JP6699853B2 - Thermoplastic elastomer composition, crosslinked product, molded product, member, weather seal, and corner member for weather seal - Google Patents

Description

The present invention relates to a thermoplastic elastomer composition containing a hydrogenated block copolymer containing a farnesene-derived monomer unit, a crosslinked product obtained by crosslinking the thermoplastic elastomer composition, and the thermoplastic elastomer composition. Which is a molded article.
The present invention also relates to a member using the thermoplastic elastomer composition, a weather seal, and a corner member for a weather seal.

The thermoplastic elastomer composition is generally excellent in chemical resistance, mechanical properties, molding processability, flexibility, vibration damping property, strain recovery property at high temperature, and softening agent retention property, so that a vibration damping member, It is used in a wide range of fields such as building materials such as packing, machine parts, automobile interior and exterior parts such as bumper parts and airbag covers, household products, and various containers.
As such a thermoplastic elastomer composition, for example, Patent Document 1 discloses that (a) an olefin rubber, (b) a vinyl aromatic compound polymer block and a conjugated diene polymer block are contained in a specific ratio, and hydrogen is contained. A thermoplastic elastomer containing the added hydrogenated block copolymer, (C) an olefin resin and (D) a softening agent in a specific ratio and dynamically heat-treated in the presence of a crosslinking agent. The composition is described. It is described that the thermoplastic elastomer composition is excellent in flexibility, fluidity, elastic recovery and mechanical strength and can be used for automobile parts, industrial parts and the like.
Further, Patent Document 2 contains (I) an olefin-based rubber, (II) a polymer block consisting of an aromatic vinyl compound unit, and a structural unit derived from isoprene or a mixture of isoprene and butadiene. A heat containing a hydrogenated product of a block copolymer containing a polymer block having a bond and a 1,2-bond content of 45% or more, (III) a polyolefin resin and (IV) a softening agent in a specific ratio. A plastic elastomer composition is disclosed. The thermoplastic elastomer composition is excellent in molding processability, flexibility, vibration damping property at room temperature, compression set at high temperature and retention of a softening agent, and a molded product having a smooth surface can be obtained by extrusion molding. It is also described that it is used for various molded articles.

By the way, although vulcanized rubber has been widely used in the field of automobile parts, dynamically cross-linking type thermoplastic elastomer (Thermoplastic Vulcanizates: TPV) has been attracting attention as a new material. In particular, a vulcanized rubber having a small compression set and excellent flexibility has been conventionally used in a weather seal which is one of automobile parts. However, due to recent regulations for reducing carbon dioxide emissions, TPVs, which have better moldability and lighter specific gravity, tend to be replaced (see Non-Patent Document 1).
Weather seals for automobiles usually have a straight portion and a corner portion. Industrially, the straight portion is manufactured by extrusion molding, but the corner portion is manufactured by injection molding, so it is necessary to select a material that can be injection molded as the material for the corner portion. However, even TPV, which has better moldability than vulcanized rubber, cannot be said to have sufficient moldability, and there is room for further improvement. Therefore, 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 for the corner portion that is excellent in moldability while maintaining various characteristics. ..

  In addition, in Patent Document 3, a hydrogenated hydrogenated polymer block (A) including a structural unit derived from an aromatic vinyl compound and a polymer block (B) including a structural unit derived from a farnesene is included. Block copolymers are described. However, in Patent Document 3, although the physical properties of the hydrogenated block copolymer itself have been examined, no studies have been made on the composition using the hydrogenated block copolymer.

JP-A-7-286078 JP, 2014-80488, A International publication 2013/183570

JSR TECHNICAL REVIEW, No.119, 2012, p.20-25

The thermoplastic elastomer compositions described in Patent Documents 1 and 2 have room for further improvement in the above-mentioned respective performances, and in particular, regarding the vibration damping property, not only near room temperature but also in a wide temperature range from a low temperature range to a high temperature range. It is desired to be expressed.
Further, the inventors of the present invention have conducted studies and found that in the thermoplastic elastomer composition described in Patent Document 2, there is room for improvement due to insufficient moldability as a material for the corner portion of the weather seal. I understood.
Further, when the material of the straight portion of the weather seal is TPV, if the thermoplastic elastomer composition described in Patent Document 2 is used as the material of the corner portion, there is room for improvement in adhesiveness with the straight portion. There was found.

An object of the present invention is to provide a thermoplastic elastomer composition having excellent vibration damping properties, particularly in a wide temperature range from a low temperature range to a high temperature range. Furthermore, it is an object of the present invention to provide a thermoplastic elastomer composition which is excellent in compression set and weather resistance at high temperatures and has good extrusion moldability, flexibility and moldability. Further, it is an object of the present invention to provide a cross-linked product obtained by cross-linking this thermoplastic elastomer composition and a molded article made of the thermoplastic elastomer or the cross-linked product.
Further, the present invention is a thermoplastic elastomer composition having high adhesion to vulcanized rubber and dynamically crosslinked thermoplastic elastomer (TPV), and having excellent flexibility and weather resistance as well as moldability. The purpose is to provide.
Further, it is an object of the present invention to provide a member having a portion made of the thermoplastic elastomer composition, a weather seal having the member, and a corner member for weather sealing having a portion made of the thermoplastic elastomer composition.

That is, the present invention has the following gist.
[1] A thermoplastic elastomer composition containing an olefin rubber (I), the following hydrogenated block copolymer (II), and a polyolefin resin (III) other than the olefin rubber (I), wherein: The mass ratio of the following hydrogenated block copolymer (II) to the olefin rubber (I) is 0.1 to 9, and the total of the above olefin rubber (I) and the following hydrogenated block copolymer (II). The thermoplastic elastomer composition, wherein the content of the polyolefin-based resin (III) is 10 to 200 parts by mass with respect to 100 parts by mass.
<Hydrogenated block copolymer (II)>
The content of the polymer block (A) consisting of a structural unit derived from an aromatic vinyl compound and the structural unit (b1) derived from farnesene is 1 to 100% by mass, and a structural unit (b2) derived from a conjugated diene other than farnesene is contained. Is a hydrogenated product of a block copolymer containing a polymer block (B) having a content of 99 to 0% by mass, wherein the carbon-carbon double bond in the polymer block (B) is 50 mol%. The above-mentioned hydrogenated copolymer.
[2] A crosslinked product obtained by crosslinking the thermoplastic elastomer composition according to the above [1].
[3] A molded product comprising the thermoplastic elastomer composition described in [1] or the crosslinked product described in [2].
[4] A member having a site (X1) made of the thermoplastic elastomer composition according to the above [1].
[5] A weather seal including the member according to [4].
[6] A corner member for a weather seal, which has a portion (X1) made of the thermoplastic elastomer composition according to the above [1].

According to the present invention, it is possible to provide a thermoplastic elastomer composition having excellent vibration damping properties, particularly in a wide temperature range from a low temperature range to a high temperature range. In addition to this, the thermoplastic elastomer composition is excellent in compression set at high temperature and weather resistance, and is also excellent in extrusion moldability, flexibility and moldability. Further, a crosslinked product obtained by crosslinking this thermoplastic elastomer composition, the thermoplastic elastomer or the crosslinked product, and a molded article excellent in the above various performances can be provided.
Further, according to the present invention, a thermoplastic elastomer having a high adhesive force with respect to a vulcanized rubber and a dynamically crosslinked thermoplastic elastomer (TPV), and having excellent flexibility and weather resistance as well as molding processability. A composition can be provided. Further, it is possible to provide a member having a site made of the thermoplastic elastomer composition.
Furthermore, since the thermoplastic elastomer composition of the present invention is suitable for weather seals, particularly for corner portions of weather seals, a weather seal having a member having a site made of the thermoplastic elastomer composition of the present invention, the present invention It is also possible to provide a corner member for a weather seal having a part made of the thermoplastic elastomer composition.

[1] Thermoplastic Elastomer Composition The thermoplastic elastomer composition of the present invention comprises an olefin rubber (I), the following hydrogenated block copolymer (II), and a polyolefin resin other than the olefin rubber (I) ( III) containing a thermoplastic elastomer composition, wherein the mass ratio of the following hydrogenated block copolymer (II) to the olefin rubber (I) is 0.1 to 9, and the olefin rubber (I) ) And the following hydrogenated block copolymer (II) in a total amount of 100 parts by mass, the content of the polyolefin resin (III) is 10 to 200 parts by mass, which is a thermoplastic elastomer composition.
<Hydrogenated block copolymer (II)>
The content of the polymer block (A) consisting of a structural unit derived from an aromatic vinyl compound and the structural unit (b1) derived from farnesene is 1 to 100% by mass, and a structural unit (b2) derived from a conjugated diene other than farnesene is contained. Is a hydrogenated product of a block copolymer containing a polymer block (B) having a content of 99 to 0% by mass, wherein the carbon-carbon double bond in the polymer block (B) is 50 mol%. The above-mentioned hydrogenated copolymer.

[Olefin rubber (I)]
As the olefin rubber (I) used in the present invention,
Copolymer rubber of ethylene and one or more α-olefins having 3 to 20 carbon atoms (hereinafter, also referred to as “ethylene/α-olefin copolymer rubber”) and its crosslinked product, and ethylene and carbon number Copolymer rubber of one or more of 3 to 20 α-olefins and one or more of non-conjugated polyenes (hereinafter, also referred to as “ethylene/α-olefin/non-conjugated polyene copolymer rubber”) and crosslinks thereof Things can be mentioned.
These may be used alone or in combination of two or more. Examples of the combination include a combination of the crosslinked product of the ethylene/α-olefin copolymer rubber and the crosslinked product of the ethylene/α-olefin/non-conjugated polyene copolymer rubber.

Examples of the α-olefin having 3 to 20 carbon atoms constituting the olefin rubber (I) include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and 1-decene. Etc. These α-olefins may be used alone or in combination of two or more.
Among them, at least one selected from propylene, 1-butene, 1-hexene and 1-octene is preferable, and at least one selected from propylene and 1-butene is more preferable.

  In the ethylene/α-olefin copolymer rubber, the molar ratio of ethylene to the α-olefin having 3 to 20 carbon atoms (ethylene/α-olefin having 3 to 20 carbon atoms) depends on the mechanical properties of the thermoplastic elastomer composition. From the viewpoint of maintaining the strain recovery property at a high temperature in a good balance, 40/60 to 93/7 is preferable, 50/50 to 85/15 is more preferable, and 60/40 to 80/20 is further preferable.

  Examples of the non-conjugated polyene constituting the ethylene/α-olefin/non-conjugated polyene copolymer rubber include 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 and 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-nonadiene, 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 Internal unsaturated of 6 to 15 carbon atoms such as -1,6-nonadiene, 6,7-dimethyl-4-ethylidene-1,6-octadiene, and 6,7-dimethyl-4-ethylidene-1,6-nonadiene. Chain polyene having a bond; 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1 Α,ω-dienes such as 12-tridecadiene and 1,13-tetradecadiene.

  Among them, one or more selected from 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 7-methyl-1,6-octadiene and 5-methyl-1,4-hexadiene are preferable, From the viewpoint of excellent reactivity with the crosslinking agent, one or more selected from 5-ethylidene-2-norbornene, dicyclopentadiene and 5-vinyl-2-norbornene is more preferable.

  In the ethylene/α-olefin/non-conjugated polyene copolymer rubber, the molar ratio of ethylene and α-olefin having 3 to 20 carbon atoms (ethylene/α-olefin having 3 to 20 carbon atoms) is flexible and is obtained. From the viewpoint of improving the vibration damping property of the thermoplastic elastomer composition, 40/60 to 90/10 is preferable, and 50/50 to 80/20 is more preferable.

  Further, the iodine value (iodine value before crosslinking) of the ethylene/α-olefin/non-conjugated polyene copolymer rubber is preferably 3 to 40 from the viewpoint of improving the mechanical strength and vibration damping property of the thermoplastic elastomer composition. , 5 to 25 are more preferable. When the iodine value is larger than the lower limit value, the mechanical strength of the molded article obtained from the thermoplastic elastomer composition is likely to be improved, and when the iodine value is smaller than the upper limit value, the vibration damping property of the thermoplastic elastomer composition is high. Is easy to improve. In addition, the "iodine value" in this specification is an iodine value measured by the method of JIS K1525 4.7.

The Mooney viscosity (ML ₁₊₄ , 100° C.) of the olefin rubber (I) is preferably 25 to 350 from the viewpoint of improving the molding processability of the thermoplastic elastomer composition and improving the mechanical strength of the obtained molded product. , 40 to 300 are more preferable.
The “Moonie viscosity (ML ₁₊₄ , 100° C.)” in the present specification is the viscosity measured by the method described in JIS K6300.

  The olefin rubber (I) may be preliminarily cross-linked, and the degree of cross-linking can be appropriately adjusted depending on the application of the composition of the present invention. Generally, when the cross-linked olefin rubber (I) is subjected to Soxhlet extraction treatment with cyclohexane for 10 hours, the mass ratio (gel fraction) of the gel remaining without being dissolved in cyclohexane is the same as that before the extraction treatment. The crosslinking degree is preferably 80% or more, particularly 95% or more, with respect to the mass of the olefin rubber after crosslinking. When the degree of crosslinking is within the above range, the thermoplastic elastomer composition of the present invention and the molded product using the same have better strain recovery properties at high temperatures.

  In the present invention, the content of the olefin rubber (I) in the thermoplastic elastomer composition is preferably 3 to 75% by mass, and 5 to 70% by mass from the viewpoint of molding processability, flexibility and vibration damping property. More preferably, 5 to 65 mass% is still more preferable, 5 to 55 mass% is still more preferable, and 7 to 45 mass% is still more preferable.

[Hydrogenated block copolymer (II)]
The hydrogenated block copolymer (II) has a content of the polymer block (A) consisting of a structural unit derived from an aromatic vinyl compound and the structural unit (b1) derived from farnesene of 1 to 100% by mass, Block copolymer containing a polymer block (B) having a content of the structural unit (b2) derived from a conjugated diene other than 99 to 0 mass% (hereinafter, also referred to as "block copolymer (P)") Hydrogenated product (hereinafter, also referred to as "hydrogenated block copolymer (II)"), in which the carbon-carbon double bond in the polymer block (B) is hydrogenated in an amount of 50 mol% or more. Is.
When the thermoplastic elastomer composition of the present invention does not contain the hydrogenated block copolymer (II), it has a high adhesive force to the vulcanized rubber and the dynamically crosslinkable thermoplastic elastomer (TPV) and is flexible. Therefore, it becomes impossible to solve at least one of the problems of excellent moldability as well as the heat resistance and weather resistance. In particular, the molding processability and the adhesive force to the TPV and the vulcanized rubber have a great influence.

<Polymer block (A)>
The polymer block (A) is composed of a structural unit derived from an aromatic vinyl compound. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-t-butylstyrene, 4-cyclohexylstyrene, 4 -Dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, 1-vinylnaphthalene, 2 -Vinylnaphthalene, vinylanthracene, N,N-diethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlorostyrene, dichlorostyrene, divinylbenzene and the like. These aromatic vinyl compounds may be used alone or in combination of two or more. Among them, styrene, α-methylstyrene and 4-methylstyrene are more preferable, and styrene is still more preferable.

<Polymer block (B)>
In the polymer block (B), the content of the structural unit (b1) derived from farnesene is 1 to 100% by mass, and the content of the structural unit (b2) derived from a conjugated diene other than farnesene is 99 to 0% by mass. Is.
The farnesene-derived structural unit (b1) in the polymer block (B) may be either α-farnesene or a β-farnesene-derived structural unit represented by the following formula (I), but a block copolymer From the viewpoint of easy production of (P), a structural unit derived from β-farnesene is preferable. Note that α-farnesene and β-farnesene may be used in combination.

  Examples of the conjugated diene constituting the structural unit (b2) derived from a conjugated diene other than farnesene include butadiene, isoprene, 2,3-dimethylbutadiene, 2-phenylbutadiene, 1,3-pentadiene, 2-methyl-1, Examples include 3-pentadiene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octatriene, myrcene and chloroprene. These may be used alone or in combination of two or more. Among them, at least one selected from isoprene, butadiene and myrcene is preferable, and at least one selected from isoprene and butadiene is more preferable.

As described above, in the polymer block (B), the content of the structural unit (b1) derived from farnesene is 1 to 100% by mass, and the content of the structural unit (b2) derived from a conjugated diene other than farnesene is 99 to 0. It is% by mass. In addition, "the content of the structural unit (b2) derived from the conjugated diene is 0 mass%" means that the structural unit (b2) derived from the conjugated diene is not contained.
When the content of the structural unit (b1) derived from farnesene in the polymer block (B) is less than 1% by mass, a thermoplastic elastomer composition having excellent vibration damping properties in a wide temperature range from a low temperature range to a high temperature range is obtained. I can't. From such a viewpoint, the content of the structural unit (b1) in the polymer block (B) is preferably 30 to 100% by mass, and more preferably 45 to 100% by mass. Further, from the viewpoint of further improving the strain recovery property at high temperatures, the content of the structural unit (b1) in the polymer block (B) is more preferably 70 to 100% by mass, further preferably 95 to 100% by mass.
Further, when the polymer block (B) contains a structural unit (b2) derived from a conjugated diene other than farnesene, the content of the structural unit (b2) is preferably 70% by mass or less, and more preferably 55% by mass or less. preferable.
The polymer block (B) is a structural unit other than the structural units (b1) and (b2) within a range that does not impair the effects of the present invention, and is derived from “other copolymerizable monomer” described below. The structural unit may be included, but it is preferable not to include it. The total amount of the structural unit (b1) and the structural unit (b2) in the polymer block (B) is preferably 95% by mass or more, more preferably 100% by mass.

The hydrogenated block copolymer (II) is a hydrogenated product of a block copolymer (P) containing at least one polymer block (A) and at least one polymer block (B). The polymer (II) is preferably a hydrogenated product of a block copolymer (P) 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 thereof. Among them, the form in which each block is linearly bonded is preferable, and when the polymer block (A) is represented by A and the polymer block (B) is represented by B, (AB) _l , A-(BA) ) _m, or B- (bonding form which is expressed by _{A-B) n} are preferred. The above l, m and n each independently represent an integer of 1 or more.
The bond form is preferably a triblock copolymer represented by A-B-A from the viewpoints of flexibility, moldability, weather resistance, vibration damping property, handleability and the like.
Further, when the block copolymer (P) has two or more polymer blocks (A) or two or more polymer blocks (B), each polymer block has a weight of the same structural unit. It may be a united block or a polymer block composed of different structural units. For example, in the two polymer blocks (A) in the triblock copolymer represented by [ABA], the aromatic vinyl compounds may be the same or different in type. Good.

  The mass ratio [(A)/(B)] of the polymer block (A) and the polymer block (B) is preferably 1/99 to 55/45, more preferably 10/90 to 50/50, and more preferably 10 /90 to 40/60 is more preferable, and 15/85 to 35/65 is even more preferable. When the mass ratio is within the above range, a thermoplastic elastomer composition having excellent vibration damping properties can be obtained in a wide temperature range from a low temperature range to a high temperature range, and the thermoplastic elastomer composition and TPV or vulcanized rubber can be obtained. The adhesiveness of is improved.

The peak top molecular weight (Mp) of the hydrogenated block copolymer (II) is preferably 4,000 to 1,500,000, and more preferably 9,000 to 1,200,000 from the viewpoint of improving moldability. It is preferably 50,000 to 1,000,000, and more preferably 50,000 to 1,000,000.
Further, from the viewpoint of strain recovery at high temperature and from the viewpoint of improving the adhesiveness between the thermoplastic elastomer composition and TPV or vulcanized rubber, the peak top molecular weight (Mp) is more preferably 170,000 to 800,000. Preferably 190,000 to 650,000 are particularly preferred.
In addition, the peak top molecular weight (Mp) in this specification means the value measured by the method described in the below-mentioned Example.

  The molecular weight distribution (Mw/Mn) of the hydrogenated block copolymer (II) is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 to 2. When the molecular weight distribution is within the above range, the viscosity of the hydrogenated block copolymer (II) varies little, and stable extrusion molding can be performed.

<Polymer block (C)>
The hydrogenated block copolymer (II) in the present invention may contain a polymer block (C) in addition to the polymer block (A) and the polymer block (B).
The polymer block (C) is composed of a structural unit (c1) derived from a conjugated diene other than farnesene. Examples of such conjugated dienes include butadiene, isoprene, 2,3-dimethyl-butadiene, 2-phenyl-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1, Examples thereof include 3-octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octatriene, myrcene and chloroprene. These may be used alone or in combination of two or more. Among them, butadiene, isoprene and myrcene are more preferable.
Here, the polymer block (C) may include a structural unit (c2) derived from a monomer other than the “conjugated diene other than farnesene”. Examples of the structural unit (c2) derived from a monomer other than the “conjugated diene other than farnesene” include a structural unit derived from a copolymerizable monomer that constitutes the polymer block (A), and others described below. It may contain one or more kinds selected from structural units derived from the copolymerizable monomer and the like.
However, the content of the structural unit (c1) derived from the "conjugated diene other than farnesene" in the polymer block (C) is preferably 50% by mass or more, more preferably 60% by mass or more, and 70% by mass or more. More preferably, it is still more preferably 80 mass% or more, still more preferably 90 mass% or more, still more preferably 95 mass% or more.
When the polymer block (C) contains the farnesene-derived structural unit (c3), its content needs to be less than 1% by mass, and due to the difference in the content of the farnesene-derived structural unit, The polymer block (B) and the polymer block (C) are clearly distinguished.
When the block copolymer (P) has the polymer block (C), its content is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less.

<Other copolymerizable monomers>
The polymer block (A), the polymer block (B) and the polymer block (C) may contain a constitutional unit derived from other copolymerizable monomer as long as the effect of the present invention is not impaired.
Examples of the copolymerizable monomer include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, Unsaturated hydrocarbon compounds such as 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicocene; acrylic acid, methacrylic acid, methyl acrylate, methacryl Methyl acid, acrylonitrile, methacrylonitrile, maleic acid, fumaric acid, crotonic acid, itaconic acid, 2-acryloylethanesulfonic acid, 2-methacryloylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamide -2-Methylpropanesulfonic acid, vinylsulfonic acid, vinyl acetate, methyl vinyl ether, and other functional group-containing unsaturated compounds; and the like. These may be used alone or in combination of two or more.

  When the block copolymer (P) contains a structural unit derived from another copolymerizable monomer, its content is preferably 40% by mass or less, and 30% by mass or less from the viewpoint of moldability. Is more preferable.

In the case where the block copolymer (P) contains the polymer block (C), the polymer relative to the total of the polymer block (A), the polymer block (B) and the polymer block (C). The mass ratio [(A)/[(A)+(B)+(C)]] of the block (A) is preferably 5/100 to 80/100 from the viewpoint of moldability and is preferably 10/100 to 50. /100 is more preferable, and 12/100 to 40/100 is even more preferable.
When the block copolymer (P) contains the polymer block (C), the mass ratio of the polymer block (C) to the polymer block (B) [(C)/(B)]. Is preferably 5/95 to 95/5, more preferably 10/90 to 70/30, further preferably 20/80 to 60/40, and more preferably 30/70 to 50/50 from the viewpoint of moldability. More preferable.

  When the block copolymer (P) includes the polymer block (C), the hydrogenated block copolymer (II) is at least two polymer blocks (A) and at least one polymer. A hydrogenated product of the block copolymer (P) containing the block (B) and at least one polymer block (C) is preferable, and two or more polymer blocks (A) and a polymer block (A) are preferably used. A hydrogenated product of a block copolymer (P) containing two or more (B) and one or more polymer blocks (C) is more preferable.

  The hydrogenated block copolymer (II) in the present invention is preferably a hydrogenated product of the block copolymer (P) having at least one polymer block (B) at the terminal. Moldability is improved by having at least one polymer block (B) at the end of the polymer chain. That is, in the present invention, the hydrogenated block copolymer (II) in the case where the block copolymer (P) contains the polymer block (C) is at least two polymer blocks (A), A block copolymer (P) containing one said polymer block (B) and at least one said polymer block (C), and having at least one said polymer block (B) at the end; It is preferably a hydrogenated product.

Also in the hydrogenated block copolymer (II) in the case where the block copolymer (P) contains the polymer block (C), the polymer block (A), the polymer block (B) and the polymer block ( The bonding form of C) is not particularly limited, and may be linear, branched, radial, or a combination of two or more thereof. When the hydrogenated block copolymer of the present invention is linear, it is preferable that the polymer blocks (B) are present at both ends thereof, and the hydrogenated block copolymer of the present invention is branched or radial. In some cases, the number of polymer blocks (B) present at the terminal is preferably 2 or more, more preferably 3 or more.
Among them, from the viewpoint of molding processability, it is preferable that each block is linearly bonded. For example, the polymer block (A) is A, the polymer block (B) is B, and the polymer block (C) is C. When expressed, a tetrablock copolymer represented by [B-A-C-A], a pentablock copolymer represented by [B-A-C-A-B], [B-A- (C-A) _1- B], [B-A-(C-A-B) _m ], [B-(A-C-A-B) _n ] (l, m and n are each independently A polyblock copolymer represented by 2 or more) and a mixture thereof. Above all, a form in which the polymer block (B) is present at both ends of the polymer chain is more preferable.

Here, in the present specification, when polymer blocks of the same kind are linearly bonded via a divalent coupling agent or the like, the entire polymer blocks bonded are treated as one polymer block. Be done. Accordingly, the polymer block, which should be strictly described as [AXA] (X represents a coupling agent residue), is generally represented by A. In the present specification, since such a polymer block containing a coupling agent residue is treated as described above, for example, the coupling agent residue is contained, and strictly speaking, [B-A-C-X-C]. The block copolymer which should be described as -AB] is described as [B-A-C-A-B], and is treated as an example of a penta block copolymer.
Further, the two or more polymer blocks (A) contained in the block copolymer (P) may be polymer blocks each having the same structural unit or may be polymer blocks having different structural units. .. Similarly, when the block copolymer (P) has two or more polymer blocks (B) or two or more polymer blocks (C), each polymer block consists of the same structural unit. It may be a polymer block or a polymer block composed of different structural units.

  In addition, the hydrogenated block copolymer (II) has a structure (in the order of processability) having the polymer block (B), the polymer block (A), and the polymer block (C) in this order ( That is, it is preferably a copolymer containing the structure B-A-C), and more preferably a linear copolymer having the above structure.

When the block copolymer (P) contains the polymer block (C), the peak top molecular weight (Mp) of the hydrogenated block copolymer (II) is 10,000 to 1 from the viewpoint of moldability. , 500,000 is preferable, 50,000 to 1,200,000 is more preferable, 70,000 to 1,100,000 is further preferable, 75,000 to 900,000 is further more preferable, 80,000 to 600 1,000 is even more preferred.
The peak top molecular weight (Mp) of the hydrogenated block copolymer (II) can be measured by the method described in Examples below.

  In the hydrogenated block copolymer (II) when the block copolymer (P) contains the polymer block (C), the peak top molecular weight of the polymer block (A) is from the viewpoint of moldability. , 2,000 to 100,000 is preferable, 4,000 to 50,000 is more preferable, and 5,000 to 30,000 is further preferable.

  Further, in the hydrogenated block copolymer (II) in the case where the block copolymer (P) contains the polymer block (C), the peak top molecular weight of the polymer block (B) is From the viewpoint, 2,000 to 200,000 is preferable, 3,000 to 150,000 is more preferable, and 4,000 to 100,000 is further preferable.

Furthermore, in the hydrogenated block copolymer (II) in the case where the block copolymer (P) contains the polymer block (C), the peak top molecular weight of the polymer block (C) is From the viewpoint, 4,000 to 200,000 is preferable, 4,500 to 150,000 is more preferable, and 5,000 to 100,000 is further preferable.
Here, when the block copolymer (P) in the present invention is a polymer block (A) and a polymer block (B) produced in this order, the peak top molecular weight of each polymer block is determined by the following procedure. The value measured in. That is, first, for the polymer block (A) polymerized first, the value measured by a known method is used as the peak top molecular weight of the polymer block (A), and the peak top molecular weight of the polymer block (B) is The value obtained by subtracting the peak top molecular weight of the polymer block (A) from the peak top molecular weight of the block copolymer (P) is the peak top molecular weight of the polymer block (B). In addition, when the block copolymer (P) in the present invention has three or more polymer blocks, the same measurement can be performed.

  When the block copolymer (P) contains the polymer block (C), the molecular weight distribution (Mw/Mn) of the hydrogenated block copolymer (II) is preferably 1 to 4, and more preferably 1 to 3. Preferably, 1-2 are more preferable. When the molecular weight distribution is within the above range, moldability is further improved.

  In the present invention, the content of the hydrogenated block copolymer (II) in the thermoplastic elastomer composition is excellent in damping property in a wide temperature range from a low temperature region to a high temperature region, and the compression set and weather resistance at high temperature are high. From the viewpoint of obtaining a thermoplastic elastomer composition having excellent properties, extrusion molding properties, flexibility, and molding processability as well, 3 to 50 mass% is preferable, and 5 to 45 mass% is preferable.

In the thermoplastic elastomer of the present invention, the mass ratio [(II)/(I)] of the hydrogenated block copolymer (II) to the olefin rubber (I) is 0.1 to 9. When the mass ratio is within the above range, the vibration damping property is excellent in a wide temperature range from the low temperature region to the high temperature region, and the compression set and the weather resistance at the high temperature are also excellent, the extrusion moldability, the flexibility, and the molding process. A thermoplastic elastomer composition having good properties can be obtained. Also, the adhesiveness between the thermoplastic elastomer composition and TPV or vulcanized rubber is improved.
From such a viewpoint, the mass ratio is preferably 0.2 to 7, more preferably 0.25 to 5, and further preferably 0.3 to 4.

[Method for producing hydrogenated block copolymer (II)]
The hydrogenated block copolymer (II) is obtained, for example, by a polymerization step of obtaining the block copolymer (P) by anionic polymerization, and carbon-carbon in the polymer block (B) in the block copolymer (P). It can be preferably produced by a step of hydrogenating a double bond in an amount of 50 mol% or more.
<Polymerization process>
The block copolymer (P) can be produced by a solution polymerization method or a method described in JP 2012-502135 A, JP 2012-502136 A, or the like. Among them, the solution polymerization method is preferable, and for example, known methods such as an ionic polymerization method such as anionic polymerization and cationic polymerization, and a radical polymerization method can be applied, and the anionic polymerization method is particularly preferable. As the anionic polymerization method, an aromatic vinyl compound, farnesene, and/or a conjugated diene other than farnesene are sequentially added in the presence of a solvent, an anionic polymerization initiator, and optionally a Lewis base to obtain a block copolymer (P ) Get.
Examples of the anionic polymerization initiator include alkali metals such as lithium, sodium and potassium; alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium; lanthanide rare earth metals such as lanthanum and neodymium; the above alkali metals and alkalis. Examples thereof include compounds containing an earth metal and a lanthanoid rare earth metal, such as an organic alkali metal compound. Of these, alkali metals and compounds containing alkali metals are preferable, and organic alkali metal compounds are more preferable.

Examples of the organic alkali metal compound include methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium, stilbenelithium, dilithiomethane, dilithionaphthalene, 1,4-dilithiobutane. , 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene and other organic lithium compounds; sodium naphthalene, potassium naphthalene and the like. Among them, organic lithium compounds are preferable, n-butyllithium and sec-butyllithium are more preferable, and sec-butyllithium is further preferable. The organic alkali metal compound may be used as an organic alkali metal amide by reacting with a secondary amine such as diisopropylamine, dibutylamine, dihexylamine or dibenzylamine.
The amount of the organic alkali metal compound used for the polymerization varies depending on the molecular weight of the block copolymer (P), but is usually 0.01 to 3 with respect to the total amount of the aromatic vinyl compound and farnesene or a conjugated diene other than farnesene. It is in the range of mass%.

  The solvent is not particularly limited as long as it does not adversely affect the anionic polymerization reaction, and examples thereof include saturated aliphatic hydrocarbons such as n-pentane, isopentane, n-hexane, n-heptane and isooctane; cyclopentane, cyclohexane and methylcyclo Examples thereof include saturated alicyclic hydrocarbons such as pentane; aromatic hydrocarbons such as benzene, toluene and xylene. These may be used alone or in combination of two or more. The amount of solvent used is not particularly limited.

  The Lewis base has a role of controlling the microstructure in the structural unit derived from farnesene and the structural unit derived from a conjugated diene other than farnesene. Examples of the Lewis base include ether compounds such as dibutyl ether, diethyl ether, tetrahydrofuran, dioxane, and ethylene glycol diethyl ether; pyridine; tertiary amines such as N,N,N′,N′-tetramethylethylenediamine and trimethylamine; Alkali metal alkoxides such as potassium t-butoxide; phosphine compounds and the like. When a Lewis base is used, its amount is usually preferably in the range of 0.01 to 1000 molar equivalents with respect to 1 mol of an anionic polymerization initiator.

The temperature of the polymerization reaction is usually -80 to 150°C, preferably 0 to 100°C, more preferably 10 to 90°C. The polymerization reaction may be carried out batchwise or continuously. Aromatic vinyl compound in the polymerization reaction system, so that the amount of farnesene and / or conjugated diene other than farnesene is in a specific range, each monomer is continuously or intermittently supplied to the polymerization reaction solution, Further, the block copolymer (P) can be produced by sequentially polymerizing each of the monomers in the polymerization reaction liquid so that the monomers have a specific ratio.
The polymerization reaction can be stopped by adding an alcohol such as methanol or isopropanol as a polymerization terminator. The block copolymer (P) is obtained by pouring the obtained polymerization reaction solution into a poor solvent such as methanol to precipitate the block copolymer (P), or washing the polymerization reaction solution with water, separating and drying the block copolymer (P). Can be isolated.

{Modified copolymer}
In the main polymerization step, an unmodified block copolymer (P) may be obtained as described above, but a functional group is introduced into the block copolymer (P) before the hydrogenation step described below. Alternatively, a modified block copolymer (P) may be obtained. Examples of functional groups that can be introduced include amino groups, alkoxysilyl groups, hydroxyl groups, epoxy groups, carboxyl groups, carbonyl groups, mercapto groups, isocyanate groups, acid anhydrides, and the like.
Examples of the method for modifying the block copolymer (P) include tin tetrachloride, tetrachlorosilane, dimethyldichlorosilane, dimethyldiethoxysilane, and tetramethoxysilane, which can react with a polymerization active terminal before adding a polymerization terminator. , Tetraethoxysilane, 3-aminopropyltriethoxysilane, tetraglycidyl-1,3-bisaminomethylcyclohexane, 2,4-tolylene diisocyanate and other coupling agents, 4,4′-bis(diethylamino)benzophenone, A method of adding a polymerization terminal modifier such as N-vinylpyrrolidone or the other modifiers described in JP2011-132298A can be mentioned. Further, the copolymer after isolation may be grafted with maleic anhydride or the like for use.
The position at which the functional group is introduced may be at the polymerization end of the block copolymer (P) or at the side chain. The above functional groups may be used alone or in combination of two or more. Usually, the modifier is preferably in the range of 0.01 to 10 molar equivalents with respect to the anionic polymerization initiator.

<Hydrogen addition process>
The hydrogenated block copolymer (II) can be obtained by subjecting the block copolymer (P) obtained by the above method or the modified block copolymer (P) to a step of hydrogenating. A known method can be used for the method of hydrogenating. For example, in a solution prepared by dissolving the block copolymer (P) in a solvent that does not affect the hydrogenation reaction, Ziegler-based catalysts; nickel, platinum, palladium, ruthenium supported on carbon, silica, diatomaceous earth, Rhodium metal catalyst: An organometallic complex having cobalt, nickel, palladium, rhodium, or ruthenium metal is present as a hydrogenation catalyst to carry out the hydrogenation reaction. In the hydrogenation step, a hydrogenation catalyst may be added to the polymerization reaction liquid containing the block copolymer (P) obtained by the method for producing the block copolymer (P) to carry out the hydrogenation reaction. .. In the present invention, palladium carbon in which palladium is supported on carbon is preferable.
In the hydrogenation reaction, the hydrogen pressure is preferably 0.1 to 20 MPa, the reaction temperature is preferably 70 to 200°C, more preferably 100 to 200°C, and the reaction time is preferably 1 to 20 hours.

The hydrogenation rate of carbon-carbon double bonds in the polymer block (B) is 50 mol% or more. When the hydrogenation rate is less than 50 mol %, it is possible to obtain a thermoplastic elastomer composition which is excellent in vibration damping property and is also excellent in compression set at high temperature, weather resistance, extrusion moldability, flexibility and molding processability. Have difficulty. From such a viewpoint, the hydrogenation rate is preferably 70 mol% or more, more preferably 80 mol% or more, and further preferably 85 mol% or more. When the hydrogenation rate is 70 mol% or more, the weather resistance tends to be further improved.
Carbon-carbon double in the polymer block (B) and polymer block (C) in the hydrogenated block copolymer (II) when the block copolymer (P) contains the polymer block (C) The hydrogenation rate of the bond is 50 mol% or more, preferably 70 mol% or more, and more preferably 90 mol% or more from the viewpoint of obtaining the hydrogenated block copolymer (II) having excellent heat resistance and weather resistance.
The hydrogenation rate can be calculated by measuring ¹ H-NMR of the block copolymer (P) and the hydrogenated block copolymer (II) after hydrogenation.

[Polyolefin resin (III)]
The thermoplastic elastomer composition of the present invention contains a polyolefin resin (III) other than the olefin rubber (I).
Examples of the polyolefin resin (III) include polyethylene, polypropylene, polybutene-1, polyhexene-1, poly-3-methyl-butene-1, poly-4-methyl-pentene-1, ethylene-vinyl acetate copolymer. Coalescence, ethylene-acrylic acid copolymer and the like are preferable. Among them, polypropylene resins such as homopolypropylene, random polypropylene, block polypropylene and the like and polyethylene resins such as high density polyethylene (HDPE), low density polyethylene (LDPE) and linear low density polyethylene (LLDPE) are preferable, and polypropylene resins Is more preferable. The polyolefin resin (III) may be used alone or in combination of two or more kinds.

The amount of the polyolefin resin (III) in the thermoplastic elastomer composition of the present invention is 10 to 200 with respect to a total of 100 parts by mass of the olefin rubber (I) and the hydrogenated block copolymer (II). It is a mass part. When the amount of the polyolefin-based resin (III) is within this range, the resulting thermoplastic elastomer composition has excellent vibration damping properties, and compression set at high temperature, weather resistance, extrusion moldability, flexibility and molding process. Sex is also improved. Also, the adhesiveness between the thermoplastic elastomer composition and TPV or vulcanized rubber is improved.
From such a viewpoint, the amount of the polyolefin resin (III) in the thermoplastic elastomer composition is 100 parts by mass based on 100 parts by mass of the olefin rubber (I) and the hydrogenated block copolymer (II). 10 to 150 parts by mass is more preferable, and 20 to 100 parts by mass is further preferable.

  The melt flow rate (MFR) of the polyolefin-based resin (III) measured at 230° C. under a load of 21.2 N is preferably 0.1 g/10 minutes or more from the viewpoint of moldability, and is 0.1. It is more preferably 1 to 50 g/10 minutes, further preferably 1 to 40 g/10 minutes, and particularly preferably 2.5 to 40 g/10 minutes. The MFR is a value measured according to JIS K7210.

[Softener (IV)]
The thermoplastic elastomer composition of the present invention preferably contains a softening agent (IV). As the softening agent (IV), for example, a known softening agent used for rubber and plastics can be used.
Known softening agents used for rubber and plastics include, for example, paraffin-based, naphthene-based, aromatic-based process oils; phthalic acid derivatives such as dioctyl phthalate and dibutyl phthalate; white oils; mineral oils; ethylene and α. -Liquid cooligomers with olefins; liquid paraffin; polybutene; low molecular weight polyisobutylene; liquid polybutadiene, liquid polyisoprene, liquid polyisoprene/butadiene copolymers, liquid styrene/butadiene copolymers, liquid styrene/isoprene copolymers, etc. And liquid hydrogenated products thereof. Among them, from the viewpoint of compatibility with the hydrogenated block copolymer (II), paraffin-based process oil; liquid co-oligomer of ethylene and α-olefin; and liquid paraffin are preferable. These softening agents (IV) may be used alone or in combination of two or more kinds.

  When the thermoplastic elastomer composition of the present invention contains the softening agent (IV), the content thereof is based on 100 parts by mass of the total of the olefin rubber (I) and the hydrogenated block copolymer (II). , 1 to 350 parts by mass, more preferably 10 to 300 parts by mass, further preferably 30 to 250 parts by mass, further preferably 50 to 200 parts by mass, still more preferably 80 to 200 parts by mass. When the amount of the softening agent (IV) is within the above range, a thermoplastic elastomer composition having excellent vibration damping properties, compression set at high temperature, weather resistance, extrusion moldability, flexibility and moldability is obtained. Obtainable.

[Crosslinking agent (V)]
The thermoplastic elastomer composition of the present invention may contain a crosslinking agent (V). Examples of the crosslinking agent (V) include radical generators, sulfur, and sulfur compounds. When the thermoplastic elastomer composition of the present invention contains a cross-linking agent (V), the content thereof can be appropriately determined depending on the cross-linking agent used, but the olefin rubber (I) and the hydrogenated block copolymer (II 0.01 to 30 parts by mass with respect to 100 parts by mass in total.
Examples of the radical generator include dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane and 2,5-dimethyl-2,5-di(t. -Butylperoxy)hexyne-3,1,3-bis(t-butylperoxyisopropyl)benzene, α,α'-bis(t-butylperoxy)diisopropylbenzene, 3,3,5-trimethylcyclohexane, n-butyl- 4,4-bis(t-butylperoxy)valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, t Examples thereof include organic peroxides such as -butylcumyl peroxide, and these may be used alone or in combination of two or more kinds.
Among them, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane and dicumyl peroxide are preferable from the viewpoint of reactivity.
When these radical generators are used, 0.01 to 15 parts by mass is more preferable with respect to 100 parts by mass of the olefin rubber (I) and the hydrogenated block copolymer (II). More preferably, it is from 10 to 10 parts by mass.

  Examples of the sulfur compound include sulfur monochloride and sulfur dichloride. When sulfur or a sulfur compound is used, 0.1 to 20 parts by mass is more preferable, and 0.2 to 20 parts by mass based on 100 parts by mass in total of the olefin rubber (I) and the hydrogenated block copolymer (II). Even more preferable is 10 parts by mass.

  Other examples of the cross-linking agent (V) are phenolic resins such as alkylphenol resins and brominated alkylphenol resins; combinations of p-quinonedioxime and lead dioxide, p,p'-dibenzoylquinonedioxime and trilead tetraoxide, and the like. Can also be used.

[Crosslinking aid (VI)]
The thermoplastic elastomer composition of the present invention may contain a crosslinking aid (VI). Examples of the cross-linking aid (VI) include polyfunctional monomers such as triallyl isocyanurate, divinylbenzene, ethylene glycol dimethacrylate, and triethylene glycol dimethacrylate; stannous chloride, ferric chloride, organic sulfone. Acid, polychloroprene, chlorosulfonated polyethylene are mentioned.

[Crosslinking accelerator (VII)]
The thermoplastic elastomer composition of the present invention may contain a crosslinking accelerator (VII). Examples of the crosslinking accelerator (VII) include thiazoles such as N,N-diisopropyl-2-benzothiazole-sulfenamide, 2-mercaptobenzothiazole, and 2-(4-morpholinodithio)benzothiazole; diphenylguanidine, Guanidines such as triphenylguanidine; aldehyde-amine type reaction products such as butyraldehyde-aniline reaction products and hexamethylenetetramine-acetaldehyde reaction products; or aldehyde-ammonia reaction products; imidazolines such as 2-mercaptoimidazoline; thiocarbanilide, diethyl Thioureas such as urea, dibutylthiourea, trimethylthiourea, diorthotolylthiourea; tetramethylthiuram monosulfide, tetramethylthiuram disulfide, thiuram mono- or polysulfides such as pentamethylenethiuram tetrasulfide; zinc dimethyldithiocarbamate, ethylphenyldithiocarbamate Examples thereof include thiocarbamate salts such as zinc, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, and tellurium diethyldithiocarbamate; xanthate salts such as zinc dibutylxanthate; zinc white. These crosslinking accelerators (VII) may be used alone or in combination of two or more.

[Other ingredients]
The thermoplastic elastomer composition of the present invention may contain another thermoplastic polymer within a range that does not impair the effects of the present invention. Examples of other thermoplastic polymers include 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 polyamides; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; acrylic resins such as polymethyl acrylate and polymethyl methacrylate; polyoxymethylene homopolymers and polyoxymethylene Polyoxymethylene resin such as copolymer; styrene homopolymer, styrene resin such as acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin; polycarbonate resin; styrene/butadiene copolymer rubber, styrene/isoprene copolymer rubber, etc. Styrene elastomer and hydrogenated products or modified products thereof; natural rubber; liquid polyisoprene rubber and hydrogenated products or modified products thereof; chloroprene rubber; acrylic rubber; acrylonitrile butadiene rubber; epichlorohydrin rubber; silicone rubber; chloro Examples include sulfonated polyethylene; urethane rubber; polyurethane elastomers; polyamide elastomers; polyester elastomers; and soft vinyl chloride resins.
Incidentally, the content of the other thermoplastic polymer, the flexibility of the thermoplastic elastomer composition, it may be used in a range that does not impair the mechanical properties, the thermoplastic elastomer composition before adding the other thermoplastic polymer It is preferably 200 parts by mass or less with respect to 100 parts by mass.

  Further, the thermoplastic elastomer composition of the present invention contains an inorganic filler and other additives, for example, a heat antiaging agent, an antioxidant, a light stabilizer, an antistatic agent, as long as the effects of the present invention are not impaired. Release agents, flame retardants, foaming agents, pigments, dyes, brighteners and the like can be added. Specific examples of the inorganic filler include talc, calcium carbonate, silica, glass fiber, carbon fiber, mica, kaolin, titanium oxide and the like. These additives may be used alone or in combination of two or more.

[Method for producing thermoplastic elastomer composition]
The method for producing the thermoplastic elastomer composition of the present invention is not particularly limited, and various conventional production methods can be mentioned. For example, after olefin rubber (I), hydrogenated block copolymer (II), polyolefin resin (III) and, if necessary, softening agent (IV) and other components are dry blended, a single-screw extruder, The thermoplastic elastomer composition can be preferably produced by melt-kneading with a kneader such as a twin-screw extruder, a kneader, a Banbury mixer, or a roll. The order in which the above components are mixed is not particularly limited, and they can be mixed in any order.

[2] Crosslinked Product The crosslinked product of the present invention is a crosslinked product obtained by crosslinking the thermoplastic elastomer composition of the present invention. The crosslinked product of the present invention can be crosslinked, for example, by the following method.
[Crosslinking method]
The thermoplastic elastomer composition of the present invention can be made into a crosslinked product by crosslinking by the following method.
As a crosslinking method, a method in which a crosslinking agent (V), a crosslinking aid (VI) and a crosslinking accelerator (VII) are appropriately added to the olefin rubber (I) and the hydrogenated block copolymer (II) and kneaded (Method 1), resin cross-linking method (Method 2), quinoid cross-linking method (Method 3), and method using active energy rays (Method 4). The product obtained by the following cross-linking method can be dissolved in an organic solvent such as cyclohexane and the presence or absence of undissolved residue can be checked to determine whether or not the cross-linked product is formed.

<Method 1>
In the thermoplastic elastomer composition of the present invention, a crosslinking agent (V), a crosslinking aid (VI) and a crosslinking accelerator (VII) are appropriately added to the olefin rubber (I) and the hydrogenated block copolymer (II). Then, the olefin rubber (I) and the hydrogenated block copolymer (II) can be crosslinked by kneading.
For example, together with a cross-linking agent (V) such as a radical generator, if necessary, a cross-linking auxiliary agent such as a polyfunctional monomer such as triallyl isocyanurate, divinylbenzene, ethylene glycol dimethacrylate, or triethylene glycol dimethacrylate. A crosslinking accelerator (VII) such as a disulfide compound such as (VI), benzothiazyl disulfide, or tetramethylthiuram disulfide may be used.
When the cross-linking aid (VI) and the cross-linking accelerator (VII) are used, the addition amount thereof is 100 parts by mass of the olefin rubber (I) and the hydrogenated block copolymer (II), respectively. 0.1 to 20 parts by mass is preferable, and 0.2 to 15 parts by mass is more preferable.
When the crosslinking is carried out by the method 1, for example, a method of melting and kneading the thermoplastic elastomer composition, the radical generator and, if necessary, another thermoplastic resin under heating may be mentioned. The heating temperature is preferably 140 to 230° C., and the melt-kneading can be carried out batchwise or continuously with a device such as an extruder, a kneader, a roll or a plastograph. A crosslinking reaction proceeds through the melt-kneading step.

When sulfur or a sulfur compound is used as the cross-linking agent (V), a cross-linking accelerator such as thiazoles, guanidines, butyraldehyde-aniline reaction products, hexamethylenetetramine-acetaldehyde reaction products, or aldehyde-amine-based reaction products ( It is preferable 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 used in a roll, a mixer such as a Banbury mixer, preferably in the range of 50 to 250°C, more preferably 80 to 200°C. After kneading in the range of, the crosslinkage can be formed by maintaining the temperature at preferably 60° C. or higher, more preferably 90 to 250° C. for usually 1 minute to 2 hours, more preferably 5 minutes to 1 hour.

<Method 2>
In the crosslinking method by resin crosslinking, a phenolic resin such as an alkylphenol resin or a brominated alkylphenol resin is used as the crosslinking agent (V), and stannous chloride, ferric chloride, an organic sulfonic acid, Chloroprene, chlorosulfonated polyethylene, etc. are used.
When crosslinking is carried out by such a method, the amount of the phenol resin added as the crosslinking agent (V) is 1 to 30 with respect to 100 parts by mass of the total of the olefin rubber (I) and the hydrogenated block copolymer (II). A mass part is preferable and a 5-20 mass part is more preferable. The amount of the crosslinking aid (VI) added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass. The crosslinking temperature is preferably 100 to 250°C, more preferably 130 to 220°C. When carrying out resin crosslinking, it is preferable to use a crosslinking accelerator (VII) in combination.

<Method 3>
In the cross-linking method by quinoid cross-linking, a combination of p-quinonedioxime and lead dioxide, a combination of p,p′-dibenzoylquinonedioxime and trilead tetraoxide, etc. is used as the crosslinker (V).
When the crosslinking is carried out by Method 3, the quinone oxime is preferably 0.1 to 10 parts by mass, more preferably 100 parts by mass of the olefin rubber (I) and the hydrogenated block copolymer (II). Is added in an amount of 0.5 to 5 parts by mass, and lead oxides are preferably added in an amount of 0.1 to 15 parts by mass, more preferably 0.5 to 10 parts by mass. 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.

[3] Molded Product The molded product of the present invention comprises the thermoplastic elastomer composition of the present invention. The molded product of the present invention may be composed of a crosslinked product of the thermoplastic elastomer composition of the present invention. The shape of the molded body may be any molded body that can be produced using the thermoplastic elastomer composition of the present invention, for example, pellets, films, sheets, plates, pipes, tubes, rod-shaped bodies, granular bodies and the like. It can be formed into a shape. The method for producing this molded article is not particularly limited, and various conventional molding methods such as injection molding, blow molding, press molding, extrusion molding, calender molding and the like can be used. Since the thermoplastic elastomer composition of the present invention has excellent moldability, a molded product can be suitably obtained by high cycle injection molding.

[4] Use of Thermoplastic Elastomer Composition and Molded Product The thermoplastic elastomer composition and the molded product of the present invention have excellent vibration damping properties in a wide temperature range from a low temperature region to a high temperature region, and a compression set at a high temperature and It is also excellent in weather resistance, and has good extrusion moldability, flexibility, and moldability, and therefore can be suitably used as a molded product such as a sheet, film, tube, hose, belt, or an adhesive. Specifically, various anti-vibration and damping materials such as anti-vibration rubber, mats, seats, cushions, dampers, pads and mount rubbers; footwear such as sports shoes and fashion sandals; televisions, stereos, vacuum cleaners, refrigerators, etc. Household appliances parts; building materials such as building doors and sealing packings for window frames; bumper parts, body panels, weather strips, grommets, instrument panels, and other automobile interior and exterior parts; scissors, drivers, Grips for toothbrushes, skis, etc.; packaging materials for food products such as food wrap films; medical devices such as infusion bags, syringes, catheters; stoppers for containers for storing foods, beverages, drugs, etc.; cap liners; hot melt adhesives It can be suitably used as an adhesive material such as an adhesive tape and an adhesive layer of a protective film.

<Physical Properties and Properties of Thermoplastic Elastomer Composition>
The thermoplastic elastomer composition of the present invention has a hardness (JIS-A) of 30 to 90, specifically 40 to 80, measured according to the method described in Examples, and has appropriate flexibility as a weather seal. In particular, for glass run corners, the upper limit of hardness is preferably 80 or less, more preferably 76 or less, and for corners of door seals, the upper limit of hardness is preferably 57 or less, more preferably 52 or less. preferable.
In addition, the thermoplastic elastomer composition of the present invention has an adhesive force to vulcanized rubber of 100 to 300 N/cm ² measured according to the method described in Examples, and an adhesive force to TPV of 100 to 400 N/cm ^2. Therefore, the adhesive strength to vulcanized rubber and TPV is excellent.
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.
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.
Furthermore, the thermoplastic elastomer composition of the present invention is also excellent in weather resistance and moldability.

[5] Member, weather seal, corner member for weather seal The present invention also provides a member having a site (X1) made of the thermoplastic elastomer composition of the present invention. The part (X1) may be a part of the member or the entire member. That is, the present invention also provides a member having, in addition to the portion (X1), a portion (Y1) made of a material different from the thermoplastic elastomer composition of the present invention.
The material of the part (Y1) is not particularly limited, but in the case of weather seal application, vulcanized rubber, dynamically crosslinked thermoplastic elastomer (TPV) and the like can be mentioned.
As the vulcanized rubber, (1) a crosslinked product of a copolymer of ethylene and one or more α-olefins having 3 to 20 carbon atoms, (2) ethylene and one α-olefin having 3 to 20 carbon atoms. The above, crosslinked products of a copolymer with one or more non-conjugated polyenes, and the like. 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 non-conjugated polyenes, and ethylene, propylene, and non-conjugated polyenes. The crosslinked product of the copolymer of is more preferable.
As the TPV, an olefin-based TPV containing an olefin-based resin and an olefin-based rubber is preferable, and an olefin-based TPV containing a polypropylene resin and an olefin-based rubber is more preferable. As the olefin-based rubber, a cross-linked product of a copolymer of ethylene, one or more α-olefins having 3 to 20 carbon atoms, and one or more non-conjugated polyenes is preferable, and ethylene, propylene and a non-conjugated polyene are used. A crosslinked product of a copolymer (EPDM) is more preferable. As the TPV, commercially available products such as "Excellink 1303B" and "Excellink 1703B" (both manufactured by JSR Corporation) can be used.
The "α-olefin having 3 to 20 carbon atoms" and the "non-conjugated polyene" are the same as those described in the olefin rubber (I), and the preferable ones are also the same.
The vulcanized rubber and TPV contain various additives such as a vulcanization aid, a vulcanization accelerator, a softening agent, an antioxidant, carbon black, zinc oxide, and a lubricant, if necessary. May be.

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

  Since the thermoplastic elastomer composition of the present invention is also excellent in moldability, the site (X1) comprising the thermoplastic elastomer composition of the present invention is preferably a site obtained by injection molding.

The present invention also provides a weather seal having the above member. More specifically, there is provided a weather seal having a corner portion including the portion (X1) and a straight portion including the portion (X2) or (Y1). The weather seal is useful for automobiles, ships, or aircraft.
The portion (X1) is particularly useful as a corner member because it has excellent flexibility and moldability, and is also useful as a corner member for weather sealing. For example, for automotive applications, it is useful as a corner member for grass run, a corner member for door seal, and the like.
The weather seal can be obtained by a known molding method, preferably extrusion molding or injection molding, from the thermoplastic elastomer composition of the present invention. In particular, injection molding is used to form the corners of the weatherseal. When forming the straight portion of the weather seal, extrusion molding is preferably used.
Further, in the case of a thermoplastic elastomer composition containing a foaming agent, foam molding is performed. As a method of foam molding, a chemical method of foaming by decomposition or reaction of a foaming agent, the chemical method and supercritical foaming are used. Alternatively, a method in which a physical method such as water foaming is used in combination can be used. By utilizing these methods, it is possible to carry out foam molding 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. Be done.

  Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. In addition, β-farnesene (purity 97.6% by weight Amiris, manufactured by Incorporated) is purified by 3Å molecular sieves and distilled under a nitrogen atmosphere to give zingiberene, bisaborene, farnesene epoxide, farnesol isomerism. Body, E, E-farnesol, squalene, ergosterol and farnesene were excluded from hydrocarbon impurities such as several dimers and used in the following polymerization.

(1) Method for measuring peak top molecular weight (Mp) and molecular weight distribution The peak top molecular weight (Mp) and molecular weight distribution (Mw/Mn) of the hydrogenated block copolymer are converted into standard polystyrene by GPC (gel permeation chromatography). The molecular weight was determined, and the peak top molecular weight (Mp) was determined from the position of the peak of the molecular weight distribution. The measuring device and conditions are as follows.
-Device: GPC device "GPC8020" manufactured by Tosoh Corporation
・Separation column: "TSKgel G4000HXL" manufactured by Tosoh Corporation
・Detector: "RI-8020" manufactured by Tosoh Corporation
・Eluent: Tetrahydrofuran ・Eluent flow rate: 1.0 ml/min ・Sample concentration: 5 mg/10 ml
・Column temperature: 40℃

(2) Method of measuring hydrogenation rate The block copolymer (P) obtained in the following production example and the hydrogenated block copolymer (II) after hydrogenation were each dissolved in a deuterated chloroform solvent and manufactured by JEOL Ltd. ¹ H-NMR was measured at 50° C. using “Lambda-500”. The hydrogenation rate of the polymer block (B) in the hydrogenated block copolymer (II) is from the peak of the proton having the carbon-carbon double bond appearing at 4.5 to 6.0 ppm in the obtained spectrum, It was calculated by the following formula.
Hydrogenation rate={1-(mol number of carbon-carbon double bond contained per 1 mol of hydrogenated block copolymer (II))/(carbon-carbon 2 contained per 1 mol of block copolymer (P) Number of mols of heavy bond)}×100 (mol%)

(3) Hardness measuring method Pellets of the thermoplastic elastomer compositions obtained in the following examples and comparative examples were injection molded at 200° C. by an injection molding machine (“EC75SX”, manufactured by Toshiba Machine Co., Ltd.) to have a length of 110 mm. A sheet-shaped test piece having a width of 110 mm and a thickness of 2 mm was prepared. Then, based on JIS K 6253, three injection-molded sheets were stacked and the hardness of 6 mm in thickness was measured.
The hardness meter used was a type A durometer, and the measured value was recorded as an instantaneous value. The smaller the hardness value, the more excellent the flexibility of the obtained molded product.
The hardness is preferably 60 or less, more preferably 50 or less from the viewpoint of flexibility of the molded body.

(4) Rebound resilience (vibration damping)
Pellets of the thermoplastic elastomer composition obtained in the following Examples and Comparative Examples were compression molded by a compression molding machine at 160° C. for 3 minutes to give a diameter of 29.0±0.5 mm and a thickness of 12.5±0.5 mm. A cylindrical test piece of was prepared. The test piece was measured for impact resilience at −30° C., 0° C. and 25° C. according to JIS K 6255 using a Lupke type impact resilience tester. The smaller the value of the impact resilience is, the more excellent the vibration damping property is.
The impact resilience is preferably 50% or less, more preferably 47% or less, still more preferably 45% or less, from the viewpoint of the vibration damping property of the molded body.

(5) Compression set The pellets of the thermoplastic elastomer compositions obtained in the following Examples and Comparative Examples were compression molded with a compression molding machine at 160° C. for 3 minutes to give a diameter of 13.0±0.5 mm and a thickness of 6. A cylindrical test piece of 3±0.3 mm was prepared. Using this cylindrical test piece, the compression set was measured after maintaining 25% compression deformation for 22 hours at each of two temperatures of 70° C. and 120° C. according to JIS K 6262. The smaller the value of compression set, the better the compression set at high temperature.
The compression set under both conditions of 70° C. and 120° C. is preferably 50% or less, more preferably 47% or less, still more preferably 45% or less.

(6) Extrudability (surface smoothness)
A slit die having a width of 30 mm and a thickness of 2.2 mm is attached to the exit portion of a single-screw extruder, and the thermoplastic elastomer compositions obtained in the following Examples and Comparative Examples are extruded under a temperature condition of 180° C. to form a ribbon. A shaped body was obtained. The surface roughness of this molded product was measured using a surface roughness measuring device (Surfcoder SE1700α manufactured by Kosaka Laboratory Ltd.) at a length of 4 mm and a measurement speed of 0.1 mm/sec. The difference between the maximum value and the minimum value of was evaluated according to the following criteria.
<Extrusion moldability evaluation criteria>
◯: When the difference is less than 20 μm (the surface is smooth)
Δ: When the difference is 20 μm or more and less than 30 μm (the surface is rough)
X: When the difference is 30 μm or more (the surface is rough)

(7) Method of measuring weather resistance By performing the same operation as the above (3), a molded body sheet (length 110 mm, width 110 mm, thickness 2 mm) was obtained. This molded sheet is allowed to stand in an atmosphere of a temperature of 200° C. for a heat resistance test for 60 minutes, and thereafter, using Suntest CPS+ (light source: xenon, irradiation intensity: 550 W/m ² ) manufactured by Toyo Seiki Seisakusho Co., Ltd. A 24-hour light exposure test was performed. The change in color before and after the test was visually observed and visually observed, and evaluated according to the following criteria.
<Evaluation criteria for weather resistance>
◯: No change.
Δ: Some yellowing is observed.

The materials used in the examples and comparative examples are as follows.
<Olefin rubber (I)>
Olefin-based elastomer (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

<Hydrogenated block copolymer (II)>
Hydrogenated block copolymers ((II)-1 to (II)-12) obtained by the following Production Examples 1 to 11 and 19
<Hydrogenated block copolymer (II)'>
Hydrogenated block copolymers ((II)'-1 to (II)'-9) obtained by the following Production Examples 12 to 18, 20 and 21.

<Polyolefin resin (III)>
Homopolypropylene, "F113G" made by Prime Polymer Co., Ltd., MFR 3.0g/10 minutes (230°C, 21.2N load)

<Softener (IV)>
Paraffin type process oil, "PW-90" manufactured by Idemitsu Kosan Co., Ltd.

<Crosslinking agent (V)>
Crosslinking agent (V)-1
2,5-Dimethyl-2,5-di(t-butylperoxy)hexane/silica (=40/60 (mass ratio)), “Perhexa 25B-40” manufactured by NOF CORPORATION
Crosslinking agent (V)-2
Alkylphenol-formaldehyde condensate, "Takkyroll 201" manufactured by Taoka Chemical Co., Ltd.

<Crosslinking aid (VI)>
Triallyl isocyanurate/silica (=40/60 (mass ratio)), "TAIC WH-60" manufactured by Nippon Kasei Co., Ltd.

<Crosslinking accelerator (VII)>
Two kinds of zinc oxide, manufactured by Sakai Chemical Industry Co., Ltd.

<Hydrogenated block copolymers (II) and (II)'>
[Production Example 1]
62.4 kg of cyclohexane as a solvent and 520 g of a 10.5 mass% cyclohexane solution (sec-butyllithium 54.6 g) as an anionic polymerization initiator were charged into a pressure-resistant container which had been purged with nitrogen and dried, and the temperature was raised to 50°C. By adding 2.34 kg of styrene (1) and polymerizing for 1 hour, subsequently adding 10.92 kg of β-farnesene and polymerizing for 2 hours, further adding 2.34 kg of styrene (2) and polymerizing for 1 hour, , A polystyrene-poly(β-farnesene)-polystyrene triblock copolymer was obtained.
To this reaction liquid, 5% by mass of palladium carbon (amount of palladium carried: 5% by mass) as a hydrogenation catalyst was added to the block copolymer, and the reaction was carried out under a hydrogen pressure of 2 MPa and 150° C. for 10 hours. ..
After allowing to cool and releasing pressure, the palladium carbon is removed by filtration, the filtrate is concentrated, and further vacuum dried to obtain a hydrogenated product of a polystyrene-poly(β-farnesene)-polystyrene triblock copolymer (hereinafter, referred to as " Hydrogenated block copolymer (II)-1") was obtained. The hydrogenated block copolymer (II)-1 was evaluated as described above. The results are shown in Table 1.

[Production Examples 2 to 18]
Hydrogenated block copolymers (II)-2 to (II)-11 and (II)'-1 to (II) were prepared in the same manner as in Production Example 1 except that the formulations shown in Tables 1 and 2 were followed. '-7 was manufactured and evaluated in the same manner. The results are shown in Tables 1 and 2.

[Production Example 19]
In a pressure-resistant container which had been purged with nitrogen and dried, 62.4 kg of cyclohexane as a solvent, 237.7 g of sec-butyllithium (10.5 mass% cyclohexane solution) as an anionic polymerization initiator, and 500.2 g of tetrahydrofuran as a Lewis base were charged. After the temperature was raised to 50° C., 7.91 kg of β-farnesene was added and polymerized for 2 hours, then 3.12 kg of styrene (1) was added and polymerized for 1 hour, and 4.57 kg of butadiene was further added for 1 hour. Polymerization was carried out. Subsequently, 25.2 g of dichlorodimethylsilane as a coupling agent was added to this polymerization reaction liquid and reacted for 1 hour to give a poly(β-farnesene)-polystyrene-polybutadiene-polystyrene-poly(β-farnesene) pentablock copolymer. A reaction solution containing
To this reaction liquid, 5% by mass of palladium carbon (amount of palladium carried: 5% by mass) as a hydrogenation catalyst was added to the pentablock copolymer, and the reaction was carried out for 10 hours under the conditions of hydrogen pressure of 2 MPa and 150°C. It was
After cooling and releasing pressure, palladium carbon was removed by filtration, the filtrate was concentrated, and further vacuum dried to obtain poly(β-farnesene)-polystyrene-polybutadiene-polystyrene-poly(β-farnesene) pentablock copolymer. A combined hydrogenated product (hereinafter, referred to as “hydrogenated block copolymer (II)-12”) was obtained. The above physical properties of the hydrogenated block copolymer (II)-12 were measured. The results are shown in Table 1.
The peak top molecular weight of the polymer block (A) of the hydrogenated block copolymer (II)-12 is 8,000, and the peak top molecular weight of the polymer block (B) is 21,100. The peak top molecular weight of the polymer block (C) is 44,000.

[Production Example 20]
In a pressure-resistant container which had been purged with nitrogen and dried, cyclohexane as a solvent and sec-butyllithium (10.5% by mass cyclohexane solution) as an anionic polymerization initiator were charged in the amounts shown in Table 2, and tetrahydrofuran was used as a Lewis base. Charged. After the temperature was raised to 60° C., styrene (1) was added and polymerized for 1 hour, then a mixture of butadiene and isoprene was added and polymerized for 2 hours, and then styrene (2) was added and polymerized for 1 hour. , A styrene-(butadiene/isoprene)-styrene block copolymer was obtained.
To this reaction liquid, 5% by mass of palladium carbon (amount of palladium carried: 5% by mass) as a hydrogenation catalyst was added to the block copolymer, and the reaction was carried out under a hydrogen pressure of 2 MPa and 150° C. for 10 hours. ..
After allowing to cool and releasing pressure, palladium carbon was removed by filtration, the filtrate was concentrated, and further vacuum dried to obtain a hydrogenated product of a styrene-(butadiene/isoprene)-styrene block copolymer (hereinafter, referred to as "hydrogenation"). A block copolymer (II)'-8" was obtained. Table 2 shows the amount of each component used and the measurement results of each physical property of the hydrogenated block copolymer (II)'-8.

[Production Example 21]
In a pressure-resistant container which had been purged with nitrogen and dried, cyclohexane as a solvent and sec-butyllithium (10.5 mass% cyclohexane solution) as an anionic polymerization initiator were charged in the amounts shown in Table 2, and N, as a Lewis base. N,N',N'-tetramethylethylenediamine was charged. After the temperature was raised to 40° C., styrene (1) was added and polymerized for 1 hour, butadiene was subsequently added and polymerized for 2 hours, and styrene (2) was further added and polymerized for 1 hour. -A reaction liquid containing a styrene block copolymer was obtained.
To this reaction liquid, 5% by mass of palladium carbon (amount of palladium carried: 5% by mass) as a hydrogenation catalyst was added to the block copolymer, and the reaction was carried out for 10 hours under a hydrogen pressure of 2 MPa and 150°C. .
After allowing to cool and releasing pressure, the palladium carbon is removed by filtration, the filtrate is concentrated, and further vacuum dried to obtain a hydrogenated product of a styrene-butadiene-styrene block copolymer (hereinafter, referred to as "hydrogenated block copolymer"). (II)'-9') was obtained. Table 2 shows the amounts of the components used and the measurement results of the physical properties of the hydrogenated block copolymer (II)'-9.

[Examples 1 to 24 and Comparative Examples 1 to 18]
(Production of thermoplastic composition)
According to the formulations shown in Tables 3 to 5, olefin rubber (I), hydrogenated block copolymer (II) or (II)', polyolefin resin (III), crosslinking agent (V), crosslinking aid (VI). ) And a crosslinking accelerator (VII) were premixed.
Then, using a twin-screw extruder (“ZSK26Mc” manufactured by Coperion Co.; cylinder number 14), the premixed composition was supplied to the hopper under the conditions of a cylinder temperature of 200° C. and a screw rotation speed of 300 rpm.
Further, the softening agent (IV) was supplied from the position of the cylinder 10 of the twin-screw extruder, melt-kneaded, extruded in a strand shape and cut to produce pellets of the thermoplastic elastomer composition.
Test pieces were prepared using the obtained pellets of the thermoplastic elastomer composition, and hardness, impact resilience, compression set, extrusion moldability (surface smoothness), and weather resistance were evaluated by the above measuring methods. The results are shown in Tables 3-5.

  From Table 3 and Table 4, the thermoplastic elastomer compositions obtained in Examples 1 to 24 have a rebound resilience (vibration damping property) in a wide temperature range from a low temperature range to a high temperature range (-30°C to 25°C). Excellent in addition to this, compression set at high temperature (70°C and 120°C) and weather resistance (200°C for 60 minutes, UV irradiation for 24 hours), and excellent extrusion moldability, flexibility, and moldability. It can be seen that these properties are well balanced.

In contrast, from Table 3, in the thermoplastic elastomer compositions obtained in Comparative Examples 1 to 4, 6 and 7, the hydrogenated block copolymer does not contain the structural unit (b1) derived from farnesene, Poor resilience (vibration damping) in a wide temperature range from low temperature to high temperature (-30°C to 25°C). In particular, the difference is remarkable at −30° C., which shows that the thermoplastic elastomer composition of the present invention and the molded product made of the same have particularly excellent vibration damping properties in a low temperature range. Further, the thermoplastic elastomer compositions obtained in Comparative Examples 1 and 3 are also inferior in compression set at higher temperatures.
Further, the thermoplastic elastomer composition obtained in Comparative Example 5 contains the structural unit (b1) derived from farnesene, but since it uses the unhydrogenated block copolymer (II)′-5. , Poor weather resistance.

  Further, comparing Tables 4 and 5, Comparative Example 8 uses hydrogenated block copolymer (II)′-2 that does not contain the structural unit (b1) derived from farnesene, and therefore is compared with Example 12. Have high hardness, poor rebound resilience at 25°C and -30°C, and insufficient extrusion moldability.

  Similarly, Comparative Examples 9, 10, 12, 14 and 15 use hydrogenated block copolymer (II)'-2 which does not contain the structural unit (b1) derived from farnesene. , 16 and 17, inferior in impact resilience at 25°C and -30°C. In addition, Comparative Examples 13, 16, 17 and 18 use the hydrogenated block copolymer (II)′-4 which does not contain the structural unit (b1) derived from farnesene, so that Examples 15, 20, 21 and 22 is inferior in impact resilience in a wide temperature range from −30° C. to 25° C. and inferior in compression set at 120° C.

  Since Comparative Example 11 does not contain the hydrogenated block copolymer (II), the impact resilience at 25° C. is inferior to that of Example 15, and the extrusion moldability is also insufficient.

[Examples 25 to 36, Comparative Examples 19 to 34]
After premixing all components in the mixing ratios shown in Table 7 or Table 8, a twin-screw extruder [“TEX-44XCT” manufactured by Japan Steel Works, Ltd., screw length (L)/screw diameter (D)=42] was added. A pellet-like thermoplastic elastomer composition was manufactured by supplying and melting and kneading at a temperature of 170 to 200° C. and a rotation speed of 300 min ⁻¹ and hot cutting.
Using the obtained pellet-shaped thermoplastic elastomer composition, each physical property and characteristic were measured or evaluated according to the following methods (8) and (9). The results are shown in Tables 7 and 8. The "hardness" in Tables 7 and 8 is measured by the method described in "(3) Hardness measuring method", and the "compression set" is the "(5) compression set" at 70°C. It was measured.

(8) Injection moldability (molding processability)
The pellets of the thermoplastic elastomer composition obtained in each example are injection-molded by an injection molding machine “EC75SX” (manufactured by Toshiba Machine Co., Ltd.) at a cylinder temperature of 230° C. to prepare a sheet having a length of 100 mm, a width of 35 mm, and a thickness of 2 mm. Then, 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 flow marks in the test piece was visually observed, and the injection moldability was evaluated according to the following criteria.
A: There is no flow mark.
B: Flow mark was present in part.
C: Flow marks were present throughout.

(9) Adhesive force Adhesive force between an adherend made of a dynamically crosslinkable thermoplastic elastomer (TPV) and a thermoplastic elastomer composition or an adherend made of a vulcanized rubber and a thermoplastic elastomer composition by the following method The adhesive strength with was measured.
<Production of adherend (test piece)>
(Production of adherend (test piece) made of TPV)
TPV-1: Using the pellets of "Excelcel 1703B" (manufactured by JSR Corporation), according to the method described in "(8) Formability", a test piece having a length of 50 mm, a width of 35 mm, and a thickness of 2 mm was prepared. This was designated as the adherend "TPV-1". When the hardness of the TPV-1 was measured according to the method described in the above "(3) Measuring method of hardness", the hardness was 71.
TPV-2: A test piece was prepared in the same manner as TPV-1 except that the pellets of "Excellink 1303B" (manufactured by JSR Corporation) were used, and this was used as an adherend "TPV-2". When the hardness of the TPV-2 was measured according to the method described in the above "(3) Method of measuring hardness", the hardness was 42.

(Production of adherend (test piece) made of vulcanized rubber)
Vulcanized EPDM-3: ethylene/propylene/diene copolymer rubber "EPT4045" (manufactured by Mitsui Chemicals, Inc.) and carbon black "Diablack H" (manufactured by Mitsubishi Chemical Corporation) in the compounding amounts shown in Table 6 below. , Anti-aging agent "Nocrac 6C" (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.), stearic acid "Lunack S-20" (manufactured by Kao Corporation) and zinc flower "zinc oxide" (manufactured by Sakai Chemical Industry Co., Ltd.) , Using a Banbury mixer at 150° C. for 6 minutes (kneading first stage). Then, after the obtained composition was taken out and cooled, a vulcanizing agent “sulfur” (fine sulfur, 200 mesh, manufactured by Tsurumi Chemical Industry Co., Ltd.) and a vulcanization accelerator (1 ) "Nox Cellar TS" (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) and vulcanization accelerator (2) "Nox Cellar MP" (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) were added, and the temperature was adjusted using a Banbury mixer. Kneading was performed for 20 minutes at 50° C. and a pressure of 1 MPa (kneading second stage) to obtain a kneaded product.
Further, using a compression molding machine, compression molding was performed under the vulcanization conditions shown in Table 6 below to obtain a sheet (length 150 mm×width 150 mm×thickness 2 mm). From this sheet, a length of 50 mm, a width of 35 mm and a thickness of 2 mm were punched out to prepare a test piece, which was used as an adherend "vulcanized EPDM-3". When the hardness of this vulcanized EPDM-3 was measured according to the method described in the above "(3) Method of measuring hardness", the hardness was 70.

<Method of measuring adhesive strength>
The adherends (50 mm in length × 35 mm in width × 2 mm in thickness) obtained as described above were mounted in a cavity of 100 mm in length, 35 mm in width, and 2 mm in thickness, and the injection molding machine “EC75SX” was placed therein. (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 a single sheet having a thickness of 2 mm, that is, each adherend (TPV-1, TPV-2 or vulcanized EPDM-3) and the thermoplastic elastomer composition. The thing is a state in which the side surface of the sheet is adhered (adhesion area: 35 mm×2 mm).
The resulting composite molded sheet (length 100 mm x width 35 mm x thickness 2 mm) was cut into a length of 100 mm x width 10 mm x thickness 2 mm, and the Instron was universally used at a temperature of 23°C and a pulling speed of 200 mm/min. Using a testing machine "Instron 5566" (manufactured by Instron Japan Co., Ltd.), the adhesive force between the thermoplastic elastomer composition and the adherend was measured.
The adhesive strength between the thermoplastic elastomer composition and TPV-1 in Table 7 is preferably 250 N / cm ² or more, more preferably 310N / cm ² or more, the thermoplastic elastomer composition and vulcanized EPDM-3 The adhesive force is preferably 220 N/cm ² or more, more preferably 240 N/cm ² or more. Further, the compression set in Table 7 is preferably 57% or less, more preferably 51% or less.
On the other hand, adhesion between the thermoplastic elastomer composition and TPV-2 in Table 8, preferably 110N / cm ² or more, more preferably 140 N / cm ² or more, the thermoplastic elastomer composition and vulcanized EPDM-3 The adhesive force is preferably 100 N/cm ² or more, more preferably 115 N/cm ² or more. The compression set in Table 8 is preferably 42% or less, more preferably 37% or less.

  As is clear from the examples and comparative examples, the thermoplastic elastomer composition of the present invention has high adhesion to vulcanized rubber and dynamically crosslinkable thermoplastic elastomer (TPV), and has flexibility and It has excellent weatherability and moldability.

Claims (22)

A thermoplastic elastomer composition containing an olefin rubber (I), the following hydrogenated block copolymer (II), and a polyolefin resin (III) other than the olefin rubber (I), wherein the olefin rubber The mass ratio of the following hydrogenated block copolymer (II) to (I) is 0.1 to 9, and the total amount of the olefin rubber (I) and the following hydrogenated block copolymer (II) is 100 parts by mass. The thermoplastic elastomer composition, wherein the content of the polyolefin resin (III) is 10 to 200 parts by mass.
<Hydrogenated block copolymer (II)>
The content of the polymer block (A) consisting of a structural unit derived from an aromatic vinyl compound and the structural unit (b1) derived from farnesene is 70 to 100% by mass, and a structural unit (b2) derived from a conjugated diene other than farnesene is contained. Is a hydrogenated product of a block copolymer containing a polymer block (B) having a content of 30 to 0 mass% and a peak top molecular weight of more than 210,000 and less than 602,000. A copolymer in which the carbon-carbon double bond in the united block (B) is hydrogenated in an amount of 50 mol% or more.   The thermoplastic elastomer composition according to claim 1, wherein the farnesene-derived structural unit (b1) in the polymer block (B) of the hydrogenated block copolymer (II) is a β-farnesene-derived structural unit. ..   The mass ratio [(A)/(B)] of the polymer block (A) and the polymer block (B) in the hydrogenated block copolymer (II) is 1/99 to 55/45. The thermoplastic elastomer composition according to 1 or 2.   The thermoplastic elastomer composition according to any one of claims 1 to 3, wherein a hydrogenation rate of carbon-carbon double bonds in the polymer block (B) is 70 mol% or more.   The thermoplastic elastomer composition according to claim 1, wherein the aromatic vinyl compound is styrene.   The thermoplastic elastomer composition according to any one of claims 1 to 5, wherein the conjugated diene other than farnesene is one or more selected from isoprene, butadiene, and myrcene.   The softening agent (IV) is further contained in an amount of 1 to 350 parts by mass based on 100 parts by mass of the olefin rubber (I) and the hydrogenated block copolymer (II). The thermoplastic elastomer composition described in 1.   The hydrogenated block copolymer (II) further contains a polymer block (C) composed of a structural unit derived from a conjugated diene other than farnesene, and at least two polymer blocks (A), at least 1 Hydrogenated block copolymers comprising at least one polymer block (B) and at least one polymer block (C), wherein at least one polymer block (B) is terminal. The thermoplastic elastomer composition according to any one of claims 1 to 7.   Mass ratio of the polymer block (A) to the total of the polymer block (A), the polymer block (B) and the polymer block (C) [(A)/[(A)+(B)+ (C)]] is 5/100-80/100, The thermoplastic elastomer composition of Claim 8.   The thermoplastic elastomer composition according to claim 8 or 9, wherein a mass ratio [(C)/(B)] of the polymer block (C) to the polymer block (B) is 5/95 to 95/5. object.   The peak top molecular weight of the polymer block (A) is 2,000 to 100,000, the peak top molecular weight of the polymer block (B) is 2,000 to 200,000, and the polymer block (C The thermoplastic elastomer composition according to any one of claims 8 to 10, wherein the peak top molecular weight of) is 4,000 to 200,000.   A crosslinked product obtained by crosslinking the thermoplastic elastomer composition according to any one of claims 1 to 11.   A molded article comprising the thermoplastic elastomer composition according to claim 1 or the crosslinked product according to claim 12.   A member having a site (X1) made of the thermoplastic elastomer composition according to claim 1.   The member according to claim 14, which has a part (Y1) made of a material different from the thermoplastic elastomer composition according to any one of claims 1 to 11, in addition to the part (X1).   The member according to claim 15, wherein the material of the portion (Y1) is a vulcanized rubber or a dynamically crosslinkable olefinic thermoplastic elastomer (TPV).   In addition to the site (X1), the thermoplastic elastomer composition according to any one of claims 1 to 11 (provided that the thermoplastic elastomer composition forming the site (X1) is the same or different. 15. The member according to claim 14, having a portion (X2) consisting of   The member according to any one of claims 14 to 17, wherein the portion (X1) is a portion obtained by injection molding.   A weather seal comprising the member according to claim 14.   The weather seal according to claim 19, comprising a corner portion formed of the portion (X1) and a straight portion formed of the portion (X2) or (Y1).   The weather seal according to claim 19 or 20, which is for an automobile, a ship, or an aircraft.   A weather seal corner member having a portion (X1) formed of the thermoplastic elastomer composition according to claim 1.