis (t-butylperoxy) valerate; Diacyl peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide and 2,4-dichlorobenzoyl peroxide; t-butyl Monoacyl alkyl pens such as peroxybenzoate Oxide; percarbonate such as t- butyl peroxy isopropyl carbonate; diacetyl peroxide, organic peroxides such as diacyl peroxides such as lauroyl peroxide. These may be used individually by 1 type and may use 2 or more types together. Of these, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and dicumyl peroxide are preferable from the viewpoint of reactivity.
When a radical generator is used, the content thereof is preferably 0.01 to 15 parts by mass, more preferably 100 parts by mass relative to the total of 100 parts by mass of the olefin rubber (I) and the hydrogenated block copolymer (II). 0.05 to 10 parts by mass.

Examples of the sulfur compound include sulfur monochloride and sulfur dichloride.
When sulfur or a sulfur compound is used, the content thereof is preferably 0.1 to 20 parts by mass, more preferably 100 parts by mass relative to the total of 100 parts by mass of the olefin rubber (I) and the hydrogenated block copolymer (II). Is 0.5 to 10 parts by mass, more preferably 1 to 10 parts by mass.

Other crosslinking agents (V) include phenolic resins such as alkylphenol resins and brominated alkylphenol resins; combinations of p-quinonedioxime and lead dioxide, p, p'-dibenzoylquinonedioxime and trilead tetroxide Etc. can also be used.

(Crosslinking aid (VI))
As the crosslinking aid (VI), a known crosslinking aid can be used. For example, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, trimellitic acid triallyl ester, 1,2,4-benzenetricarboxylic acid triallyl ester, triallyl isocyanurate, 1,6-hexanediol dimethacrylate, 1, 9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, divinylbenzene, glycerol dimethacrylate, 2-hydroxy-3-acryloyl Polyfunctional monomers such as oxypropyl methacrylate; stannous chloride, ferric chloride, organic sulfonic acid, polychloropropyl Emissions, and the like chlorosulfonated polyethylene. Of these, triallyl isocyanurate is preferable.
The crosslinking aid (VI) may be used by impregnating diatomaceous earth, white carbon or the like. In particular, the polyfunctional monomer (and triallyl isocyanurate) is preferably impregnated in diatomaceous earth or white carbon, and more preferably impregnated in white carbon.
As the crosslinking aid (VI), one kind may be used alone, or two or more kinds may be used in combination.
When the crosslinking aid (VI) is used, the content thereof is preferably 0.1 to 40 parts by mass with respect to a total of 100 parts by mass of the olefin rubber (I) and the hydrogenated block copolymer (II). More preferred is 0.5 to 20 parts by mass, and further preferred is 2 to 20 parts by mass.

(Crosslinking accelerator (VII))
Examples of the crosslinking accelerator (VII) include thiazoles such as N, N-diisopropyl-2-benzothiazole-sulfenamide, 2-mercaptobenzothiazole, 2- (4-morpholinodithio) benzothiazole; diphenylguanidine, Guanidines such as triphenylguanidine; aldehyde-amine reactants such as butyraldehyde-aniline reactant, hexamethylenetetramine-acetaldehyde reactant or aldehyde-ammonia reactants; imidazolines such as 2-mercaptoimidazoline; thiocarbanilide, diethyl Thioureas such as urea, dibutylthiourea, trimethylthiourea, diorthotolylthiourea; dibenzothiazyl disulfide; tetramethylthiuram monosulfide, tetramethylthiuramdi Thiuram monosulfides or thiuram polysulfides such as luffide, pentamethylenethiuram tetrasulfide; thiocarbamates such as zinc dimethyldithiocarbamate, zinc ethylphenyldithiocarbamate, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, tellurium diethyldithiocarbamate; Xanthates such as zinc dibutylxanthate; zinc white and the like. Crosslinking accelerator (VII) may be used individually by 1 type, and may use 2 or more types together.

[Other ingredients]
The thermoplastic elastomer composition of the present invention may further contain another thermoplastic polymer. Other thermoplastic polymers include, for example, polyphenylene ether resins; polyamide 6, polyamide 6 · 6, polyamide 6 · 10, polyamide 11, polyamide 12, polyamide 6 · 12, polyhexamethylenediamine terephthalamide, polyhexamethylene Polyamide resins such as diamine isophthalamide and xylene group-containing polyamide; Polyester resins such as polyethylene terephthalate and polybutylene terephthalate; Acrylic resins such as polymethyl acrylate and polymethyl methacrylate; Polyoxymethylene homopolymer, Polyoxymethylene Polyoxymethylene resins such as copolymers; Styrene resins such as styrene homopolymers, acrylonitrile-styrene resins, acrylonitrile-butadiene-styrene resins; Bonate resin; Styrenic elastomers such as styrene / butadiene copolymer rubber and styrene / isoprene copolymer rubber and hydrogenated products or modified products thereof (except liquid ones); natural rubber; chloroprene rubber; acrylic Examples thereof include rubber, acrylonitrile / butadiene rubber, epichlorohydrin rubber, silicone rubber, chlorosulfonated polyethylene, urethane rubber, polyurethane elastomer, polyamide elastomer, polyester elastomer, and soft vinyl chloride resin.
In addition, when other thermoplastic polymers are contained, the content may be used within a range that does not impair the flexibility and mechanical strength of the thermoplastic elastomer composition, and before adding the other thermoplastic polymers. The amount is preferably 200 parts by mass or less, more preferably 100 parts by mass or less, and still more preferably 50 parts by mass or less with respect to 100 parts by mass of the thermoplastic elastomer composition.

The thermoplastic elastomer composition of the present invention may further contain various additives as long as the effects of the present invention are not impaired. Examples of such additives include lubricants, foaming agents, nucleating agents, antioxidants, heat stabilizers, light resistance agents, weathering agents, metal deactivators, ultraviolet absorbers, light stabilizers, copper damage prevention agents, and fillers. , Reinforcing agents, antistatic agents, antibacterial agents, fungicides, dispersants, coloring agents and the like. One of these may be contained alone, or two or more may be contained.

Among these, a lubricant is preferable because it improves the fluidity of the thermoplastic elastomer composition and suppresses thermal degradation. Examples of the lubricant include silicone oils; hydrocarbon lubricants such as paraffin wax, microwax and polyethylene wax; butyl stearate, stearic acid monoglyceride, pentaerythritol tetrastearate, stearyl stearate, unsaturated fatty acid monoamide, and the like. It is done. These may be used individually by 1 type and may use 2 or more types together.
When the lubricant is contained, the content thereof is preferably 0.01 to 3 parts by weight, more preferably 0.05 to 1 part by weight, and still more preferably 100 parts by weight of the thermoplastic elastomer composition excluding the lubricant. 0.1 to 0.8 part by mass.

In addition, the foaming agent may be used in the production of a weather seal. Examples of the foaming agent include inorganic foaming agents such as ammonium carbonate, ammonium hydrogen carbonate, sodium hydrogen carbonate, ammonium nitrite, sodium borohydride, and azides; N, N′-dinitrosopentamethylenetetramine, N, N ′ -N-nitroso compounds such as dimethyl-N, N'-dinitrosotephthalamide; azo compounds such as azobisisobutyronitrile, azodicarbonamide, barium azodicarboxylate; trichloromonofluoromethane, dichloromonofluoro Fluorinated alkanes such as methane; sulfonylhydrazine compounds such as paratoluenesulfonyl hydrazide, diphenylsulfone-3,3′-disulfonylhydrazide, 4,4′-oxybis (benzenesulfonylhydrazide), allylbis (sulfonylhydrazide), etc. Sulfonyl semicarbazide compounds such as p-toluylenesulfonyl semicarbazide and 4,4′-oxybis (benzenesulfonyl semicarbazide); organic foams such as triazole compounds such as 5-morpholyl-1,2,3,4-thiatriazole Agents: Thermally expandable fine particles encapsulated in microcapsules in which a heat-expandable compound such as isobutane and pentane is made of a thermoplastic resin such as vinylidene chloride, acrylonitrile, acrylic acid ester, and methacrylic acid ester. These may be used individually by 1 type and may use 2 or more types together.
Thus, when making a weather seal into a foam, you may contain a nucleating agent as needed. Examples of the nucleating agent include metal oxides, composite oxides, metal carbonates such as talc, silica, alumina, mica, titania, zinc oxide, zeolite, calcium carbonate, magnesium carbonate, barium sulfate, and aluminum hydroxide. A metal sulfate, a metal hydroxide, etc. can be used. By using the nucleating agent, the cell diameter of the foam cell of the foam tends to be easily adjusted, and it is easy to obtain a foam having appropriate flexibility.

[Crosslinking method]
As described above, the polymer block (B) portion of the olefin rubber (I) and the hydrogenated block copolymer (II) may be crosslinked. As a crosslinking method, a method in which a crosslinking agent (V), a crosslinking assistant (VI) and a crosslinking accelerator (VII) are appropriately added to the olefin rubber (I) and the hydrogenated block copolymer (II) and kneaded. (Crosslinking method 1), resin crosslinking method (crosslinking method 2), quinoid crosslinking method (crosslinking method 3), methods using active energy rays (crosslinking method 4), and the like. Hereinafter, these crosslinking methods will be described in order.

<About crosslinking method 1>
In the thermoplastic elastomer composition of the present invention, a crosslinking agent (V), a crosslinking assistant (VI) and a crosslinking accelerator (VII) are appropriately added to the olefin rubber (I) and the hydrogenated block copolymer (II). Then, the polymer block (B) of the olefin rubber (I) and the hydrogenated block copolymer (II) can be crosslinked.
For example, a crosslinking aid (VI) such as the polyfunctional monomer, dibenzothiazyl disulfide and tetramethylthiuram disulfide (so-called disulfide type) as necessary together with the crosslinking agent (V) such as the radical generator. A crosslinking accelerator (VII) such as a compound) may be used.
In the case of performing crosslinking by such a method, for example, a method of melt-kneading a thermoplastic elastomer composition containing a radical generator and, if necessary, another thermoplastic resin, under heating can be mentioned. The heating temperature is preferably 140 to 230 ° C. Melt-kneading can be carried out batchwise or continuously with an apparatus such as an extruder, kneader, roll, plastograph or the like. The crosslinking reaction proceeds by such a melt-kneading process.

When sulfur or a sulfur compound is used as the crosslinking agent (V), crosslinking accelerators such as thiazoles, guanidines, butyraldehyde-aniline reactants, hexamethylenetetramine-acetaldehyde reactants, aldehyde-amine reactants ( It is highly preferred to use VII) together.
When cross-linking is carried out by such a method, the cross-linking agent (V), the cross-linking accelerator (VII) and the like are preferably used at 50 to 250 ° C. (more preferably 80 to 200 ° C.) using a mixer such as a roll or a Banbury mixer. After kneading, crosslinking can be formed by maintaining the temperature at 60 ° C. or higher (more preferably 90 to 250 ° C.), usually for 1 minute to 2 hours (more preferably 5 minutes to 1 hour).

<About crosslinking method 2>
In the crosslinking method by the resin crosslinking method, phenolic resins such as alkylphenol resins and brominated alkylphenol resins are used as the crosslinking agent (V), and stannous chloride, ferric chloride, organic sulfonic acid, Polychloroprene or chlorosulfonated polyethylene is used.
When crosslinking is carried out by such a method, the crosslinking temperature is preferably 100 to 250 ° C, more preferably 130 to 220 ° C. When resin crosslinking is performed, it is extremely preferable to use a crosslinking accelerator (VII) in combination.

<About crosslinking method 3>
In the crosslinking method by the quinoid crosslinking method, a combination of p-quinonedioxime and lead dioxide, p, p′-dibenzoylquinonedioxime and trilead tetroxide, or the like is used as the crosslinking agent (V).
When crosslinking is carried out by such a method, the crosslinking temperature is preferably 90 to 250 ° C, more preferably 110 to 220 ° C. When performing quinoid crosslinking, it is preferable to use a crosslinking accelerator (VII) in combination.

<About crosslinking method 4>
Examples of active energy rays that can be used in the crosslinking method using active energy rays include particle rays, electromagnetic waves, and combinations thereof. Examples of the particle beam include an electron beam (EB) and an α ray, and examples of the electromagnetic wave include an ultraviolet ray (UV), a visible ray, an infrared ray, a γ ray, and an X ray. Among these, an electron beam (EB) or an ultraviolet ray (UV) is preferable.
There is no restriction | limiting in particular in irradiation time and irradiation amount, According to the grade of bridge | crosslinking, it can select arbitrarily.

(Method for producing thermoplastic elastomer composition)
There is no restriction | limiting in particular in the manufacturing method of the thermoplastic elastomer composition of this invention.
For example, [1] Manufacture a thermoplastic elastomer composition containing olefin rubber (I), hydrogenated block copolymer (II), polyolefin resin (III) and softener (IV) in specific proportions. A mixture of olefin rubber (I), polyolefin resin (III) and softening agent (IV) which has been previously cross-linked is prepared, to which hydrogenated block copolymer (II) and polyolefin resin (III) are prepared. And a method of melt-mixing after further adding a mixture of the softening agent (IV).
[2] Olefin rubber (I), polyolefin resin (III), softener (IV), and, if necessary, crosslinking agent (V), crosslinking aid (VI) and crosslinking accelerator (VII) Etc., and then adding hydrogenated block copolymer (II), or hydrogenated block copolymer (II) and softener (IV), and dynamically crosslinking the mixture under melting conditions. The olefin-based rubber (I) is preferably cross-linked at the same time that each component can be mixed uniformly.
Here, “dynamically cross-linking under melting conditions” in the present specification means cross-linking while applying a shear stress to the mixture in a molten state by kneading.

As a device for performing dynamic crosslinking for producing the thermoplastic elastomer composition of the present invention, any of melt-kneading devices capable of uniformly mixing each component can be used, for example, a single screw extruder, a twin screw extruder, or the like. Machine, kneader, Banbury mixer, etc. Among them, it is preferable to use a twin screw extruder that has a large shearing force during kneading and can be operated continuously.
A weather seal can be obtained from the obtained thermoplastic elastomer composition by a known molding method, preferably extrusion molding or injection molding. In particular, when forming a corner portion of a weather seal, injection molding is used. When forming the straight portion of the weather seal, extrusion molding is preferably used.
In the case of a thermoplastic elastomer composition containing a foaming agent, foam molding is performed. The foam molding method includes a chemical method of foaming by decomposition or reaction of the foaming agent, the chemical method and supercritical foaming. Or the method of using together with physical methods, such as water foaming, is mentioned. Using these methods, foam molding can be performed by a method usually used for foam molding, such as injection foam molding and extrusion foam molding. For example, a foam for forming a corner portion of a weather seal is obtained by injection-foaming a thermoplastic elastomer composition dry blended with a foaming agent into a mold having a cavity having a desired shape. It is done.

(Physical properties and properties of thermoplastic elastomer composition)
The thermoplastic elastomer composition of the present invention has a hardness (JIS-A) measured according to the method described in the examples of 30 to 90, specifically 40 to 80, and has a flexibility suitable as a weather seal. In particular, for a glass run corner, the upper limit of hardness is preferably 80 or less, more preferably 76 or less, and for a door seal corner, the upper limit of hardness is preferably 57 or less, more preferably 52 or less. preferable.
Further, since the adhesive strength to vulcanized rubber measured according to the method described in the examples is 100 to 300 N / cm ² and the adhesive strength to TPV is 100 to 400 N / cm ² , the adhesive strength to vulcanized rubber and TPV Excellent power. In particular, if a corner portion of the glass run, adhesion to TPV is preferably 250 N / cm ² or more, more preferably 310N / cm ² or more, adhesion to vulcanized EPDM is 220 N / cm ² or more, 240 N / cm ² or more is more preferable (see Table 3). Further, if a corner portion of the door seal, adhesion to TPV is preferably 110N / cm ² or more, more preferably 140 N / cm ² or more, adhesion to vulcanized EPDM is 100 N / cm ² or more, 115 N / cm ² or more is more preferable (see Table 4).
Furthermore, the thermoplastic elastomer composition of the present invention is also excellent in weather resistance and moldability.

[Members, weather seals, weather seal corner members]
This invention provides the member which has the site | part (X1) which consists of a thermoplastic elastomer composition of this invention. Part (X1) may be a part of the member or the whole. That is, this invention also provides the member which has the site | part (Y1) which consists of a material different from the thermoplastic elastomer composition of this invention other than a site | part (X1).
There are no particular restrictions on the material of the site (Y1), but in the case of weather seal applications, vulcanized rubber, dynamic cross-linked thermoplastic elastomer (TPV), and the like can be mentioned.
The vulcanized rubber includes (1) a cross-linked product of ethylene and one or more α-olefins having 3 to 20 carbon atoms, and (2) ethylene and one α-olefin having 3 to 20 carbon atoms. Examples thereof include a cross-linked product of a copolymer of the above and one or more non-conjugated polyenes. In particular, the vulcanized rubber is preferably a cross-linked product of a copolymer of ethylene, one or more α-olefins having 3 to 20 carbon atoms and one or more nonconjugated polyenes. More preferred is a crosslinked product of the above copolymer.
The TPV is preferably an olefinic TPV containing an olefinic resin and an olefinic rubber, and more preferably an olefinic TPV containing a polypropylene resin and an olefinic rubber. The olefin-based rubber is preferably a cross-linked product of ethylene, one or more α-olefins having 3 to 20 carbon atoms and one or more nonconjugated polyenes, and includes ethylene, propylene and nonconjugated polyenes. A cross-linked product of a copolymer (EPDM) is more preferred. As the TPV, commercially available products such as “Excellink 1303B” and “Excellink 1703B” (both manufactured by JSR Corporation) can also be used.
The “alpha-olefin having 3 to 20 carbon atoms” and “non-conjugated polyene” are the same as those described in the olefin rubber (I), and the preferred ones are also the same.
Vulcanized rubber and TPV contain various additives such as vulcanization aids, vulcanization accelerators, softeners, anti-aging agents, carbon black, zinc oxide, and lubricants as necessary. May be.

The present invention also provides a member having a part (X2) made of the thermoplastic elastomer composition of the present invention in addition to the part (X1). The material of the part (X2) may be the same as or different from the thermoplastic elastomer composition forming the part (X1). When the material of the part (X2) is different from the thermoplastic elastomer composition forming the part (X1), it becomes a member using two or more thermoplastic elastomer compositions of the present invention.

Since the thermoplastic elastomer composition of the present invention is excellent in molding processability, the part (X1) made of the thermoplastic elastomer composition of the present invention is preferably a part obtained by injection molding.

The present invention also provides a weather seal containing the member. More specifically, a weather seal having a corner portion made of the portion (X1) and a straight portion made of the portion (X2) or (Y1) is provided.
The weather seal is useful for automobiles, ships or aircraft.
Since the part (X1) is excellent in flexibility and molding processability, it is particularly useful as a corner member and is useful as a weather seal corner member. For example, if it is used for automobiles, it is useful as a corner member of a glass run, a corner member of a door seal or the like.

Any of the items described in this specification can be adopted arbitrarily. That is, not only one preferable item but also a preferable item and other preferable items can be used in combination.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The physical properties were measured by the following methods.

(1) Peak top molecular weight (Mp)
According to gel permeation chromatography (GPC) measurement under the following conditions, peaks in terms of polystyrene in the polymer blocks (A1) and (A2) before hydrogenation and in the hydrogenated block copolymer (II) after hydrogenation The top molecular weight (Mp) was determined. The Mp (A2) of the polymer block (A2) is obtained by subtracting the Mp of the polymer block [A1-B] before hydrogenation from the Mp of the hydrogenated block copolymer (II) after hydrogenation. Asked.
(GPC measurement equipment and measurement conditions)
・ Device: GPC device “HLC-8320” (manufactured by Tosoh Corporation)
Separation column: Column “TSKgelSuperHZM-M” (manufactured by Tosoh Corporation)
・ Eluent: Tetrahydrofuran ・ Eluent flow rate: 0.7 ml / min
Sample concentration: 5 mg / 10 mL
-Column temperature: 40 ° C
-Detector: Differential refractive index (RI) detector-Calibration curve: Created using standard polystyrene

(2) Content of polymer block (A) The hydrogenated block copolymer (II) was dissolved in CDCl ₃ and ¹ H-NMR spectrum was measured [apparatus: JNM-Lambda 500 (manufactured by JEOL Ltd.) ), Measurement temperature: 50 ° C.], and the content of the polymer block (A) was calculated from the peak intensity derived from styrene.

(3) Hydrogenation rate of hydrogenated block copolymer (II) Measure the iodine value of the block copolymer before and after hydrogenation, and use the measured value to determine the hydrogenated block copolymer (II) according to the following formula: The hydrogenation rate (%) of was calculated.
Hydrogenation rate (%) = {1− (iodine value of block copolymer after hydrogenation / iodine value of block copolymer before hydrogenation)} × 100
(Iodine number measurement method)
The iodine value was measured by the Wiis method using a cyclohexane solution of the block copolymer before and after hydrogenation.

(4) Vinyl bond content of polymer block (B) The block copolymer before hydrogenation was dissolved in CDCl ₃ and ¹ H-NMR spectrum was measured [apparatus: JNM-Lambda 500 (manufactured by JEOL Ltd.) , Measurement temperature: 50 ° C.], the total peak area of the structural unit derived from isoprene and / or butadiene, the 3,4-bond unit and 1,2-bond unit in the isoprene structural unit, and 1,2- in the butadiene structural unit In the case of a bond unit or a structural unit derived from a mixture of isoprene and butadiene, the vinyl bond content (of 3,4-bond units and 1,2-bond units is determined from the ratio of peak areas corresponding to each of the bond units. The total content) was calculated.

(5) Molecular weight distribution (Mw / Mn)
The weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were determined by gel permeation chromatography (GPC) in terms of standard polystyrene.
The measurement apparatus and conditions were the same as the GPC measurement apparatus and measurement conditions in the measurement of the peak top molecular weight (Mp).

(6) Glass transition temperature (° C)
Using a differential scanning calorimeter “DSC6200” (manufactured by Seiko Instruments Inc.), the hydrogenated block copolymer (II) is precisely weighed, and from −120 ° C. to 100 ° C. at a heating rate of 10 ° C./min. The temperature was raised, the temperature at the inflection point of the measurement curve was read and taken as the glass transition temperature.

[Each component used in Examples]
Below, the detail or manufacturing method of each component used by the Example and the comparative example is shown.

[Olefin rubber (I)]
Olefin rubber (I): ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber “JSR EP37F” (manufactured by JSR Corporation, iodine value = 8, Mooney viscosity (ML _{1 + 4} , 100 ° C.) = 100 , Ethylene content 54 mol%)

[Hydrogenated block copolymer (II)]
(II) -1: Hydrogenated product of styrene- (butadiene / isoprene) -styrene block copolymer (see Production Example 1 and Table 1)
(II) -2: Hydrogenated product of styrene-butadiene-styrene block copolymer (see Production Example 2 and Table 1)
(II) -3: Hydrogenated product of styrene-isoprene-styrene block copolymer (see Production Example 3 and Table 1)
(II) -4: Hydrogenated product of styrene-isoprene-styrene block copolymer (see Production Example 4 and Table 1)

[Hydrogenated block copolymer (for comparison)]
(II ′)-5: Hydrogenated product of styrene- (butadiene / isoprene) -styrene block copolymer (see Production Example 5 and Table 1)
(II ′)-6: Hydrogenated product of styrene-isoprene-styrene block copolymer (see Production Example 6 and Table 1)
(II ′)-7: Hydrogenated product of styrene-isoprene-styrene block copolymer (see Production Example 7 and Table 1)

[Production Example 1] Production of hydrogenated block copolymer (II) -1 In a pressure-resistant container purged with nitrogen and dried, in a use amount shown in Table 1, cyclohexane as a solvent and sec-butyl as an anionic polymerization initiator Lithium (10.5 mass% cyclohexane solution) was charged, and tetrahydrofuran was charged as a Lewis base. After the temperature was raised to 60 ° C., styrene (A1) was added and polymerized for 1 hour, followed by adding a mixture of butadiene and isoprene for 2 hours, and further adding styrene (A2) and polymerizing for 1 hour. A reaction solution containing a styrene- (butadiene / isoprene) -styrene block copolymer was obtained.
To this reaction solution, 5% by mass of palladium carbon (palladium supported amount: 5% by mass) as a hydrogenation catalyst was added to the block copolymer, and the reaction was performed for 10 hours under conditions of a hydrogen pressure of 2 MPa and 150 ° C. .
After allowing to cool and release the pressure, the palladium carbon is removed by filtration, the filtrate is concentrated, and further dried under vacuum to obtain a hydrogenated styrene- (butadiene / isoprene) -styrene block copolymer (hydrogenated block copolymer). Compound (II) -1) was obtained. The amount of each component used and the measurement results of the physical properties of the hydrogenated block copolymer (II) -1 are shown in Table 1.

[Production Example 2] Production of hydrogenated block copolymer (II) -2 In a pressure-resistant vessel purged with nitrogen and dried, in a use amount shown in Table 1, cyclohexane as a solvent and sec-butyl as an anionic polymerization initiator Lithium (10.5 mass% cyclohexane solution) was charged, and N, N, N ′, N′-tetramethylethylenediamine was charged as a Lewis base. After the temperature was raised to 40 ° C., styrene (A1) was added for polymerization for 1 hour, butadiene was subsequently added for polymerization for 2 hours, and styrene (A2) was further added for polymerization for 1 hour. -A reaction solution containing a styrene block copolymer was obtained.
To this reaction solution, 5% by mass of palladium carbon (palladium supported amount: 5% by mass) as a hydrogenation catalyst was added to the block copolymer, and the reaction was performed for 10 hours under conditions of a hydrogen pressure of 2 MPa and 150 ° C. .
After allowing to cool and release the pressure, palladium carbon is removed by filtration, the filtrate is concentrated, and further dried under vacuum to give a hydrogenated styrene-butadiene-styrene block copolymer (hydrogenated block copolymer (II)). -2). Table 1 shows the amount of each component used and the measurement results of the physical properties of the hydrogenated block copolymer (II) -2.

[Production Example 3] Production of hydrogenated block copolymer (II) -3 In a pressure-resistant container purged with nitrogen and dried, in a use amount shown in Table 1, cyclohexane as a solvent and sec-butyl as an anionic polymerization initiator Lithium (10.5 mass% cyclohexane solution) was charged, and tetrahydrofuran was charged as a Lewis base. After the temperature was raised to 60 ° C., styrene (A1) was added and polymerized for 1 hour, then isoprene was added to conduct polymerization for 2 hours, and further styrene (A2) was added and polymerized for 1 hour to obtain styrene-isoprene. -A reaction solution containing a styrene block copolymer was obtained.
To this reaction solution, 5% by mass of palladium carbon (palladium supported amount: 5% by mass) as a hydrogenation catalyst was added to the block copolymer, and the reaction was performed for 10 hours under conditions of a hydrogen pressure of 2 MPa and 150 ° C. .
After allowing to cool and release the pressure, palladium carbon is removed by filtration, the filtrate is concentrated, and further dried under vacuum to obtain a hydrogenated styrene-isoprene-styrene block copolymer (hydrogenated block copolymer (II)). -3)). Table 1 shows the amount of each component used and the measurement results of the physical properties of the hydrogenated block copolymer (II) -3.

[Production Example 4] Production of hydrogenated block copolymer (II) -4 By performing the same operation as in Production Example 3, except that the amount of each component used was changed as shown in Table 1, A hydrogenated product of styrene-isoprene-styrene block copolymer (referred to as hydrogenated block copolymer (II) -4) was obtained. The amount of each component used and the measurement results of the physical properties of the hydrogenated block copolymer (II) -4 are shown in Table 1.

[Production Example 5 (for comparison)] Production of hydrogenated block copolymer (II ')-5 The same operation as in Production Example 1 except that the amounts used of each component were changed as shown in Table 1. To obtain a hydrogenated product of styrene- (butadiene / isoprene) -styrene block copolymer (referred to as hydrogenated block copolymer (II ′)-5). Table 1 shows the amount of each component used and the measurement results of the physical properties of the hydrogenated block copolymer (II ′)-5.

[Production Example 6 (for comparison)] Production of hydrogenated block copolymer (II ')-6 The same operation as in Production Example 3 except that the amount of each component used was changed as shown in Table 1. To obtain a hydrogenated product of styrene-isoprene-styrene block copolymer (referred to as hydrogenated block copolymer (II ′)-6). Table 1 shows the amount of each component used and the measurement results of the physical properties of the hydrogenated block copolymer (II ′)-6.

[Production Example 7 (for comparison)] Production of hydrogenated block copolymer (II ')-7 The same operation as in Production Example 3 except that the amounts used of the respective components were changed as shown in Table 1. To obtain a hydrogenated product of styrene-isoprene-styrene block copolymer (referred to as hydrogenated block copolymer (II ′)-7). Table 1 shows the amount of each component used and the measurement results of the physical properties of the hydrogenated block copolymer (II ′)-7.

[Polyolefin resin (III)]
Polyolefin resin (III): Random polypropylene (propylene ethylene random copolymer) “J226T” (MFR [230 ° C., load 21.2 N] = 20 g / 10 min, manufactured by Prime Polymer Co., Ltd.)
[Softener (IV)]
Softener (IV): Paraffinic process oil “Diana Process PW-90” (kinematic viscosity = 95.54 mm ² / s (40 ° C.), manufactured by Idemitsu Kosan Co., Ltd.)
[Crosslinking agent (V)]
Cross-linking agent (V): 2,5-dimethyl-2,5-di (t-butylperoxy) hexane / silica (mass ratio: 40/60) “Perhexa® 25B-40” (manufactured by NOF Corporation) )
[Crosslinking aid (VI)]
Crosslinking aid (VI): triallyl isocyanurate / white carbon (mass ratio: 60/40) “Tyke (registered trademark) WH-60” (manufactured by Nippon Kasei Co., Ltd.)
[Lubricant]
Lubricant: Unsaturated fatty acid monoamide “Diamid (registered trademark) L-200” (manufactured by Nippon Kasei Co., Ltd.)

[Examples 1 to 16, Comparative Examples 1 to 14]
All components were premixed by dry blending using a super mixer V-20 (manufactured by Kawata Co., Ltd.) at the blending ratio (unit: parts by mass) shown in Table 3 or Table 4, and then a twin screw extruder [Japan Co., Ltd. Pellets by supplying to steelworks “TEX-44XCT”, screw length (L) / screw diameter (D) = 42], melting and kneading at a temperature of 170 to 200 ° C. and a rotation speed of 300 min ⁻¹ and hot cutting. A thermoplastic elastomer composition was produced.
Each physical property and characteristic was measured or evaluated according to the following method using the obtained pellet-shaped thermoplastic elastomer composition. The results are shown in Table 3 and Table 4.

[Measurement or evaluation method of physical properties and characteristics]
(7) Hardness (JIS-A)
The pellets of the thermoplastic elastomer composition obtained in each example were injection molded at a cylinder temperature of 230 ° C. using an injection molding machine “EC75SX” (manufactured by Toshiba Machine Co., Ltd.) to produce a sheet having a length of 100 mm, a width of 35 mm, and a thickness of 2 mm. did. Next, according to JIS K6253-3 (2012), three sheets of the obtained sheets were stacked to form a 6 mm-thick laminate, and the hardness was measured. The hardness meter used was a type A durometer, and the measured value was recorded as an instantaneous value.
It shows that the molded object obtained is excellent in a softness | flexibility, so that hardness is small.

(8) Moldability The pellets of the thermoplastic elastomer composition obtained in each example were injection molded at a cylinder temperature of 230 ° C. with an injection molding machine “EC75SX” (manufactured by Toshiba Machine Co., Ltd.), 100 mm long, 35 mm wide, A sheet having a thickness of 2 mm was prepared, and the sheet was cut into a length of 50 mm and a width of 35 mm to prepare a test piece. The presence or absence of a flow mark in the test piece was visually observed, and molding processability was evaluated according to the following criteria.
A: No flow mark B: Low flow mark C: Many flow marks

(9) Adhesive strength Adhesive strength with an adherend made of a dynamically crosslinked thermoplastic elastomer (TPV) or an adherend made of vulcanized rubber was measured by the following method.
(Adherent consisting of TPV)
TPV-1: Using a pellet of “Excelin 1703B” (manufactured by JSR Corporation), a test piece having a length of 50 mm, a width of 35 mm, and a thickness of 2 mm was prepared according to the method described in “(8) Moldability”, This was designated as an adherend “TPV-1.” The hardness of the TPV-1 measured according to the method described in “(7) Hardness” was 71.
TPV-2: A test piece was prepared in the same manner as TPV-1 except that pellets of “Excelin 1303B” (manufactured by JSR Corporation) were used, and this was used as an adherend “TPV-2”. The hardness of the TPV-2 measured according to the method described in “(7) Hardness” was 42.
(Adhered body made of vulcanized rubber)
Vulcanized EPDM-3: Ethylene / propylene / diene copolymer rubber “EPT4045” (Mitsui Chemicals Co., Ltd.), carbon black “Diablack H” (Mitsubishi Chemical Co., Ltd.) in the blending amounts shown in Table 2 below. Anti-aging agent “NOCRACK 6C” (manufactured by Ouchi Shinko Chemical Co., Ltd.), stearic acid “LUNAC S-20” (manufactured by Kao Corporation) and zinc white “Zinc Oxide” (manufactured by Sakai Chemical Industry Co., Ltd.) The mixture was kneaded for 6 minutes at 150 ° C. using a Banbury mixer (first kneading stage). Next, after the obtained composition was taken out and cooled, a vulcanizing agent “sulfur” (fine sulfur, 200 mesh, manufactured by Tsurumi Chemical Co., Ltd.) and a vulcanization accelerator (1) were blended in the amounts shown in Table 2 below. ) Add “Noxeller TS” (Ouchi Shinko Chemical Co., Ltd.) and vulcanization accelerator (2) “Noxeller MP” (Ouchi Shinko Chemical Co., Ltd.), and use a Banbury mixer to adjust the temperature. The mixture was kneaded at 50 ° C. and a pressure of 1 MPa for 20 minutes (kneading second stage) to obtain a kneaded product.
Further, using a compression molding machine, compression molding was carried out under the vulcanization conditions shown in Table 2 below to obtain a sheet (length 150 mm × width 150 mm × thickness 2 mm). A test piece was prepared by punching out 50 mm in length, 35 mm in width, and 2 mm in thickness from this sheet, and this was used as an adherend “vulcanized EPDM-3”. The hardness of this vulcanized EPDM-3 measured according to the method described in “(7) Hardness” was 70.

<Measurement method of adhesive strength>
Each adherend (50 mm long × 35 mm wide × 2 mm thick) obtained as described above is mounted in a cavity of 100 mm long × 35 mm wide × 2 mm thick, and injection molding machine “EC75SX” is provided there. (Manufactured by Toshiba Machine Co., Ltd.), a thermoplastic elastomer was injection molded at 230 ° C. to obtain a composite molded sheet. The sheet of the composite molded body is completely melted into one sheet having a thickness of 2 mm, that is, each adherend (TPV-1, TPV-2 or vulcanized EPDM-3) and a thermoplastic elastomer composition. A thing is the state which adhere | attached in the side surface of the sheet | seat (adhesion area: 35 mm x 2 mm).
The obtained composite molded sheet (length 100 mm × width 35 mm × thickness 2 mm) was cut into length 100 mm × width 10 mm × thickness 2 mm, and Instron universal under a temperature condition of 23 ° C. and a tensile speed condition of 200 mm / min. The adhesion between the thermoplastic elastomer composition and the adherend was measured using a tester “Instron 5566” (manufactured by Instron Japan).

(10) Weather resistance A sheet (length 100 mm × width 35 mm × thickness 2 mm) was obtained by performing the same operation as described in “(8) Molding processability”. The sheet was subjected to a light exposure test for 24 hours using “Sun Test CPS +” (light source: xenon, irradiation intensity: 550 W / m ² , manufactured by Toyo Seiki Seisakusho Co., Ltd.). The tactile sensation of the change before and after the test was investigated, and the weather resistance was evaluated according to the following criteria.
A: No change B: Some stickiness C: Stickiness

From Table 3 and Table 4, the thermoplastic elastomer compositions of the examples all have high adhesion to TPV-1, TPV-2 and vulcanized EPDM-3, and have flexibility and weather resistance. It can be seen that the moldability is also excellent.
Further, when Example 6 and Example 8 are compared, the ratio of the peak top molecular weight (Mp) in the polymer blocks (A1) and (A2) in the hydrogenated block copolymer (II) [Mp (A1) / It can be seen that Example 8 in which Mp (A2)] satisfies 1/10 to 8/10 is more excellent in moldability.
The thermoplastic elastomer compositions obtained in Examples 1 to 8 are particularly useful for glass run corners in automobiles. In addition, the thermoplastic elastomer compositions obtained in Examples 9 to 16 are particularly useful for corner portions of door seals in automobiles.
On the other hand, in Comparative Examples 1, 2, 8 and 9 using a hydrogenated block copolymer having a low hydrogenation rate, the adhesive strength to TPV may be insufficient (see Comparative Example 2), and the weather resistance is also low. It turns out that it is insufficient (refer comparative examples 1, 2, 8, and 9). In Comparative Examples 3, 4, 10 and 11 using a hydrogenated block copolymer in which the vinyl bond content of the polymer block (B) is less than 45%, the flexibility may be insufficient (Comparative Example). 3 and 10), and the adhesive strength to TPV and vulcanized rubber may be poor (see Comparative Examples 4 and 11). In Comparative Examples 5, 6, 12 and 13 using a hydrogenated block copolymer having a peak top molecular weight (Mp) exceeding 200,000, molding processability is poor and flexibility may be insufficient (Comparative Example). 12). Further, in Comparative Examples 7 and 14 in which the hydrogenated block copolymer (II) was not used, the molding processability was poor and the adhesive strength to the vulcanized rubber may be insufficient (see Comparative Example 14). I understood.

The thermoplastic elastomer composition of the present invention has high adhesion to vulcanized rubber and dynamically cross-linked thermoplastic elastomer (TPV), and is excellent in molding processability as well as flexibility and weather resistance. It is useful for weather seals, particularly for corners of weather seals.

Claims

Olefin rubber (I),
The following hydrogenated block copolymer (II),
Polyolefin resin (III) and softener (IV)
A thermoplastic elastomer composition comprising:
The content ratio [(I) / (II)] of the olefin rubber (I) and the hydrogenated block copolymer (II) is 90/10 to 10/90 by mass ratio,
The content of polyolefin resin (III) is 10 to 200 parts by mass and the content of softener (IV) is 100 parts by mass in total of olefin rubber (I) and hydrogenated block copolymer (II). A thermoplastic elastomer composition having a content of 15 to 300 parts by mass.
Hydrogenated block copolymer (II): mainly from a polymer block (A) mainly composed of a structural unit derived from an aromatic vinyl compound and a structural unit derived from at least one selected from the group consisting of isoprene and butadiene. And a hydrogenated product of a block copolymer having a polymer block (B) having a total content of 3,4-bond units and 1,2-bond units of 45% or more, Water having a peak top molecular weight of 50,000 to 200,000 determined by standard polystyrene conversion by an association chromatography and hydrogenated 70 mol% or more of the carbon-carbon double bonds in the polymer block (B). A block copolymer.
The thermoplastic elastomer composition according to claim 1, wherein the hydrogenated block copolymer (II) has a glass transition temperature of -45 to 0 ° C.
The thermoplastic elastomer composition according to claim 1 or 2, wherein the content of the polymer block (A) in the hydrogenated block copolymer (II) is 5 to 40% by mass.
The thermoplastic elastomer composition according to any one of claims 1 to 3, wherein the content of the polymer block (A) in the hydrogenated block copolymer (II) is 5 to 18% by mass.
The polymer block (A) in the hydrogenated block copolymer (II) has two polymer blocks (A1) and (A2) having the same or different peak top molecular weights determined in terms of standard polystyrene by gel permeation chromatography. And the hydrogenated block copolymer (II) is composed of the polymer block (A1), the polymer block (B), and the polymer block (A2). The thermoplastic elastomer composition according to any one of claims 1 to 4, which is a hydrogenated product of the polymer [A1-B-A2].
In the hydrogenated block copolymer (II),
The polymer block (A1) in which the polymer block (A) is mainly composed of a structural unit derived from an aromatic vinyl compound and has a peak top molecular weight of Mp (A1) determined in terms of standard polystyrene by gel permeation chromatography. And a polymer block (A2) having a peak top molecular weight of Mp (A2), which is mainly composed of a structural unit derived from an aromatic vinyl compound, and calculated in terms of standard polystyrene by gel permeation chromatography,
The thermoplastic elastomer composition according to claim 5, wherein a ratio [Mp (A1) / Mp (A2)] of the Mp (A1) to the Mp (A2) satisfies 1/10 to 8/10.
The thermoplastic elastomer composition according to any one of claims 1 to 6, wherein the olefin rubber (I) and the polymer block (B) of the hydrogenated block copolymer (II) are crosslinked. .
The olefin rubber (I) is a copolymer rubber of (I-1) ethylene and one or more α-olefins having 3 to 20 carbon atoms or a cross-linked product thereof; and (I-2) ethylene and carbon 8. The system according to claim 1, which is at least one selected from the group consisting of a copolymer rubber of at least one α-olefin of 3 to 20 and at least one non-conjugated polyene or a crosslinked product thereof. The thermoplastic elastomer composition according to claim 1.
The polyolefin resin (III) is at least one selected from the group consisting of a polyethylene resin, a polypropylene resin, poly (1-butene) and poly (4-methyl-1-pentene). 9. The thermoplastic elastomer composition according to any one of 1 to 8.
A member having a portion (X1) made of the thermoplastic elastomer composition according to any one of claims 1 to 9.
The member according to claim 10, which has a part (Y1) made of a material different from the thermoplastic elastomer composition according to any one of claims 1 to 9, in addition to the part (X1).
The member according to claim 11, wherein the material of the part (Y1) is a vulcanized rubber or a dynamically crosslinked olefin-based thermoplastic elastomer (TPV).
The thermoplastic elastomer composition according to any one of claims 1 to 9, in addition to the part (X1) (provided that the thermoplastic elastomer composition forming the part (X1) is the same or different) The member according to claim 10, wherein the member has a portion (X2) made of.
The member according to any one of claims 10 to 13, wherein the part (X1) is a part obtained by injection molding.
A weather seal containing the member according to any one of claims 10 to 14.
Having a portion (X1) comprising the thermoplastic elastomer composition according to any one of claims 1 to 9, and
In addition to the part (X1), it has a part (Y1) made of a material different from the thermoplastic elastomer composition according to any one of claims 1 to 9, or in addition to the part (X1) The thermoplastic elastomer composition according to any one of claims 1 to 9, which may be the same as or different from the thermoplastic elastomer composition forming the portion (X1). A weather seal containing a member having the site (X2),
A weather seal having a corner portion made of the portion (X1) and a straight portion made of the portion (X2) or (Y1).
The weather seal according to claim 15 or 16, which is for automobiles, ships or aircraft.
A weather sealing corner member having a portion (X1) made of the thermoplastic elastomer composition according to any one of claims 1 to 9.