JP2018024776A - Thermoplastic elastomer composition, laminated structure and method for producing laminated structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition which is excellent in flexibility, tensile characteristics, moldability, heat resistance and weather resistance and has strong adhesive force; a laminated structure; and a method for producing the laminated structure.SOLUTION: There are provided a thermoplastic elastomer composition, where a content of a thermoplastic elastomer (II) is 100-300 pts.mass with respect to 100 pts.mass of a hydrogenated block copolymer (I), the hydrogenated block copolymer (I) contains a polymer block (A1) containing a structural unit derived from an aromatic vinyl compound and a polymer block (B1) containing 1-100 mass% of a structural unit (b1) derived from farnesene and 99-0 mass% of a structural unit (b2) derived from conjugated diene other than the farnesene and is a hydrogenated product of a block copolymer (P) in which a mass ratio [(A1)/(B1)] is 1/99 to 70/30, a hydrogenation ratio is 50 mol% or more, and the thermoplastic elastomer (II) is at least one selected from the group consisting of a thermoplastic polyurethane elastomer and a thermoplastic polyester elastomer; a laminated structure; and a method for producing the laminated structure.SELECTED DRAWING: None

Description

  The present invention relates to a thermoplastic elastomer composition containing a hydrogenated block copolymer containing a polymer block containing a structural unit derived from an aromatic vinyl compound and a polymer block containing a structural unit derived from farnesene, The present invention relates to a laminated structure and a method for producing the laminated structure.

  Ceramics, metals, and synthetic resins having excellent durability, heat resistance, and mechanical strength are widely used in various applications such as home appliances, electronic parts, machine parts, and automobile parts. These members are bonded or combined with elastomer members with excellent flexibility for fixing to other structural members, for impact absorption, damage prevention or sealing, etc., depending on the application, component configuration and usage method, etc. There are cases where it is used.

As such an elastomer member, a styrenic thermoplastic elastomer that is excellent in flexibility, tensile properties, and moldability may be suitably used. Here, the styrenic thermoplastic elastomer is an aromatic vinyl compound-conjugated diene block copolymer having a polymer block composed of a structural unit derived from an aromatic vinyl compound and a polymer block composed of a structural unit derived from a conjugated diene. Or the hydrogenated substance is pointed out.
However, since styrenic thermoplastic elastomer is a low-polarity material, it has a problem in that it does not have sufficient adhesive strength to synthetic resins, ceramics, metals, etc. having high polarity and is difficult to melt and bond as it is.
Therefore, a thermoplastic resin composition containing an aromatic vinyl compound-conjugated diene block copolymer or a hydrogenated product thereof and a polyurethane elastomer in order to bond a highly polar synthetic resin, ceramics or metal, and a styrene thermoplastic elastomer. Things have been proposed. However, since the aromatic vinyl compound-conjugated diene block copolymer or a hydrogenated product thereof and the polyurethane elastomer are inferior in compatibility, characteristics such as molding processability and adhesiveness cannot be sufficiently exhibited.
Therefore, an aromatic vinyl compound-conjugated diene block copolymer or a hydrogenated product thereof and a thermoplastic elastomer, a specific addition polymerization polymer block, and a polyurethane block copolymer having a polyurethane block made of a polyurethane elastomer are provided. The thermoplastic resin composition to contain is disclosed (patent documents 1 to 3).
In addition, in order to improve flexibility, moldability, high polarity synthetic resin, adhesion to ceramics and metals, aromatic vinyl compound-conjugated diene block copolymer or its hydrogenated product and polar group-containing olefinic polymer A thermoplastic elastomer composition containing a coalescence is disclosed (Patent Document 4).

Japanese Patent Laid-Open No. 11-302495 JP 2003-41089 A JP 2004-346109 A International Publication No. 2015/087955 Pamphlet

However, the methods disclosed in Patent Documents 1 to 4 do not have sufficient flexibility, tensile properties, molding processability, heat resistance, and weather resistance, and are more adhesive to highly polar synthetic resins, ceramics, metals, and the like. There is a need for improvement.
The present invention has been made in view of the above circumstances, and has excellent flexibility, tensile properties, molding processability, heat resistance, weather resistance, and is strong against highly polar synthetic resins, ceramics, metals, and the like. An object of the present invention is to provide a thermoplastic elastomer composition having a sufficient adhesive force, a laminated structure, and a method for producing the laminated structure.

The gist of the present invention is the following [1] to [23].
[1] A thermoplastic elastomer composition containing a hydrogenated block copolymer (I) and a thermoplastic elastomer (II),
The content of the thermoplastic elastomer (II) is 100 to 300 parts by mass with respect to 100 parts by mass of the hydrogenated block copolymer (I),
The hydrogenated block copolymer (I) contains 1 to 100% by mass of a polymer block (A1) containing a structural unit derived from an aromatic vinyl compound and a structural unit (b1) derived from farnesene, other than farnesene A polymer block (B1) containing 99 to 0% by mass of a structural unit (b2) derived from conjugated diene of
A hydrogenated block copolymer (P) having a mass ratio [(A1) / (B1)] of the polymer block (A1) to the polymer block (B1) of 1/99 to 70/30. Yes,
The hydrogenation rate of the carbon-carbon double bond in the polymer block (B1) is 50 mol% or more,
The thermoplastic elastomer composition, wherein the thermoplastic elastomer (II) is at least one selected from the group consisting of a thermoplastic polyurethane elastomer and a thermoplastic polyester elastomer.

[2] The thermoplastic elastomer composition according to [1], further containing 1 to 200 parts by mass of a polar group-containing polymer (III) with respect to 100 parts by mass of the hydrogenated block copolymer (I). .
[3] The thermoplastic elastomer composition according to [1] or [2], further comprising 1 to 100 parts by mass of a softening agent (IV) with respect to 100 parts by mass of the hydrogenated block copolymer (I). object.
[4] The thermoplastic elastomer composition according to [3], wherein the bioratio of the softening agent (IV) is 70% by weight or more.
[5] The thermoplastic elastomer composition according to any one of [1] to [4], wherein the hydrogenation rate of the carbon-carbon double bond in the polymer block (B1) is 70 mol% or more.
[6] The thermoplastic resin according to any one of [1] to [5], wherein the aromatic vinyl compound is at least one selected from the group consisting of styrene, α-methylstyrene, and 4-methylstyrene. Elastomer composition.
[7] The thermoplastic elastomer composition according to any one of [1] to [6], wherein the farnesene is β-farnesene.
[8] The thermoplastic elastomer composition according to any one of [1] to [7], wherein the conjugated diene other than farnesene is at least one selected from the group consisting of isoprene, butadiene, and myrcene.
[9] The peak top molecular weight (Mp) determined by gel permeation chromatography of the hydrogenated block copolymer (I) in terms of standard polystyrene is 4,000 to 1,500,000, [1] to [8] The thermoplastic elastomer composition according to any one of [8].
[10] The thermoplastic elastomer composition according to any one of [1] to [9], wherein the hydrogenated block copolymer (I) has a molecular weight distribution (Mw / Mn) of 1 to 6.
[11] Hydrogen of a triblock copolymer in which the hydrogenated block copolymer (I) has blocks in the order of the polymer block (A1), the polymer block (B1), and the polymer block (A1). The thermoplastic elastomer composition according to any one of [1] to [10], which is an additive.

[12] Hydrogenated block copolymer (P) in which the hydrogenated block copolymer (I) includes the polymer block (A1), the polymer block (B1), and the polymer block (C1). And
In the polymer block (C1), the content of the structural unit (c1) derived from farnesene is less than 1% by mass, and the content of the structural unit (c2) derived from conjugated diene other than farnesene is 1 to 100% by mass. A polymer block,
The mass ratio [(A1) / ((B1) + (C1))] of the polymer block (A1) and the total amount of the polymer block (B1) and the polymer block (C1) is 1/99. ~ 70/30,
The block copolymer (P) comprises at least two polymer blocks (A1), at least one polymer block (B1), and at least one polymer block (C1); and Having at least one polymer block (B1) at its end;
The heat according to any one of [1] to [10], wherein the hydrogenation rate of the carbon-carbon double bond in the polymer block (B1) and the polymer block (C1) is 50 mol% or more. Plastic elastomer composition.

[13] The polymer group (B2) in which the polar group-containing polymer (III) contains a polymer block (A2) containing a structural unit derived from an aromatic vinyl compound and a structural unit derived from a conjugated diene other than farnesene. [1] to [12], which are a block copolymer (D) containing a block copolymer having hydrogen or a hydrogenated product thereof and a block copolymer (III-a) containing a thermoplastic polyurethane elastomer block (E). ] The thermoplastic-elastomer composition in any one of.
[14] The above [1] to [12], wherein the polar group-containing polymer (III) is a polymer (III-b) having a functional group derived from an α, β-unsaturated carboxylic acid or a derivative thereof. The thermoplastic elastomer composition according to any one of the above.
[15] The thermoplastic elastomer composition according to [14], wherein the α, β-unsaturated carboxylic acid or derivative thereof is at least one selected from the group consisting of (meth) acrylic acid esters and maleic anhydride. object.
[16] The polar group-containing polymer (III-b) is an ethylene- (meth) acrylic acid alkyl ester copolymer containing a structural unit derived from ethylene and a structural unit derived from a (meth) acrylic acid alkyl ester. The thermoplastic elastomer composition according to [14] or [15].
[17] The thermoplastic elastomer composition according to [14], wherein the polar group-containing polymer (III-b) is an acid-modified polymer obtained by grafting maleic anhydride to a side chain.
[18] The polymer constituting the acid-modified polymer is a polymer block (A3) containing a structural unit derived from an aromatic vinyl compound and a polymer block containing a structural unit derived from a conjugated diene compound other than farnesene ( B3) or a block copolymer (III-b1) containing a polymer block (F) containing a hydrogenated product thereof, and at least one selected from the group consisting of polyolefin (III-b2) The thermoplastic elastomer composition according to the above [17].
[19] The block copolymer (III-b1) is a hydrogenated product of a polystyrene-polybutadiene-polystyrene triblock copolymer (SEBS), or a hydrogenated product of a polystyrene-polyisoprene-polystyrene triblock copolymer. The thermoplastic elastomer according to [18], which is at least one selected from the group consisting of (SEPS) and a hydrogenated product (SEEPS) of a polystyrene-poly (isoprene / butadiene) -polystyrene triblock copolymer. Composition.

[20] Laminated structure having a layer formed of the thermoplastic elastomer composition according to any one of [1] to [19] and a layer formed of a material other than the thermoplastic elastomer composition body.
[21] The laminated structure according to [20], wherein the other material is at least one selected from the group consisting of a synthetic resin and a metal.
[22] A method for producing a laminated structure, comprising subjecting the thermoplastic elastomer composition according to any one of [1] to [19] to melt lamination molding on a material other than the thermoplastic elastomer composition.
[23] The method for manufacturing a laminated structure according to [22], wherein the melt lamination molding is performed by an injection insert molding method.

  According to the present invention, a thermoplastic elastomer composition that is excellent in flexibility, tensile properties, moldability, heat resistance, weather resistance, and has strong adhesion to highly polar synthetic resins, ceramics, metals, etc. A laminated structure and a method for producing the laminated structure can be provided.

[Thermoplastic elastomer composition]
The thermoplastic elastomer composition of the present invention is a thermoplastic elastomer composition containing a hydrogenated block copolymer (I) and a thermoplastic elastomer (II), wherein the content of the thermoplastic elastomer (II) is 100 to 300 parts by mass with respect to 100 parts by mass of the hydrogenated block copolymer (I), and the hydrogenated block copolymer (I) is a polymer block containing a structural unit derived from an aromatic vinyl compound. (A1) and a polymer block (B1) containing 1 to 100% by mass of the structural unit (b1) derived from farnesene and 99 to 0% by mass of the structural unit (b2) derived from a conjugated diene other than farnesene. Water of the block copolymer (P) having a mass ratio [(A1) / (B1)] of the polymer block (A1) and the polymer block (B1) of 1/99 to 70/30. A hydrogenated content of carbon-carbon double bonds in the polymer block (B1) is 50 mol% or more, and the thermoplastic elastomer (II) is a thermoplastic polyurethane elastomer and a thermoplastic polyester elastomer. Is at least one selected from the group consisting of

<Hydrogenated block copolymer (I)>
The hydrogenated block copolymer (I) (hereinafter also simply referred to as “hydrogenated block copolymer (I)”) is a polymer block (A1) (hereinafter referred to as “hydrogenated block copolymer (I)”) containing a structural unit derived from an aromatic vinyl compound. Simply referred to as “polymer block (A1)”, containing 1 to 100% by mass of farnesene-derived structural units (b1), and containing 99 to 0% by mass of structural units derived from conjugated dienes other than farnesene (b2). Polymer block (B1) (hereinafter also simply referred to as “polymer block (B1)”), and the mass ratio of the polymer block (A1) to the polymer block (B1) [(A1) / (B1 )] Is a hydrogenated product of the block copolymer (P) (hereinafter also simply referred to as “block copolymer (P)”) having a ratio of 1/99 to 70/30, and is contained in the polymer block (B1). Hydrogenation of carbon-carbon double bonds There is greater than or equal to 50 mol%.

[Polymer block (A1)]
The polymer block (A1) contains 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- Examples thereof include vinyl naphthalene, vinyl anthracene, N, N-diethyl-4-aminoethyl styrene, vinyl pyridine, 4-methoxy styrene, monochlorostyrene, dichlorostyrene and divinylbenzene. These aromatic vinyl compounds may be used alone or in combination of two or more. Among these, styrene, α-methylstyrene, and 4-methylstyrene are preferable, and styrene is more preferable.

  The polymer block (A1) contains structural units derived from monomers other than the aromatic vinyl compound, for example, other monomers such as monomers constituting the polymer block (B1) described later. Also good. However, the content of the structural unit derived from the aromatic vinyl compound in the polymer block (A1) is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and 90% by mass or more. Is still more preferable, and it is still more preferable that it is 100 mass%.

[Polymer block (B1)]
The polymer block (B1) contains a structural unit (b1) derived from farnesene (hereinafter, also simply referred to as “structural unit (b1)”). Such farnesene may be either α-farnesene or β-farnesene represented by the following formula (I), but β-farnesene is preferred from the viewpoint of ease of production of the block copolymer (P). Note that α-farnesene and β-farnesene may be used in combination.

  Content of the structural unit (b1) derived from farnesene in a polymer block (B1) is 1-100 mass%. When the content of the structural unit (b1) derived from farnesene is less than 1% by mass, flexibility and molding processability are lowered, and it has a strong adhesion to highly synthetic resins, ceramics, metals, and the like. A thermoplastic elastomer composition cannot be obtained. From this viewpoint, the content of the structural unit (b1) derived from farnesene in the polymer block (B1) is preferably 10 to 100% by mass, more preferably 20 to 100% by mass, and still more preferably 30 to 100% by mass. 50-100 mass% is still more preferable, and 70-100 mass% is still more preferable. Moreover, when farnesene is derived from biotechnology, the amount of conjugated dienes other than farnesene such as petroleum-derived butadiene and isoprene can be suppressed, and the dependence on petroleum can be reduced. From this viewpoint, the content of the structural unit (b1) derived from farnesene in the polymer block (B1) is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and further 70 to 100% by mass. Preferably, 80-100 mass% is still more preferable.

The polymer block (B1) may contain a structural unit (b2) derived from a conjugated diene other than farnesene (hereinafter also simply referred to as “structural unit (b2)”). Examples of such conjugated dienes include isoprene, butadiene, 2,3-dimethyl-butadiene, 2-phenyl-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3 -Octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octatriene, myrcene, chloroprene and the like. These may be used alone or in combination of two or more. Among these, isoprene, butadiene and myrcene are preferable, and isoprene and butadiene are more preferable.
The content of the structural unit (b2) derived from a conjugated diene other than farnesene in the polymer block (B1) is 0 to 99 mass%, preferably 1 to 90 mass%, more preferably 5 to 80 mass%, 10-70 mass% is still more preferable, 15-50 mass% is still more preferable, 20-30 mass% is still more preferable.
When the structural unit (b2) is contained in the polymer block (B1), the content of the structural unit (b1) derived from farnesene in the polymer block (B1) is preferably 10 to 99% by mass, % By mass is more preferable, 20 to 95% by mass is further preferable, 30 to 90% by mass is still more preferable, 50 to 85% by mass is still more preferable, and 70 to 80% by mass is still more preferable.

  The polymer block (B1) may contain other structural units other than the structural unit (b1) and the structural unit (b2). The total content of the structural unit (b1) and the structural unit (b2) in the polymer block (B1) is preferably 60% by mass or more, more preferably 80% by mass or more, and still more preferably 100% by mass.

The hydrogenated block copolymer (I) is a hydrogenated product of a block copolymer (P) containing at least one polymer block (A1) and each polymer block (B1). The hydrogenated block copolymer (I) is a hydrogenated product of a block copolymer (P) containing at least two polymer blocks (A1) and at least one polymer block (B1). Is preferred.
The bonding form of the polymer block (A1) and the polymer block (B1) is not particularly limited, and may be linear, branched, radial, or a combination of two or more thereof. Among these, a form in which each block is linearly bonded is preferable. When the polymer block (A1) is represented by A1 and the polymer block (B1) is represented by B1, (A1-B1) _l , A1- (B1 -A1) The bond form represented by _m or B1- (A1-B1) _n is preferred. In addition, said l, m, and n represent an integer greater than or equal to 1 each independently.
From the viewpoints of flexibility, molding processability, handleability, and the like, the bonding form preferably has a block in the order of the polymer block (A1), the polymer block (B1), and the polymer block (A1). The added block copolymer (I) is preferably a hydrogenated product of a triblock copolymer represented by A1-B1-A1.
In the case where the block copolymer (P) has two or more polymer blocks (A1) or two or more polymer blocks (B1), each polymer block is a polymer comprising the same structural unit. It may be a block or a polymer block composed of different structural units. For example, in the two polymer blocks (A1) in the triblock copolymer represented by A1-B1-A1, the types of aromatic vinyl compounds may be the same or different.

  The mass ratio [(A1) / (B1)] of the polymer block (A1) and the polymer block (B1) in the block copolymer (P) is from 1/99 to 70/30. Within such a range, it is possible to obtain a thermoplastic elastomer composition having excellent flexibility and molding processability, and having a strong adhesive force to highly polar synthetic resins, ceramics, metals and the like. From this viewpoint, the mass ratio [(A1) / (B1)] of the polymer block (A1) and the polymer block (B1) is preferably 1/99 to 60/40, and preferably 5/95 to 55/45. More preferably, 10 / 90-50 / 50 is still more preferable, and 15 / 85-40 / 60 is still more preferable.

[Polymer block (C1)]
In addition to the polymer block (A1) and the polymer block (B1), the hydrogenated block copolymer (I) is further referred to as a polymer block (C1) (hereinafter also referred to as “polymer block (C1)”). ) May be a hydrogenated product of the block copolymer (P). In the polymer block (C1), the content of the structural unit (c1) derived from farnesene is less than 1% by mass, and the content of the structural unit (c2) derived from conjugated diene other than farnesene is 1 to 100% by mass. .
Further, by including the polymer block (C1), it is possible to obtain a thermoplastic elastomer composition having a strong adhesive force to a synthetic resin, ceramics, metal or the like having high tensile properties, moldability, and polarity.
Farnesene constituting the structural unit (c1) derived from farnesene (hereinafter also simply referred to as “structural unit (c1)”) and structural units derived from conjugated dienes other than farnesene (c2) (hereinafter simply referred to as “structural unit (c2)”) The conjugated diene constituting the structural unit (b1) derived from farnesene and the same conjugated diene constituting the structural unit (b2) derived from conjugated dienes other than farnesene are exemplified. .
As the conjugated diene constituting the structural unit (c2) derived from a conjugated diene other than farnesene, isoprene, butadiene and myrcene are preferable, isoprene and butadiene are more preferable, polar resins, and adhesiveness to metals. From the viewpoint, butadiene is more preferable.

Here, “the content of the structural unit (c1) derived from farnesene is less than 1% by mass” in the polymer block (C1) means that the content of the structural unit (c1) is 0% by mass, that is, the structural unit ( The case of not containing c1) is also included. The content of the structural unit (c1) derived from farnesene in the polymer block (C1) is preferably 0% by mass.
The content of the structural unit (c2) derived from a conjugated diene other than farnesene in the polymer block (C1) is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, and still more preferably 90 to 100% by mass. More than 99 mass% and 100 mass% are still more preferable, and it is still more preferable that it is 100 mass%.
The polymer block (C1) may contain other structural units other than the structural unit derived from farnesene (c1) and the structural unit derived from conjugated dienes other than farnesene (c2). The structure in the polymer block (C1) 60 mass% or more is preferable, as for the total content of a unit (c1) and a structural unit (c2), 80 mass% or more is more preferable, and 100 mass% is still more preferable.

The hydrogenated block copolymer (I) is preferably a hydrogenated product of a block copolymer (P) having at least one polymer block (B1) at its terminal. Moldability is improved by having at least one polymer block (B1) at the end of the polymer chain. From this viewpoint, when the hydrogenated block copolymer (I) is linear, it is more preferable to have the polymer block (B1) at both ends. When the hydrogenated block copolymer (I) is branched or radial, the number of polymer blocks (B1) present at the terminal is preferably 2 or more, and more preferably 3 or more.
When the block copolymer (P) further includes a polymer block (C1), the block copolymer (P) includes at least two polymer blocks (A1) and at least one polymer block (B1). And a block copolymer comprising at least one polymer block (C1), preferably at least two polymer blocks (A1), at least one polymer block (B1), and at least one polymer. More preferably, the block contains a block (C1) and has at least one polymer block (B1) at the terminal.

When the block copolymer (P) includes the polymer block (A1), the polymer block (B1), and the polymer block (C1), the bonding form of the plurality of polymer blocks is not particularly limited and is linear, It may be branched, radial, or a combination of two or more thereof. Among these, the form which each block couple | bonded linearly is preferable.
The block copolymer (P) has a structure having blocks in the order of the polymer block (B1), the polymer block (A1), and the polymer block (C1) (that is, the structure of B1-A1-C1). Is preferred.

When the polymer block (A1) is represented by A1, the polymer block (B1) by B1, and the polymer block (C1) by C1, a tetrablock copolymer represented by B1-A1-C1-A1, B1 -A1-C1-A1-B1 represented by a pentablock copolymer, B1-A1- (C1-A1) _p- B1, B1-A1- (C1-A1-B1) _q , B1- (A1-C1 -A1-B1) _r (p, q, r each independently represents an integer of 2 or more) is preferred, and a pentablock copolymer represented by B1-A1-C1-A1-B1 is more preferred.

Here, in the present specification, when the same kind of polymer block is linearly bonded via a divalent coupling agent or the like, the entire bonded polymer block is handled as one polymer block. It is. Accordingly, the polymer block that should be expressed strictly as A1-X-A1 (X represents a coupling agent residue) is expressed as A1 as a whole. In the present specification, this type of polymer block containing a coupling agent residue is handled as described above. The block copolymer to be expressed as A1-B1 is expressed as B1-A1-C1-A1-B1, and is treated as an example of a pentablock copolymer.
Further, the two or more polymer blocks (A1) of the block copolymer (P) may be polymer blocks composed of the same structural unit or polymer blocks composed of different structural units. . Similarly, when the block copolymer (P) has two or more polymer blocks (B1) or two or more polymer blocks (C1), each polymer block is composed of the same structural unit. Even if it is a polymer block, the polymer block which consists of a different structural unit may be sufficient.

When the block copolymer (P) includes the polymer block (A1), the polymer block (B1), and the polymer block (C1), the mass ratio of the polymer block (A1) to the polymer block (B1) [(A1) / (B1)] is 1/99 to 70/30, preferably 5/95 to 60/40, more preferably 10/90 to 50/50, and 20/80 to 40/60. More preferably, 25/75 to 35/65 is even more preferable. Within such a range, it is possible to obtain a thermoplastic elastomer composition having excellent flexibility and molding processability, and having a strong adhesive force to highly polar synthetic resins, ceramics, metals and the like.
Mass ratio of polymer block (A1) to the total amount of polymer block (A1), polymer block (B1) and polymer block (C1) [(A1) / ((A1) + (B1) + (C1) )] Is preferably 5/100 to 80/100, more preferably 10/100 to 50/100, and still more preferably 12/100 to 40/100.
The mass ratio [(C1) / (B1)] of the polymer block (C1) and the polymer block (B1) is preferably 5/95 to 95/5, more preferably 10/90 to 70/30. 20/80 to 60/40 is more preferable, and 30/70 to 50/50 is still more preferable.

  In the block copolymer (P), the mass ratio [(A1) / ((B1) + (C1) of the polymer block (A1) and the total amount of the polymer block (B1) and the polymer block (C1)]. ))] Is preferably 1/99 to 70/30. Within such a range, it is possible to obtain a thermoplastic elastomer having a strong adhesion to synthetic resins, ceramics, metals and the like having high tensile properties, moldability, and polarity. From this viewpoint, the mass ratio [(A1) / ((B1) + (C1))] is more preferably 1/99 to 60/40, further preferably 10/90 to 40/60, and 10/90 to 30/70 is still more preferable, and 15/85 to 25/75 is still more preferable.

  Total content of structural unit (b1) and structural unit (c1) with respect to the total amount of polymer block (B1) and polymer block (C1) in block copolymer (P) [((b1) + (c1) ) / ((B1) + (C1))] is preferably 30 to 99% by mass. Within such a range, excellent tensile properties, moldability, and adhesion to metal are excellent. From this viewpoint, the mass ratio [((b1) + (c1)) / ((B1) + (C1))] is more preferably 40 to 90% by mass, further preferably 45 to 80% by mass, and 50 to 50%. 70 mass% is still more preferable, and 55-65 mass% is still more preferable.

  The total content of the polymer block (A1), the polymer block (B1) and the polymer block (C1) in the block copolymer (P) is preferably 80% by mass or more, more preferably 90% by mass or more. 95 mass% or more is more preferable, and 100 mass% is still more preferable.

  The hydrogenated block copolymer (I) is a block copolymer comprising a polymer block (A1), a polymer block (B1), and a polymer block (C1) from the viewpoint of tensile properties, moldability, and adhesion to metal. It is a hydrogenated product of the polymer (P), the polymer block (C1) has a content of structural units (c1) derived from farnesene of less than 1% by mass, and structural units derived from conjugated dienes other than farnesene (c2) ) Is a polymer block having a content of 1 to 100% by mass, and the mass ratio of the polymer block (A1) to the total amount of the polymer block (B1) and the polymer block (C1) [(A1) / ((B1) + (C1))] is 1/99 to 70/30, and the block copolymer (P) has at least two polymer blocks (A1) and at least one of the weights. Combined block (B ), And at least one polymer block (C1) and having at least one polymer block (B1) at the terminal, and the carbon block in the polymer block (B1) and the polymer block (C1) — The hydrogenation rate of the carbon double bond is preferably 50 mol% or more.

The block copolymer (P) is composed of other monomers in addition to the polymer block (A1), the polymer block (B1), and the polymer block (C1) as long as the effects of the present invention are not impaired. It may contain a polymer block.
Examples of such other monomers include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1- Unsaturated hydrocarbon compounds such as tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene; acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate , Acrylonitrile, methacrylonitrile, maleic acid, fumaric acid, crotonic acid, itaconic acid, 2-acryloylethanesulfonic acid, 2-methacryloylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamide-2 -Methylpropane sulfonic acid, vinyl sulfonic acid, vinegar Functional group-containing unsaturated compounds such as vinyl acid and methyl vinyl ether; These may be used alone or in combination of two or more.
When the block copolymer (P) has another polymer block, the content thereof is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass.

[Production Method of Hydrogenated Block Copolymer (I)]
The hydrogenated block copolymer (I) includes, for example, a polymerization step for obtaining the block copolymer (P) by anionic polymerization, and the polymer block (B1) in the block copolymer (P), or the polymer block When it contains (C1), it can be suitably produced by a step of hydrogenating a carbon-carbon double bond in the polymer block (B1) and the polymer block (C1).

(Polymerization process)
The block copolymer (P) can be produced by a solution polymerization method or a method described in JP-A-2012-502135, JP-A-2012-502136. Among these, a solution polymerization method is preferable, and known methods such as an ion polymerization method such as anionic polymerization and cationic polymerization, and a radical polymerization method can be applied. Among these, the anionic polymerization method is preferable. In the anionic polymerization method, an aromatic vinyl compound, farnesene and / or conjugated dienes other than farnesene are sequentially added in the presence of a solvent, an anionic polymerization initiator, and, if necessary, a Lewis base, to form a block copolymer (P )
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; lanthanoid rare earth metals such as lanthanum and neodymium; And compounds containing earth metals and lanthanoid rare earth metals. Of these, compounds containing alkali metals and alkaline earth metals are preferred, and organic alkali metal compounds are more preferred.

Examples of the organic alkali metal compound include methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium, stilbenelithium, dilithiomethane, dilithionaphthalene, and 1,4-dilithiobutane. Organic lithium compounds such as 1,4-dilithio-2-ethylcyclohexane and 1,3,5-trilithiobenzene; sodium naphthalene, potassium naphthalene and the like. Among these, an organic lithium compound is preferable, n-butyl lithium and sec-butyl lithium are more preferable, and sec-butyl lithium is particularly 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, and 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, farnesene and conjugated dienes other than farnesene. It is the range of mass%.

  The solvent is not particularly limited as long as it does not adversely affect the anionic polymerization reaction. For example, saturated aliphatic hydrocarbons such as n-pentane, isopentane, n-hexane, n-heptane and isooctane; cyclopentane, cyclohexane and methylcyclopentane And saturated alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene. These may be used alone or in combination of two or more. There is no restriction | limiting in particular in the usage-amount of a solvent.

  The Lewis base has a role of controlling the microstructure in the structural unit derived from farnesene and the structural unit derived from conjugated dienes 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; potassium Examples include alkali metal alkoxides such as t-butoxide; phosphine compounds. When using a Lewis base, it is preferable that the quantity is 0.01-1000 molar equivalent normally with respect to 1 mol of anionic polymerization initiators normally.

The temperature of the polymerization reaction is usually in the range of −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. Each monomer is continuously or intermittently supplied into the polymerization reaction solution so that the amount of aromatic vinyl compound, farnesene and / or conjugated diene other than farnesene in the polymerization reaction system falls within a specific range, Or a block copolymer (P) can be manufactured by superposing | polymerizing sequentially so that each monomer may become a specific ratio in a polymerization reaction liquid.
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 liquid into a poor solvent such as methanol to precipitate the block copolymer (P), or washing the polymerization reaction liquid with water, separating, and drying. Can be isolated.

  As described above, the hydrogenated block copolymer (I) preferably includes a structure having the polymer block (B1), the polymer block (A1), and the polymer block (C1) in this order. Including a step of obtaining a block copolymer by producing a combined block (B1), a polymer block (A1), and a polymer block (C1) in this order, and a step of hydrogenating the obtained block copolymer. More preferably, it is produced by a method. In the case where the hydrogenated block copolymer (I) has the polymer block (B1) only at one end of the polymer chain, the other polymer blocks were polymerized so as to be linearly bonded. Later, the polymer block (B1) may be finally obtained by a method of manufacturing.

The hydrogenated block copolymer (I) comprises at least two polymer blocks (A1), at least one polymer block (B1), and at least one polymer block (C1), and at least 1 When the block copolymer (P) is a hydrogenated product of the block copolymer (P) having one polymer block (B1) at its terminal, a method for producing the block copolymer (P) includes a polymer block (B1) and a polymer. A method of polymerizing the block (A1), the polymer block (C1), and the polymer block (A1) in this order, or the polymer block (B1), the polymer block (A1), and the polymer block (C1). Examples include a method of polymerizing in order and producing the polymer block (C1) by coupling ends of the polymer block (C1) using a coupling agent. In the present invention, the latter method using a coupling agent is preferable from the viewpoint of efficient production.
Examples of the coupling agent include divinylbenzene; polyvalent epoxy compounds such as epoxidized 1,2-polybutadiene, epoxidized soybean oil, and tetraglycidyl-1,3-bisaminomethylcyclohexane; tin tetrachloride, tetrachlorosilane, Halides such as trichlorosilane, trichloromethylsilane, dichlorodimethylsilane, dibromodimethylsilane; methyl benzoate, ethyl benzoate, phenyl benzoate, diethyl oxalate, diethyl malonate, diethyl adipate, dimethyl phthalate, dimethyl terephthalate Ester compounds such as dimethyl carbonate, diethyl carbonate, diphenyl carbonate and the like; diethoxydimethylsilane, trimethoxymethylsilane, triethoxymethylsilane, tetramethoxysilane, tetraethoxy Orchids, tetrabutoxysilane, tetrakis (2-ethylhexyl oxy) silane, bis (triethoxysilyl) ethane, an alkoxysilane compounds such as 3-aminopropyltriethoxysilane; 2,4-tolylene diisocyanate, and the like.

In the main polymerization step, an unmodified block copolymer (P) may be obtained as described above, or a block copolymer (P) modified as follows may be obtained.
In the case of the modified block copolymer (P), the block copolymer (P) may be modified before the hydrogenation step described later. 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, and acid anhydride groups.
Examples of the modification method of the block copolymer include, for example, tin tetrachloride, tetrachlorosilane, dichlorodimethylsilane, dimethyldiethoxysilane, tetramethoxysilane, tetraethoxy, which can react with a polymerization active terminal before adding a polymerization terminator. Coupling agents such as silane, 3-aminopropyltriethoxysilane, tetraglycidyl-1,3-bisaminomethylcyclohexane, 2,4-tolylene diisocyanate, 4,4′-bis (diethylamino) benzophenone, N-vinyl Examples thereof include a method of adding a polymerization terminal modifier such as pyrrolidone or other modifiers described in JP2011-132298A. In addition, maleic anhydride or the like can be grafted onto the isolated copolymer.
The position where the functional group is introduced may be the polymerization terminal of the block copolymer (P) or the side chain. Moreover, the said functional group may combine 1 type (s) or 2 or more types. The modifying agent is preferably in the range of 0.01 to 10 molar equivalents relative to 1 mol of the anionic polymerization initiator.

(Hydrogenation process)
The hydrogenated block copolymer (I) can be obtained by subjecting the block copolymer (P) obtained by the above method or the modified block copolymer (P) to a hydrogenation step. A known method can be used for the hydrogenation. For example, in a solution in which the block copolymer (P) is dissolved in a solvent that does not affect the hydrogenation reaction, a Ziegler catalyst; nickel, platinum, palladium, ruthenium supported on carbon, silica, diatomaceous earth, etc. Rhodium metal catalyst: An organic metal complex having cobalt, nickel, palladium, rhodium or ruthenium metal is present as a hydrogenation catalyst to carry out a hydrogenation reaction. In the hydrogenation step, the hydrogenation reaction may be performed by adding a hydrogenation catalyst to the polymerization reaction solution containing the block copolymer (P) obtained by the method for producing the block copolymer (P). . 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 100 to 200 ° C., and the reaction time is preferably 1 to 20 hours.

The hydrogenation rate of the carbon-carbon double bond in the polymer block (B1) is 50 to 100 mol%, preferably 70 to 100 mol%, and preferably 75 to 100 mol% from the viewpoints of heat resistance and weather resistance. Is more preferable, 80-100 mol% is still more preferable, 85-100 mol% is still more preferable, 90-100 mol% is still more preferable.
When the block copolymer (P) includes the polymer block (C1), the hydrogenation rate of the carbon-carbon double bond in the polymer block (B1) and the polymer block (C1) is heat resistance and weather resistance. From this viewpoint, it is 50 to 100 mol%, preferably 70 to 100 mol%, more preferably 75 to 100 mol%, still more preferably 80 to 100 mol%, still more preferably 85 to 100 mol%, and 90 to 100 mol% is still more preferable.
The hydrogenation rate can be calculated by measuring ¹ H-NMR of the block copolymer (P) and the hydrogenated block copolymer (I) after hydrogenation.

The peak top molecular weight (Mp) of the hydrogenated block copolymer (I) is preferably from 4,000 to 1,500,000, more preferably from 9,000 to 1,000,000, from the viewpoint of moldability. 000 to 800,000 is more preferable, and 50,000 to 500,000 is still more preferable.
1-6 are preferable, as for molecular weight distribution (Mw / Mn) of hydrogenated block copolymer (I), 1-4 are more preferable, 1-3 are still more preferable, and 1-2 are still more preferable. When the molecular weight distribution is within the above range, the viscosity variation of the hydrogenated block copolymer (I) is small and easy to handle.
In addition, the peak top molecular weight (Mp) and molecular weight distribution (Mw / Mn) in this specification mean the value measured by the method described in the Example mentioned later.

  The peak top molecular weight of the polymer block (A1) is preferably from 2,000 to 100,000, more preferably from 4,000 to 80,000, still more preferably from 5,000 to 50,000, from the viewpoint of moldability. 6,000 to 30,000 is even more preferable.

  The peak top molecular weight of the polymer block (B1) is preferably from 2,000 to 200,000, more preferably from 3,000 to 150,000, and even more preferably from 4,000 to 100,000, from the viewpoint of moldability. .

  Furthermore, the peak top molecular weight of the polymer block (C1) is preferably 4,000 to 200,000, more preferably 4,500 to 150,000, and 5,000 to 100,000 from the viewpoint of moldability. Further preferred.

<Thermoplastic elastomer (II)>
The thermoplastic elastomer composition of the present invention contains a thermoplastic elastomer (II).
The thermoplastic elastomer (II) is at least one selected from the group consisting of a thermoplastic polyurethane elastomer and a thermoplastic polyester elastomer.

(Thermoplastic polyurethane elastomer)
A thermoplastic polyurethane elastomer is a thermoplastic polyurethane obtained by the reaction of a polymeric diol, an organic diisocyanate and a chain extender. The polymer diol used for forming the thermoplastic polyurethane elastomer preferably has a number average molecular weight of 1,000 to 6,000. Thereby, a thermoplastic elastomer composition excellent in mechanical properties, heat resistance and the like can be obtained.
Here, the number average molecular weight of the polymer diol referred to in the present specification is a number average molecular weight calculated based on a hydroxyl value measured by SITE based on JIS K1557-1: 2007.

  Examples of the polymer diol used for producing the thermoplastic polyurethane elastomer include polyester diol, polyether diol, polyester ether diol, polycarbonate diol, polyester polycarbonate diol, and the like. These polymer diols may be used alone or in combination of two or more.

  The polyester diol used in the production of the thermoplastic polyurethane elastomer is obtained by reacting at least one dicarboxylic acid component selected from the group consisting of aliphatic dicarboxylic acids, aromatic dicarboxylic acids and esters thereof with a low molecular diol. Examples thereof include polyester diols and polyester diols obtained by ring-opening polymerization of lactones. More specifically, examples of the polyester diol include aliphatic dicarboxylic acids having 6 to 12 carbon atoms such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; terephthalic acid At least one selected from the group consisting of aromatic dicarboxylic acids such as isophthalic acid and orthophthalic acid and esters thereof, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1, At least one aliphatic diol having 2 to 10 carbon atoms such as 6-hexanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, and the like. Polyester diol, polycaprolactone diol, polyvale obtained by polycondensation reaction Mention may be made of the lactone diol, and the like.

As said polyether diol used for manufacture of a thermoplastic polyurethane elastomer, polyethylene glycol, polypropylene glycol, polytetramethylene glycol etc. can be mentioned, for example.
Examples of the polycarbonate diol used for the production of the thermoplastic polyurethane elastomer include at least one aliphatic diol such as 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, and the like. Mention may be made of polycarbonate diols obtained by reacting seeds with carbonates such as diphenyl carbonate and alkyl carbonate or phosgene.

  The organic diisocyanate used in the production of the thermoplastic polyurethane elastomer is not particularly limited, but at least one selected from the group consisting of aromatic diisocyanates having a molecular weight of 500 or less, alicyclic diisocyanates and aliphatic diisocyanates is preferable. Specific examples of organic diisocyanates include 4,4′-diphenylmethane diisocyanate, toluene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate (4,4′-dicyclohexylmethane diisocyanate). , Isophorone diisocyanate, hexamethylene diisocyanate, and the like. Among these, 4,4′-diphenylmethane diisocyanate is preferable.

  As the chain extender used in the production of the thermoplastic polyurethane elastomer, any chain extender conventionally used in the production of thermoplastic polyurethane elastomers can be used, and the kind thereof is not particularly limited. Among them, the chain extender is preferably at least one selected from the group consisting of aliphatic diols, alicyclic diols, and aromatic diols. Specific examples of the chain extender include ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-1,3-propanediol, 1,6-hexanediol, neopentyl glycol, Examples include diols such as 1,9-nonanediol, cyclohexanediol, and 1,4-bis (β-hydroxyethoxy) benzene. Among these, an aliphatic diol having 2 to 6 carbon atoms is preferable, and 1,4-butanediol is more preferable. These chain extenders may be used alone or in combination of two or more.

  The thermoplastic polyurethane elastomer comprises a polymer diol, a chain extender and an organic diisocyanate in a range of moles of polymer diol: moles of chain extender = 1: 0.2 to 8 and [with polymer diol and The total number of moles of chain extender]: [number of moles of organic diisocyanate] = 1: A thermoplastic polyurethane elastomer obtained by reacting in a range of 0.98 to 1.04 is preferable. As a result, there is no sudden rise in melt viscosity at the time of melt molding such as extrusion molding and injection molding of the thermoplastic elastomer composition of the present invention, and products such as target molded products and laminated structures can be produced smoothly. Furthermore, the heat resistance of the product obtained thereby becomes good.

  The thermoplastic polyurethane elastomer preferably has a hardness (type A hardness; measured at 25 ° C.) of 55 to 90. When the hardness of the thermoplastic polyurethane elastomer is 55 or more, the mechanical properties of a product such as a molded article or a laminated structure obtained from the thermoplastic elastomer composition are good. Further, when the hardness of the thermoplastic polyurethane elastomer is 90 or less, the flexibility of a product such as a molded product or a laminated structure obtained from the thermoplastic elastomer composition is increased.

  As a thermoplastic polyurethane elastomer, a thermoplastic polyurethane elastomer having a poly (3-methyl-1,5-pentaneadipate) diol having a number average molecular weight of 2,000 or more as a soft segment, that is, adipic acid and 3-methyl-1,5 -When a polyester diol having a number average molecular weight of 2,000 or more obtained by polycondensation with pentanediol and a thermoplastic polyurethane elastomer obtained by reacting the chain extender and organic diisocyanate are used, flexibility, tensile properties, A thermoplastic elastomer composition excellent in molding processability and adhesiveness can be obtained.

  The production method of the thermoplastic polyurethane elastomer is not particularly limited, and is produced by the prepolymer method or the one-shot method using the above-described polymer diol, organic diisocyanate, and chain extender, using a known urethanization reaction. May be. Among these, it is preferable to perform melt polymerization substantially in the absence of a solvent, and it is more preferable to manufacture by continuous melt polymerization using a multi-screw extruder.

  A commercially available thermoplastic polyurethane elastomer may be used. Specific examples include “Kuramylon U” (trade name) manufactured by Kuraray Co., Ltd., “Elastollan” (trade name) manufactured by BASF Polyurethane Elastomers Co., Ltd. “Rezamin P” (trade name) manufactured by Dainichi Seika K.K.

(Thermoplastic polyester elastomer)
In the present invention, the thermoplastic polyester elastomer that can be used as the thermoplastic elastomer (II) is not particularly limited as long as it is a thermoplastic polyester elastomer. As such a thermoplastic polyester elastomer, (i) a thermoplastic polyester elastomer having an aromatic crystalline polyester as a hard segment and a polyether as a soft segment (hereinafter also referred to as “polyester-polyether type thermoplastic polyester elastomer”), And (ii) a thermoplastic polyester elastomer (hereinafter, also referred to as “polyester-polyester type thermoplastic polyester elastomer”) having an aromatic crystalline polyester as a hard segment and an aliphatic polyester as a soft segment. Among these, the (i) polyester-polyether thermoplastic polyester elastomer is preferable from the viewpoints of availability and hydrolysis resistance.

  The method for producing the polyester-polyether thermoplastic polyester elastomer is not particularly limited, but at least one selected from the group consisting of aliphatic diols having 2 to 12 carbon atoms and alicyclic diols, aromatic dicarboxylic acids or alkyls thereof. It can be obtained by using an ester and a polyalkylene ether glycol having a number average molecular weight of 400 to 6,000 as raw materials, producing an oligomer by esterification or transesterification, and polycondensing the oligomer. .

  The C2-C12 aliphatic diol and alicyclic diol used in the production of the polyester-polyether thermoplastic polyester elastomer are not particularly limited as long as they are usually used in the production of thermoplastic polyester elastomers. Examples thereof include ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like. Among these, ethylene glycol and 1,4-butanediol are preferable, and those having 1,4-butanediol as a main component are more preferable. These diols may be used alone or in combination of two or more.

  The aromatic dicarboxylic acid used for producing the polyester-polyether type thermoplastic polyester elastomer is not particularly limited as long as it is conventionally used as a raw material for the thermoplastic polyester elastomer. For example, terephthalic acid, isophthalic acid, Examples thereof include phthalic acid and 2,6-naphthalenedicarboxylic acid. Among these, as the aromatic dicarboxylic acid, terephthalic acid and 2,6-naphthalenedicarboxylic acid are preferable, and those having terephthalic acid as a main component are more preferable. These aromatic dicarboxylic acids may be used alone or in combination of two or more.

  Examples of aromatic dicarboxylic acid alkyl esters used in the production of polyester-polyether thermoplastic polyester elastomers include dimethyl esters such as dimethyl terephthalate, dimethyl isophthalate, dimethyl phthalate, and 2,6-dimethyl naphthalate. Can do. Among these, dimethyl terephthalate and 2,6-dimethyl naphthalate are preferable, and those having dimethyl terephthalate as a main component are more preferable. These alkyl esters of aromatic dicarboxylic acids may be used alone or in combination of two or more.

  The polyalkylene ether glycol preferably has a number average molecular weight of 400 to 6,000, more preferably 500 to 4,000, and still more preferably 600 to 3,000. When the number average molecular weight is 400 or more, a polyester-polyether type thermoplastic polyester elastomer having good elasticity, particularly high breaking strength, can be obtained. When the number average molecular weight is 6,000 or less, phase separation in the thermoplastic elastomer composition can be suppressed, and a decrease in physical properties of the thermoplastic elastomer composition can be suppressed.

  Examples of the polyalkylene ether glycol used for the production of the polyester-polyether type thermoplastic polyester elastomer include polyethylene glycol, poly (1,2-propylene ether) glycol, poly (1,3-propylene ether) glycol, and polytetramethylene. Examples include ether glycol, polyhexamethylene ether glycol, a block or random copolymer of ethylene oxide and propylene oxide, and a block or random copolymer of ethylene oxide and tetrahydrofuran. Among these, the polyester-polyether type thermoplastic polyester elastomer is preferably formed using polytetramethylene ether glycol.

  In the polyester-polyether type thermoplastic polyester elastomer, the content of the structural portion derived from the polyalkylene ether glycol is preferably 5 to 95% by mass, more preferably 10 to 85% by mass, with respect to the mass. More preferred is mass%. When the content of the structural portion derived from the polyalkylene ether glycol is 95% by mass or less, a polyester-polyether type thermoplastic polyester elastomer can be obtained by polycondensation.

  In addition to the above, the polyester-polyether type thermoplastic polyester elastomer may be formed by copolymerizing a small amount of a trifunctional diol, other diol, other dicarboxylic acid or ester thereof, and further a fat such as adipic acid. A group dicarboxylic acid, an alicyclic dicarboxylic acid or an alkyl ester thereof may be used as a copolymerization component.

  In the polyester-polyester type thermoplastic polyester elastomer (ii), the hard segment made of an aromatic crystalline polyester is made of the same polyester as the above-mentioned aromatic crystalline polyester in the polyester-polyether type thermoplastic polyester elastomer. Constructed, the soft segment is composed of aliphatic polyester. Examples of the aliphatic polyester constituting the soft segment include a polyester oligomer obtained by condensation of an aliphatic dicarboxylic acid or alicyclic dicarboxylic acid and an aliphatic diol; a polyester oligomer synthesized from an aliphatic lactone or an aliphatic monool carboxylic acid. be able to.

Examples of polyester oligomers in which an aliphatic dicarboxylic acid or alicyclic dicarboxylic acid and an aliphatic diol, which constitute a soft segment of a polyester-polyester type thermoplastic polyester elastomer, are condensed with succinic acid, oxalic acid, adipic acid, Aliphatic dicarboxylic acids such as sebacic acid; at least one selected from the group consisting of alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, dicyclohexyl-4,4′-dicarboxylic acid And a polyester oligomer obtained by condensation of at least one selected from the group consisting of diols such as ethylene glycol, propylene glycol, tetramethylene glycol, and pentamethylene glycol.
Examples of polyester oligomers synthesized from aliphatic lactones or aliphatic monool carboxylic acids that constitute the soft segment of polyester-polyester thermoplastic polyester elastomers are synthesized from ε-caprolactone, ω-oxycaproic acid, etc. Examples thereof include polycaprolactone-based polyester oligomers.

  The esterification reaction, transesterification reaction, polycondensation reaction and the like for producing the thermoplastic polyester elastomer can be carried out according to conventional methods. 120-250 degreeC is preferable and, as for the reaction temperature of esterification reaction or transesterification, 150-230 degreeC is more preferable. The polycondensation reaction is usually performed at a temperature of 200 to 280 ° C. for 2 to 6 hours under a reduced pressure of 1333 Pa or less (10 torr or less). As a catalyst in these reactions, at least one selected from the group consisting of metal alcoholate compounds such as tin, titanium, zinc, manganese, chlorides, oxides, etc. can be used, An organotitanium compound is preferred, and tetrabutyl titanate is more preferred.

  In the production of the thermoplastic polyester elastomer, phosphoric acid, phosphorous acid, hypophosphorous acid, or a metal salt thereof may be added as an auxiliary agent. In particular, when the reaction is carried out by adding an alkali metal hypophosphite, a thermoplastic polyester elastomer having a low content of terminal carboxyl groups and excellent in hydrolysis resistance can be obtained. Examples of the alkali metal hypophosphite include sodium hypophosphite, potassium hypophosphite, lithium hypophosphite and the like. Among these, sodium hypophosphite is preferable. The amount of alkali metal hypophosphite added is preferably 1 to 1,000 ppm, more preferably 3 to 200 ppm, and still more preferably 5 to 80 ppm with respect to the thermoplastic polyester elastomer produced. When the addition amount of the alkali metal hypophosphite is 1 ppm or more, the addition effect can be sufficiently obtained, and when it is 1,000 ppm or less, the effect is exhibited without inhibiting the polycondensation reaction. be able to.

  The method for adding the alkali metal hypophosphite salt is not particularly limited, and the alkali metal hypophosphite salt may be added to the molten polymer under production in any state such as a solution, a slurry, or a solid. . Further, the alkali metal hypophosphite may be added at any time as long as it is at least before the end of the polycondensation reaction, that is, before the esterification reaction or before the transesterification reaction and before the end of the polycondensation reaction. . From the viewpoint of suppressing the decrease in polymerizability, it is preferable to add in a slurry state immediately before the start of the polycondensation reaction under reduced pressure.

  The production of the thermoplastic polyester elastomer includes other additives such as hindered phenol antioxidants, hindered amine antioxidants, phosphorus antioxidants, sulfur antioxidants, triazole light stabilizers and the like. You may carry out in presence of another additive. In particular, the thermoplastic polyester elastomer used in the present invention can contain a hindered phenolic antioxidant in a proportion of 0.01 to 1% by mass with respect to the thermoplastic polyester elastomer.

  A commercially available thermoplastic polyester elastomer may be used. Specific examples include, but are not limited to, “Perprene P” and “Perprene S” (trade name) manufactured by Toyobo Co., Ltd., “Hytrel” (trade name) manufactured by Toray DuPont Co., Ltd., Japan Name “Lomod” (trade name) manufactured by GE Plastics, “Nichigo Polyester” (trade name) manufactured by Nippon Synthetic Chemical Industry Co., Ltd., “Teijin Polyester Elastomer” (trade name) manufactured by Teijin Limited Can do.

In the thermoplastic elastomer composition of the present invention, the content of the thermoplastic elastomer (II) is 100 to 300 parts by mass with respect to 100 parts by mass of the hydrogenated block copolymer (I). When the content of the thermoplastic elastomer (II) is less than 100 parts by mass, it is not possible to obtain a thermoplastic elastomer composition having sufficient adhesion to polar resins, metals and the like. On the other hand, when the thermoplastic elastomer (II) is more than 300 parts by mass, the adhesiveness is improved, but the thermoplastic elastomer composition becomes hard and the flexibility and moldability are lowered. From this viewpoint, the content of the thermoplastic elastomer (II) is preferably 120 to 250 parts by mass and more preferably 150 to 200 parts by mass with respect to 100 parts by mass of the hydrogenated block copolymer (I).
In the thermoplastic elastomer composition of the present invention, the total content of the hydrogenated block copolymer (I) and the thermoplastic elastomer (II) is preferably 50% by mass or more, and 55% by mass in the total amount of the thermoplastic elastomer composition. % Or more is more preferable, 60% by mass or more is more preferable, and from the viewpoint of stably obtaining good adhesiveness, 99% by mass or less is preferable, 90% by mass or less is more preferable, and 80% by mass or less is still more preferable.

<Polar group-containing polymer (III)>
The thermoplastic elastomer composition of the present invention may contain a polar group-containing polymer (III). Thereby, it is excellent in a softness | flexibility, a tensile characteristic, and a moldability, and can show strong adhesive force also to a highly polar synthetic resin, ceramics, a metal, etc.
It is not necessarily clear in detail that such an effect can be obtained, but by containing the polar group-containing polymer (III), an adherend of a highly polar synthetic resin, ceramic, metal, etc. and the present invention When the compatibility with the thermoplastic elastomer composition is good, and the adherend has a polar group, the polar group contained in the polar group-containing polymer (III) and the polar group on the adherend surface There may be a reason such as forming a chemical bond with.

The polar group of the polar group-containing polymer (III) includes (meth) acryloyloxy group; hydroxyl group; urethane group; amide group; halogen group such as fluoro, chloro and bromo; carboxyl group; ester group; Etc. Among these, (meth) acryloyloxy group, urethane group, carboxyl group, ester group, and acid anhydride group are preferable from the viewpoint of improving adhesion to highly polar synthetic resins, ceramics, metals, etc., urethane group, carboxyl group Group and acid anhydride group are more preferable.
In the present specification, “(meth) acryloyl” means “acryloyl or methacryloyl”.

[Block copolymer (III-a)]
As the polar group-containing polymer (III) having a urethane group as a polar group, a polymer block (A2) containing a structural unit derived from an aromatic vinyl compound (hereinafter, also simply referred to as “polymer block (A2)”) And a block comprising a polymer block (B2) containing a structural unit derived from a conjugated diene other than farnesene (hereinafter also simply referred to as “polymer block (B2)”) or a polymer block containing a hydrogenated product thereof (D) (hereinafter also simply referred to as “polymer block (D)”) and a block copolymer (III) including a thermoplastic polyurethane elastomer block (E) (hereinafter also simply referred to as “elastomer block (E)”) -A) is preferred.

Examples of the aromatic vinyl compound constituting the structural unit derived from the aromatic vinyl compound in the polymer block (A2) include the same aromatic vinyl compounds as those constituting the polymer block (A1).
Examples of the conjugated diene constituting the structural unit derived from a conjugated diene other than farnesene in the polymer block (B2) include the same conjugated dienes as the structural unit (b2) derived from a conjugated diene other than farnesene. .
The polymer block (A2) may contain structural units derived from monomers other than the aromatic vinyl compound, for example, other monomers such as monomers constituting the polymer block (B2). . However, the content of the structural unit derived from the aromatic vinyl compound in the polymer block (A2) is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and 90% by mass or more. Is still more preferable, and it is still more preferable that it is 100 mass%.
The polymer block (B2) may contain structural units derived from monomers other than conjugated dienes other than farnesene, for example, other monomers such as monomers constituting the polymer block (A2). Good. However, the content of structural units derived from conjugated dienes other than farnesene in the polymer block (B2) is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and 90% by mass. The above is still more preferable, and it is still more preferable that it is 100 mass%.

In the polymer block (D), the polymer block (A2) and the polymer block (B2) are formed from the viewpoints of heat resistance and rubber physical properties of products such as molded articles and laminated structures obtained from the thermoplastic elastomer composition. The mass ratio ((A2) / (B2)) is preferably 10/90 to 90/10, more preferably 20/80 to 80/20, and still more preferably 30/70 to 70/30.
The total content of the polymer block (A2) and the polymer block (B2) in the polymer block (D) is preferably 60% by mass or more, more preferably 80% by mass or more, and still more preferably 100% by mass.

The elastomer block (E) may be any block containing a thermoplastic polyurethane elastomer, but when a thermoplastic polyurethane elastomer is used as the thermoplastic elastomer (II), the same or similar heat as the thermoplastic polyurethane elastomer described above. It is preferably formed from a plastic polyurethane elastomer. Thereby, the compatibility of the polymers in a thermoplastic elastomer composition becomes favorable, and the mechanical characteristics of products, such as a molded article obtained from a thermoplastic elastomer composition, and a laminated structure, will be excellent.
The number average molecular weight of the elastomer block (E) is preferably from 200 to 150,000, and more preferably from 500 to 100,000, from the viewpoint of rubber physical properties of the thermoplastic elastomer composition.

  The block copolymer (III-a) includes at least one polymer block (D) and elastomer block (E). The block copolymer (III-a) may be a polyblock copolymer in which the total number of the polymer block (D) and the elastomer block (E) is 3 or more. From the viewpoint of properties and mechanical properties, a diblock copolymer in which one polymer block (D) and one elastomer block (E) are bonded is preferable.

The block copolymer (III-a) is, for example, a block copolymer having a thermoplastic polyurethane elastomer, a polymer block (A2) and a polymer block (B2), and having a functional group, preferably a hydroxyl group at the terminal. After blending or a hydrogenated product thereof (hereinafter also referred to as “terminal-modified block copolymer”) by kneading and reacting under melting conditions, the polyurethane block copolymer is extracted and extracted from the resulting polyurethane reaction product. It can be obtained by collecting.
At that time, the melt-kneading of the thermoplastic polyurethane elastomer and the terminal-modified block copolymer can be performed using a melt-kneading apparatus such as a single-screw extruder, a twin-screw extruder, a kneader, or a Banbury mixer. The melt-kneading conditions can be selected according to the type of thermoplastic polyurethane elastomer and terminal-modified block copolymer used, the type of apparatus, etc., but it can be carried out at a temperature of 180 to 250 ° C. for about 1 to 15 minutes. preferable.

  In addition to the method described above, the block copolymer (III-a) can be used for, for example, a reaction in producing a thermoplastic polyurethane elastomer by reacting a polymer diol, an organic diisocyanate and a chain extender in an extruder or the like. A polyurethane-based reaction product containing a polyurethane-based block copolymer is formed by adding a terminal-modified block copolymer in the system at the beginning or in the middle of the reaction, and the polyurethane-based reaction product is converted into a polyurethane-based reaction product. It can also be obtained by extracting and recovering the block copolymer.

  In the above, the extraction and recovery of the polyurethane block copolymer from the polyurethane reaction product may be performed, for example, by pulverizing the polyurethane reaction product to an appropriate size as required, and then pulverizing the polyurethane reaction product with a polyurethane such as dimethylformamide. Treatment with a good solvent to extract and remove the unreacted thermoplastic polyurethane elastomer, and then treatment with a good solvent for the terminal-modified block copolymer such as cyclohexane to extract and remove the unreacted terminal-modified block copolymer; This can be done by drying the remaining solid.

  The terminal-modified block copolymer can be produced, for example, by the following anionic polymerization method. That is, when an alkyl lithium compound or the like is used as a polymerization initiator and an aromatic vinyl compound and a conjugated diene are sequentially polymerized in an inert organic solvent such as n-hexane or cyclohexane, and a desired molecular structure and molecular weight are reached, A compound having an oxirane skeleton such as ethylene oxide, propylene oxide, styrene oxide, or a lactone compound such as ε-caprolactone, β-propiolactone, dimethylpropiolactone (pivalolactone) is added, and then alcohols and carboxylic acids It can be produced by adding an active hydrogen-containing compound such as water to stop the polymerization. The block copolymer thus obtained is preferably composed of a combination of an alkylaluminum compound or an alkyllithium compound and a transition metal compound such as cobalt or nickel in an inert organic solvent such as n-hexane or cyclohexane. A hydrogenated terminal-modified block copolymer can be obtained by hydrogenation in the presence of a hydrogenation catalyst such as a Ziegler catalyst under the conditions of a reaction temperature of 20 to 250 ° C. and a hydrogen pressure of 0.1 to 20 MPa. it can.

  If the terminal-modified block copolymer has a linear structure, it may have one hydroxyl group at one end of the molecule or two hydroxyl groups at both ends of the molecule. It may be. Further, when the terminal-modified block copolymer has a branched or radial structure, it may have one or a plurality of hydroxyl groups at the molecular end, that is, the number of branches. For example, in the case of a linear structure, the number of terminal hydroxyl groups per molecule of the terminal-modified block copolymer is preferably 0.5 to 1, more preferably 0.7 to 1. .

[Polymer (III-b)]
As the polar group-containing polymer (III) having a carboxyl group or an acid anhydride group as a polar group, a polymer (III-b) having a functional group derived from an α, β-unsaturated carboxylic acid or a derivative thereof ( Hereinafter, simply referred to as “polymer (III-b)” is preferable.
Examples of the α, β-unsaturated carboxylic acid or derivatives thereof include α, β-unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, fumaric acid, and itaconic acid; α, β such as (meth) acrylic acid ester -Unsaturated carboxylic acid ester; α, β-unsaturated carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride. Among these, at least one selected from the group consisting of α, β-unsaturated carboxylic acid esters and α, β-unsaturated carboxylic acid anhydrides is preferred, and from the group consisting of (meth) acrylic acid esters and maleic anhydride. At least one selected is more preferable.
In the present specification, “(meth) acryl” means “acryl or methacryl”.

  Specific examples of (meth) acrylic acid esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-hexyl acrylate, and acrylic acid. Acrylic acid alkyl esters such as isohexyl, n-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, methacrylic acid Examples include methacrylic acid alkyl esters such as isobutyl, n-hexyl methacrylate, isohexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, and 2-ethylhexyl methacrylate.

As a method for introducing a functional group derived from α, β-unsaturated carboxylic acid or a derivative thereof into a polymer chain, α, β-unsaturated carboxylic acid or a derivative thereof and a monomer having no polar group are used. It may be a method of random copolymerization, block copolymerization or graft copolymerization by a known method.
As a monomer which does not have a polar group, a C2-C10 olefin is preferable and a C2-C8 olefin is more preferable. Examples of such olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, and cyclohexene. Among these, ethylene and propylene are preferable, and ethylene is more preferable. These olefins may be used alone or in combination of two or more.

  Examples of the polymer (III-b) include a copolymer containing a structural unit derived from an olefin and a structural unit derived from an α, β-unsaturated carboxylic acid or a derivative thereof. For example, ethylene- (meth) acrylic acid copolymer; ethylene- (meth) acrylic acid methyl copolymer, ethylene- (meth) acrylic acid ethyl copolymer and other structural units derived from ethylene and (meth) acrylic acid alkyl Examples include ethylene- (meth) acrylic acid alkyl ester copolymers containing ester-derived structural units; ethylene- (meth) acrylic acid copolymer metal ion cross-linked resins (ionomers), and the like. Among these, an ethylene- (meth) acrylic acid alkyl ester copolymer is more preferable.

  The content of the structural unit derived from the α, β-unsaturated carboxylic acid or derivative thereof is preferably 0.01 to 10% by mass in all the structural units of the polar group-containing polymer (III-b). If it is 0.01 mass% or more, it can adhere | attach with resin, ceramics, a metal, etc. which have polarity by low temperature heat processing, and can obtain the thermoplastic elastomer composition which has strong adhesive force. If the content of the structural unit derived from α, β-unsaturated carboxylic acid or derivative thereof is 10% by mass or less, the affinity with the hydrogenated block copolymer (I) is improved, and the tensile properties are improved. The resulting thermoplastic elastomer composition is excellent in flexibility and moldability. From these viewpoints, the content of the structural unit derived from the α, β-unsaturated carboxylic acid or derivative thereof is more preferably 0.01 to 7% by mass, and still more preferably 0.01 to 5% by mass. In order to optimize the content of structural units derived from α, β-unsaturated carboxylic acid or derivatives thereof, polyolefins containing a high concentration of structural units derived from α, β-unsaturated carboxylic acids or derivatives thereof, You may use what was diluted with the polyolefin which does not have the unit derived from (beta) -unsaturated carboxylic acid or its derivative (s) as a polar group containing polymer (III-b).

As another method for introducing a functional group derived from α, β-unsaturated carboxylic acid or a derivative thereof into the polymer chain, α, β-unsaturated carboxylic acid anhydride is grafted to the side chain of the polymer chain. Examples of the method include acid modification. The polar group-containing polymer (III-b) obtained by such a method is preferably an acid-modified polymer obtained by grafting maleic anhydride to the side chain of the polymer chain.
Examples of the polymer constituting the acid-modified polymer include an aromatic vinyl compound-conjugated diene block copolymer and polyolefin. Among these, a polymer block (A3) containing a structural unit derived from an aromatic vinyl compound (hereinafter also simply referred to as “polymer block (A3)”) and a heavy polymer containing a structural unit derived from a conjugated diene other than farnesene. A block copolymer having a combined block (B3) (hereinafter also simply referred to as “polymer block (B3)”) or a polymer block (F) containing a hydrogenated product thereof (hereinafter simply referred to as “polymer block (F)”) It is preferably at least one selected from the group consisting of block copolymers (III-b1) and polyolefins (III-b2), and more preferably block copolymers (III-b1). .

In the polymer block (A3) of the block copolymer (III-b1), the aromatic vinyl compound constituting the structural unit derived from the aromatic vinyl compound is the aromatic vinyl compound constituting the polymer block (A1). The same thing is mentioned.
In the polymer block (B3) of the block copolymer (III-b1), a conjugated diene constituting a structural unit derived from a conjugated diene other than farnesene constitutes a structural unit (b2) derived from a conjugated diene other than the aforementioned farnesene. Examples thereof include those similar to the conjugated dienes, and among them, isoprene and butadiene are preferable, and butadiene is more preferable.
The polymer block (A3) may contain structural units derived from monomers other than the aromatic vinyl compound, for example, other monomers such as monomers constituting the polymer block (B3). . However, the content of the structural unit derived from the aromatic vinyl compound in the polymer block (A3) is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and 90% by mass or more. Is still more preferable, and it is still more preferable that it is 100 mass%.
The polymer block (B3) contains structural units derived from monomers other than conjugated dienes other than farnesene, for example, other monomers such as monomers constituting the polymer block (A3). Also good. However, the content of structural units derived from conjugated dienes other than farnesene in the polymer block (B3) is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and 90% by mass. The above is even more preferable.

In the polymer block (F), the polymer block (A3) and the polymer block (B3) are formed from the viewpoint of heat resistance and rubber physical properties of a product such as a molded article and a laminated structure obtained from the thermoplastic elastomer composition. The mass ratio [(A3) / (B3)] is preferably 10/90 to 90/10, more preferably 20/80 to 80/20, and still more preferably 30/70 to 70/30.
The total content of the polymer block (A3) and the polymer block (B3) in the polymer block (F) is preferably 60% by mass or more, more preferably 80% by mass or more, and still more preferably 100% by mass.

  As block copolymer (III-b1), polystyrene-polybutadiene-polystyrene triblock copolymer hydrogenated product (SEBS), polystyrene-polyisoprene-polystyrene triblock copolymer hydrogenated product (SEPS) , And at least one selected from the group consisting of hydrogenated polystyrene-poly (isoprene / butadiene) -polystyrene triblock copolymer (SEEPS), hydrogen of polystyrene-polybutadiene-polystyrene triblock copolymer Additives (SEBS) are more preferred. These may be used alone or in combination of two or more.

  As an olefin which comprises polyolefin (III-b2), a C2-C10 olefin is preferable and a C2-C8 olefin is more preferable. Examples of such olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, and cyclohexene. These olefins may be used alone or in combination of two or more. Among these, ethylene and propylene are preferable.

  When the polymer constituting the acid-modified polymer is polyolefin (III-b2), the polar group-containing polymer (III-b) is low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, ethylene-propylene. Examples thereof include a polyolefin obtained by modifying a polyolefin such as a copolymer with maleic anhydride.

  In the thermoplastic elastomer composition of the present invention, the content of the polar group-containing polymer (III) is preferably 0.1 to 200 parts by mass with respect to 100 parts by mass of the hydrogenated block copolymer (I). When the content of the polar group-containing olefin polymer (III) is 0.1 parts by mass or more, a thermoplastic elastomer composition having stable adhesion to metal and capable of stably obtaining good adhesion. Can be obtained. On the other hand, when the content of the polar group-containing polymer (III) is 200 parts by mass or less, sufficient adhesiveness is obtained, the thermoplastic elastomer composition is not hard, and good flexibility and moldability are obtained. It is done. From this viewpoint, the content of the polar group-containing polymer (III) is more preferably 1 to 200 parts by mass, and still more preferably 5 to 150 parts by mass with respect to 100 parts by mass of the hydrogenated block copolymer (I). 10 to 150 parts by mass are more preferable, and 15 to 100 parts by mass are still more preferable.

<Softener (IV)>
Since the thermoplastic elastomer composition of the present invention contains the hydrogenated block copolymer (I) and the thermoplastic elastomer (II), it is excellent in flexibility even if it does not contain a softening agent. ) May be contained. As the softener (IV), softeners generally used for rubber and plastics can be used. For example, paraffinic, naphthenic, and aromatic process oils; phthalic acid derivatives such as dioctyl phthalate and dibutyl phthalate; white oil; mineral oil; liquid co-oligomer of ethylene and α-olefin; liquid paraffin; polybutene; low molecular weight poly Isobutylene; liquid polybutadiene such as liquid polybutadiene, liquid polyisoprene, liquid polyisoprene-butadiene copolymer, liquid styrene-butadiene copolymer, liquid styrene-isoprene copolymer, and hydrogenated products thereof. Among these, from the viewpoint of compatibility with the hydrogenated block copolymer (I), paraffinic process oil; liquid co-oligomer of ethylene and α-olefin; liquid paraffin; low molecular weight polyisobutylene and its hydrogenated product And hydrogenated paraffinic process oil is more preferable.
The softener (IV) preferably uses plant-derived raw materials at a high ratio, and the content (bio ratio) of plant-derived components in the softener (IV) is preferably 70% by mass or more, and 80% by mass or more. Is more preferable, and 90 mass% or more is still more preferable.

When the thermoplastic elastomer composition of the present invention contains the softening agent (IV), the content thereof is 0.1 to 300 parts by weight of the softening agent (IV) with respect to 100 parts by weight of the hydrogenated block copolymer (I). Part is preferred. When the softening agent (IV) is within this range, the flexibility and moldability of the thermoplastic elastomer composition are further improved. From this viewpoint, the content of the softening agent (IV) is more preferably 1 to 300 parts by mass, still more preferably 5 to 250 parts by mass, and still more preferably 100 parts by mass of the hydrogenated block copolymer (I). Preferably it is 10-200 mass parts, More preferably, it is 30-150 mass parts, More preferably, it is 50-120 mass parts.
When the thermoplastic elastomer composition of the present invention contains the polar group-containing polymer (III) and the softening agent (IV), the hydrogenated block copolymer (I), the thermoplastic elastomer (II), and the polar group-containing polymer The total content of (III) and softening agent (IV) is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more in the total amount of the thermoplastic elastomer composition.

(Other optional ingredients)
The thermoplastic elastomer composition of the present invention is a range other than the inorganic filler (V), the antioxidant (VI), and the hydrogenated block copolymer (I) as necessary, as long as the effects of the present invention are not impaired. Other hydrogenated block copolymers (I ′), other thermoplastic polymers, tackifying resins, lubricants, light stabilizers, processing aids, colorants such as pigments and dyes, flame retardants, antistatic agents, A matting agent, silicone oil, an antiblocking agent, an ultraviolet absorber, a release agent, a foaming agent, an antibacterial agent, an antifungal agent, and a fragrance may be contained.

<Inorganic filler (V)>
The inorganic filler (V) can be contained for the purpose of improving physical properties such as heat resistance and weather resistance of the thermoplastic elastomer composition of the present invention, adjusting the hardness, and improving economics as an extender. Examples of the inorganic filler (V) include calcium carbonate, talc, magnesium hydroxide, aluminum hydroxide, mica, clay, natural silicic acid, synthetic silicic acid, titanium oxide, carbon black, barium sulfate, glass balloon, and glass fiber. Etc. You may use the said inorganic filler individually by 1 type or in combination of 2 or more types.
When the inorganic filler (V) is contained, the content thereof is preferably in a range where the flexibility of the thermoplastic elastomer composition is not impaired, and relative to 100 parts by mass of the hydrogenated block copolymer (I). The amount is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, still more preferably 100 parts by mass or less, and particularly preferably 50 parts by mass or less.

<Antioxidant (VI)>
Examples of the antioxidant (VI) include hindered phenol-based, phosphorus-based, lactone-based, and hydroxyl-based antioxidants. Among these, hindered phenol antioxidants are preferable. When the antioxidant (VI) is contained, the content thereof is preferably in a range not colored when the thermoplastic elastomer composition is melt-kneaded, with respect to 100 parts by mass of the hydrogenated block copolymer (I). The amount is preferably 0.1 to 5 parts by mass.

<Hydrogenated block copolymer (I ')>
The thermoplastic elastomer composition of the present invention comprises other hydrogenated block copolymer (I ′) other than the hydrogenated block copolymer (I) (hereinafter, simply referred to as “hydrogenated block copolymer (I ′)”). May be included).
Examples of the other hydrogenated block copolymer (I ′) include, for example, the polymer block (A1) that does not include the above-described polymer block (B1) but contains a structural unit derived from an aromatic vinyl compound, and farnesene-derived A block comprising a polymer block (C1) having a content of the structural unit (c1) of less than 1% by mass and a content of the structural unit (c2) derived from a conjugated diene other than farnesene being 1 to 100% by mass. Examples thereof include hydrogenated products of copolymers. In addition, suitable aspects, such as a polymer block (A1) in other hydrogenated block copolymer (I '), a polymer block (C1), and a hydrogenation rate, are suitable in hydrogenated block copolymer (I). Same as embodiment.
By containing other hydrogenated block copolymer (I ′), it is possible to contain a large amount of softening agent (IV) without lowering the adhesiveness, resulting in superior flexibility and good adhesiveness. A thermoplastic elastomer composition having the same can be obtained.

The total content of the polymer block (A1) and the polymer block (C1) in the block copolymer is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, 100 mass% is still more preferable.
As a bonding form of the polymer block (A1) and the polymer block (C1) in the hydrogenated block copolymer (I ′), the polymer block (A1) is used from the viewpoints of flexibility, molding processability, handleability, and the like. The polymer block (C1) and the polymer block (A1) preferably have blocks in this order, and the hydrogenated block copolymer (I ′) is a hydrogen of a triblock copolymer represented by A1-C1-A1. Additives are preferred.
When other hydrogenated block copolymer (I ′) is contained, the content thereof is preferably 1 to 200 parts by mass, more preferably 10 to 100 parts by mass of the hydrogenated block copolymer (I). -150 mass, More preferably, it is 30-100 mass parts.

Examples of the other thermoplastic polymer include an olefin polymer having no polar group, a styrene polymer, a polyphenylene ether resin, and polyethylene glycol. Among these, when the thermoplastic elastomer composition of the present invention contains an olefin polymer having no polar group, the molding processability is further improved. Examples of the olefin polymer having no polar group include, for example, polyethylene, polypropylene, polybutene, block copolymers of propylene and other α-olefins such as ethylene and 1-butene, and random copolymers. 1 type (s) or 2 or more types can be used.
When the other thermoplastic polymer is contained, the content thereof is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, more preferably 100 parts by mass with respect to 100 parts by mass of the hydrogenated block copolymer (I). Is 20 parts by mass or less, more preferably 10 parts by mass or less.

Examples of the tackifying resin include rosin resins, terpene phenol resins, terpene resins, aromatic hydrocarbon-modified terpene resins, aliphatic petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, coumarone-indene resins. , Phenolic resins, xylene resins and the like.
The softening point of the tackifying resin is preferably 85 to 160 ° C, more preferably 100 to 150 ° C, and still more preferably 105 to 145 ° C, from the viewpoint of moldability.
When the tackifying resin is contained, the content thereof is preferably in a range in which the mechanical properties of the thermoplastic elastomer composition are not impaired, preferably with respect to 100 parts by mass of the hydrogenated block copolymer (I). Is 100 parts by mass or less, more preferably 70 parts by mass or less, still more preferably 30 parts by mass or less, and particularly preferably 10 parts by mass or less.

  The method for producing the thermoplastic elastomer composition of the present invention is not particularly limited. The hydrogenated block copolymer (I), the thermoplastic elastomer (II), and, if necessary, the polar-containing polymer (III), the softener ( IV), inorganic filler (V), antioxidant (VI), hydrogenated block copolymer (I ′), and any other method that can uniformly mix other components may be used. The melt kneading method is preferably used. The melt kneading can be performed using a melt kneading apparatus such as a single screw extruder, a twin screw extruder, a kneader, a batch mixer, a roller, a Banbury mixer, and preferably by melt kneading at 170 to 270 ° C. The thermoplastic elastomer composition of the present invention can be obtained.

  The thermoplastic elastomer composition of the present invention has a hardness according to JIS K 6253-2: 2012 type A durometer method (hereinafter also referred to as “A hardness”), preferably 75 or less, more preferably 70 or less, and still more preferably. 65 or less, more preferably 60 or less. If the A hardness is too high, it is difficult to obtain good flexibility, elasticity, and mechanical properties, and strong adhesion to synthetic resins, especially resins containing inorganic fillers such as glass fibers, ceramics, metals, etc. There exists a tendency for the suitable use as a thermoplastic elastomer composition to have becomes difficult.

  The thermoplastic elastomer composition of the present invention can be widely applied as various molded articles. In the molded product, the shape, structure, use and the like are not particularly limited. The thermoplastic elastomer composition of the present invention is excellent in flexibility, tensile properties, molding processability, heat resistance, weather resistance, and has a strong adhesive force against highly polar synthetic resins, ceramics, metals, etc. And a layered structure having a layer formed of the thermoplastic elastomer composition of the present invention and a layer formed of a material other than the thermoplastic elastomer composition.

[Laminated structure]
The laminate of the present invention has a layer formed of the thermoplastic elastomer composition of the present invention and a layer formed of another material other than the thermoplastic elastomer composition. The laminated structure of the present invention may be a laminated structure obtained by adhering two or more layers composed of the thermoplastic elastomer composition and a material other than the thermoplastic elastomer composition.
The shape of the laminated structure is not particularly limited, and examples thereof include a film shape, a sheet shape, and a tube shape. Among these, a film-like laminated structure is preferable.

Examples of materials other than the thermoplastic elastomer composition to be adhered include synthetic resins, ceramics, metals, and fabrics.
Examples of the synthetic resin used in the laminated structure of the present invention include polyurethane resin, polyamide resin, polyester resin, polycarbonate resin, polyphenylene sulfide resin, polyacrylate resin, polymethacrylate resin, polyether resin, (meth) acrylonitrile-butadiene- Styrene resin, (meth) acrylonitrile-styrene resin, (meth) acrylic ester-butadiene-styrene resin, (meth) acrylic ester-styrene resin, (meth) acrylic acid methyl-butadiene-styrene resin, epoxy resin, phenol resin Diallyl phthalate resin, polyimide resin, melamine resin, polyacetal resin, polysulfone resin, polyethersulfone resin, polyetherimide resin, polyphenylene ether resin, poly Relate resins, polyether ether ketone resins, polystyrene resins, rubber-reinforced polystyrene resin, syndiotactic polystyrene resins. These synthetic resins may be used alone or in combination of two or more. As the polyamide resin, for example, polyamide 6 (PA6), polyamide 66 (PA66) and the like are preferable.
In the present specification, “(meth) acrylonitrile” means “acrylonitrile or methacrylonitrile”.

Other synthetic resins include, for example, polyethylene, polypropylene, polybutene-1, polyhexene-1, poly-3-methyl-butene-1, poly-4-methyl-pentene-1, ethylene and 3 to 20 carbon atoms. Α-olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene, 6- A copolymer with one or more of methyl-1-heptene, isooctene, isooctadiene, decadiene, etc.), ethylene-propylene-diene copolymer (EPDM), ethylene-vinyl acetate copolymer, ethylene- A polyolefin resin such as an acrylic acid copolymer is preferably used.
In the layer formed of the synthetic resin, additives such as a heat stabilizer, a light stabilizer, an ultraviolet absorber, an antioxidant, a lubricant, and a colorant are added as necessary within the range not impairing the object of the present invention. , Antistatic agent, flame retardant, water repellent, waterproofing agent, hydrophilicity imparting agent, conductivity imparting agent, thermal conductivity imparting agent, electromagnetic wave shielding property imparting agent, translucency modifier, fluorescent agent, slidability imparting An agent, transparency imparting agent, anti-blocking agent, metal deactivator, antibacterial agent and the like may be further added.

The ceramic used for the laminated structure of the present invention means a nonmetallic inorganic material, and examples thereof include metal oxides, metal carbides, and metal nitrides. Examples thereof include glass, cements, alumina, zirconia, zinc oxide ceramics, barium titanate, lead zirconate titanate, silicon carbide, silicon nitride, and ferrites.
Examples of the metal used for the laminated structure of the present invention include iron, copper, aluminum, magnesium, nickel, chromium, zinc, and alloys containing them as components. Also, the layer formed of metal is a laminated structure having a metal surface formed by plating such as copper plating, nickel plating, chrome plating, tin plating, zinc plating, platinum plating, gold plating, silver plating, etc. Also good.

Although there is no restriction | limiting in particular in the kind of fabric of the fabric used for the laminated structure of this invention, For example, a textile fabric, a knitted fabric, felt, a nonwoven fabric etc. are mentioned. Moreover, as a raw material of a fabric, a natural fiber may be sufficient, a synthetic fiber may be sufficient, and it may consist of a natural fiber and a synthetic fiber. Although it does not restrict | limit in particular, As natural fiber, 1 type, or 2 or more types chosen from the group which consists of cotton, silk (silk), hemp, and hair is mentioned.
The synthetic fiber is preferably at least one selected from polyester fiber, acrylic fiber (polyacrylonitrile), polyurethane fiber, polyamide fiber, polyolefin fiber, and vinylon fiber. Examples of the polyamide fiber include nylon 6, nylon 66, and the like. Examples of polyolefin fibers include polyethylene fibers and polypropylene fibers.
As other materials other than the thermoplastic elastomer composition, a synthetic resin and a metal are preferable from the viewpoint of exerting the effect of the present invention, which is a strong adhesive force.

The method for producing the laminated structure of the present invention is not particularly limited, but it is preferable to produce the thermoplastic elastomer composition of the present invention by melt lamination molding with respect to the other materials. Examples thereof include molding methods such as an injection insert molding method, an extrusion lamination method, a coextrusion molding method, a calendar molding method, a slush molding method, a press molding method, and a melt casting method.
For example, when a laminated structure is manufactured by an injection insert molding method, an adherend that has been formed in a predetermined shape and size in advance is placed in a mold, and the thermoplastic elastomer composition of the present invention is placed there. A method of manufacturing a laminated structure by injection molding is adopted. In addition, when a laminated structure is manufactured by an extrusion lamination method, a predetermined shape attached to the extruder with respect to the surface of the adherend that has been formed in advance with a predetermined shape and dimensions, or its edge. It is also possible to produce a laminated structure by directly extruding the molten thermoplastic elastomer composition of the present invention extruded from a die having slag. In the case of producing a laminated structure by a coextrusion molding method, the laminated structure can also be produced by extruding simultaneously melted resin using two extruders. When a laminated structure is manufactured by a calendering method, the thermoplastic elastomer composition of the present invention is melted and rolled with a heating roll and is melted through several rolls, and is formed into a predetermined shape and size in advance. A laminated structure can be produced by heat-sealing the surface of the adherend. When a laminated structure is produced by a press molding method, a molded body made of the thermoplastic elastomer composition of the present invention is molded in advance by an injection molding method or an extrusion molding method, and the molded body is previously It can also be produced by heating and pressurizing an adherend that has been formed into a shape and size using a press molding machine or the like. Such a forming method is particularly suitable when the adherend is ceramic or metal.
As a molding method by melt lamination molding, an injection insert molding method is preferable.
The injection molding temperature in the injection insert molding method is not particularly limited, but is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, and still more preferably 250 ° C. or higher from the viewpoint of obtaining sufficient adhesiveness.

Further, when the adherend is a polar resin or a polyolefin resin, they can be melted simultaneously and co-extruded or co-injected. Alternatively, one of them may be formed in advance and melt coated thereon or solution coated. In addition, two-color molding, insert molding, or the like can be employed.
The adhesive strength of the layer formed of the thermoplastic elastomer composition in the laminated structure of the present invention is a value measured according to JIS K 6854-2: 1999, and is preferably 20 N / 25 mm or more. When it is 20 N / 25 mm or more, it has a sufficient adhesive force that can be practically used. This adhesive force is more preferably 30 N / 25 mm or more, still more preferably 35 N / 25 mm or more, and still more preferably 40 N / 25 mm or more.

The thermoplastic elastomer composition of the present invention and the laminated structure of the present invention can be widely applied to various uses. For example, a light metal such as a synthetic resin, a synthetic resin containing glass fiber, aluminum, or a magnesium alloy is used for housing materials such as electronic / electric equipment, OA equipment, home appliances, sports equipment, electric tools, and automobile members. A laminated structure in which the thermoplastic elastomer composition of the present invention is bonded to these housing materials can be used. More specifically, such as large displays, notebook computers, portable telephones, PHS, PDAs (mobile information terminals such as electronic notebooks), electronic dictionaries, video cameras, digital still cameras, portable radio cassette players, inverters, etc. It is preferably used for applications such as a shock-absorbing material, a covering material having an anti-slip function, a waterproof material, and a design material, which are bonded to the housing.
Further, it is useful for a wide range of applications as a molded body or a structure bonded to glass, such as window moldings and gaskets for automobiles and buildings, glass sealing materials, anticorrosive materials, and the like. Further, it can be suitably used as a sealant for a joint between glass and an aluminum sash, a metal opening or the like in a window of an automobile or a building, or a connection between a glass and a metal frame in a solar cell module or the like. Furthermore, it can be suitably used for various information terminal devices such as notebook computers, mobile phones, video cameras, and secondary battery separators used in hybrid vehicles, fuel cell vehicles, and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. In addition, β-farnesene (purity 97.6% by mass, Amiris, Inc.) was purified by 3 molecular sieves and distilled under a nitrogen atmosphere, so that gingivalene, bisabolene, farnesene epoxide, farnesol. Except for hydrocarbon impurities such as isomers, several dimers of E, E-farnesol, squalene, ergosterol and farnesene, they were used for the following polymerization.

Each component used for an Example and a comparative example is as follows.
<Hydrogenated block copolymer (I)>
Hydrogenated block copolymers (I-1) to (I-7) of Production Examples 1 to 7 described later
<Hydrogenated block copolymer (I ')>
Hydrogenated block copolymers (I′-1) to (I′-5) of Production Examples 8 to 12 described later
<Thermoplastic elastomer (II)>
Thermoplastic elastomer (II-1): Thermoplastic polyurethane elastomer (trade name: Elastollan C80a, manufactured by BASF Japan Ltd.)
Thermoplastic elastomer (II-2): Thermoplastic polyester elastomer (trade name: Hytrel 4047, manufactured by Toray DuPont Co., Ltd.)
<Polar group-containing polymer (III)>
Polar group-containing polymer (III-1): Polar group-containing polymer of Production Example 13 described later Polar group-containing polymer (III-2): Polar group-containing polymer of Production Example 14 described later Polar group-containing polymer ( III-3): Reactive ethylene-ethyl acrylate copolymer (trade name: GBF-401, manufactured by NUC Corporation)

<Softener (IV)>
Softener (IV-1): Hydrogenated paraffin process oil (trade name: Diana Process Oil PW-90, manufactured by Idemitsu Kosan Co., Ltd.)
Softener (IV-2): Sunflower oil SL (J-Oil Mills Co., Ltd.)
<Inorganic filler (V)>
Calcium carbonate (trade name: Escalon # 200, Sankyo Seimitsu Co., Ltd.)
<Antioxidant (VI)>
Hindered phenolic antioxidant (trade name: ADK STAB AO-60, manufactured by ADEKA Corporation)

Moreover, the detail of each measuring method in a manufacture example is as follows.
(1) Measurement of molecular weight distribution and peak top molecular weight (Mp), etc. The peak top molecular weight (Mp) and molecular weight distribution (Mw / Mn) of hydrogenated block copolymer (I) or (I ′) and styrene block are GPC. The molecular weight was determined in terms of standard polystyrene by gel permeation chromatography, and the peak top molecular weight (Mp) was determined from the position of the peak of the molecular weight distribution. The measuring apparatus 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 ° C

(2) Measuring method of hydrogenation rate In each example and comparative example, the block copolymer (P) or (P ′) and the hydrogenated block copolymer (I) or (I ′) after hydrogenation are respectively ¹ H-NMR was measured at 50 ° C. using “Lambda-500” manufactured by JEOL Ltd. after dissolving in deuterated chloroform solvent. The hydrogenation rate of the carbon-carbon double bond in the polymer block (B1) and the polymer block (C1) of the hydrogenated block copolymer (I) or (I ′) is 4.5 of the obtained spectrum. It calculated from the following formula from the peak of the proton possessed by the carbon-carbon double bond appearing at ˜6.0 ppm.
Hydrogenation rate (mol%) = {1- (hydrogenated block copolymer (I) or (I ′) moles of carbon-carbon double bond contained per mole) / (block copolymer (P ) Or (P ′) moles of carbon-carbon double bonds contained per mole)} × 100

<Hydrogenated block copolymer (I)>
[Production Example 1]
In a pressure-resistant container that was purged with nitrogen and dried, 50.0 kg of cyclohexane as a solvent, 15.5 g of sec-butyllithium (10.5 mass% cyclohexane solution) as an anionic polymerization initiator, heated to 50 ° C., and then styrene ( 1) 1.32 kg was added and polymerized for 1 hour, then β-farnesene 6.18 kg was added and polymerized for 2 hours, styrene (2) 1.32 kg was added and polymerized for 1 hour, polystyrene- A reaction solution containing poly (β-farnesene) -polystyrene triblock copolymer (P1) was obtained. To this reaction solution, 5% by mass of palladium carbon (palladium supported amount: 5% by mass) as a hydrogenation catalyst was added to the block copolymer (P1), and the reaction was performed for 10 hours under the conditions of hydrogen pressure of 2 MPa and 150 ° C. Went. After allowing to cool and release the pressure, the palladium carbon is removed by filtration, the filtrate is concentrated, and further dried under vacuum to obtain a hydrogenated polystyrene-poly (β-farnesene) -polystyrene triblock copolymer (hereinafter, “ Hydrogenated block copolymer (I-1) ") was obtained. The above physical properties of the hydrogenated block copolymer (I-1) were measured. The results are shown in Table 1.

[Production Examples 2 to 4]
The block copolymers (P2) to (P4) were obtained in the same manner as in Production Example 1 except that the composition described in Table 1 was followed, and hydrogenated and added to the hydrogenated block copolymer (I-2). ) To (I-4) were produced. However, in Production Example 4, instead of β-farnesene in Production Example 1, a mixture of β-farnesene and butadiene was used. Said physical property was measured about the obtained hydrogenated block copolymer (I-2)-(I-4). The results are shown in Table 1.

[Production Example 5]
In a pressure vessel that was purged with nitrogen and dried, 50.0 kg of cyclohexane as a solvent, 190.5 g of sec-butyllithium (10.5 mass% cyclohexane solution) as an anionic polymerization initiator, and 0.40 kg of tetrahydrofuran as a Lewis base were charged. After the temperature was raised to 50 ° C., 6.34 kg of β-farnesene was added and polymerization was performed for 2 hours. Subsequently, 2.50 kg of styrene (1) was added for polymerization for 1 hour, and 3.66 kg of butadiene was further added for 1 hour. Polymerization was performed. Subsequently, 0.02 kg of dichlorodimethylsilane as a coupling agent was added to this polymerization reaction solution and reacted for 1 hour, so that a poly (β-farnesene) -polystyrene-polybutadiene-polystyrene-poly (β-farnesene) pentablock copolymer was obtained. (Hereinafter, referred to as “block copolymer (P5)”). To this reaction solution, 5% by mass of palladium carbon (palladium supported amount: 5% by mass) as a hydrogenation catalyst was added to the block copolymer (P5), and the reaction was performed for 4 hours under conditions of hydrogen pressure of 2 MPa and 150 ° C. Went. After allowing to cool and release, palladium carbon is removed by filtration, the filtrate is concentrated, and further dried under vacuum, so that poly (β-farnesene) -polystyrene-polybutadiene-polystyrene-poly (β-farnesene) pentablock copolymer A combined hydrogenated product (I-5) (hereinafter referred to as “hydrogenated block copolymer (I-5)”) was obtained. Said physical property was measured about the obtained hydrogenated block copolymer (I-5). The results are shown in Table 1.

[Production Example 6]
The hydrogenated block copolymer (I-6) (hereinafter referred to as “hydrogenated block copolymer (I-6)”) was prepared in the same manner as in Production Example 5 except that the hydrogenation reaction time was changed to 10 hours. ) Said physical property was measured about the obtained hydrogenated block copolymer (I-6). The results are shown in Table 1.

[Production Example 7]
In a pressure vessel which was purged with nitrogen and dried, 50.0 kg of cyclohexane as a solvent and 190.5 g of sec-butyllithium (10.5 mass% cyclohexane solution) as an anionic polymerization initiator were charged, and the temperature was raised to 50 ° C. 5.77 kg of β-farnesene was added and polymerization was performed for 2 hours. Subsequently, 2.50 kg of styrene (1) was added for polymerization for 1 hour, and 4.23 kg of isoprene was further added for polymerization for 1 hour. Subsequently, 0.02 kg of dichlorodimethylsilane as a coupling agent was added to this polymerization reaction solution and reacted for 1 hour, so that poly (β-farnesene) -polystyrene-polyisoprene-polystyrene-poly (β-farnesene) pentablock copolymer was used. A reaction solution containing a coalescence (hereinafter referred to as “block copolymer (P7)”) was obtained. To this reaction solution, 5% by mass of palladium carbon (palladium supported amount: 5% by mass) as a hydrogenation catalyst was added to the block copolymer (P7), and the reaction was performed for 10 hours under conditions of hydrogen pressure of 2 MPa and 150 ° C. Went. After allowing to cool and release, palladium carbon is removed by filtration, the filtrate is concentrated, and further dried under vacuum, so that poly (β-farnesene) -polystyrene-polyisoprene-polystyrene-poly (β-farnesene) pentablock A hydrogenated product (I-7) of a polymer (hereinafter referred to as “hydrogenated block copolymer (I-7)”) was obtained. With respect to the obtained hydrogenated block copolymer (I-7), the above physical properties were measured. The results are shown in Table 1.

<Hydrogenated block copolymer (I ')>
[Production Example 8]
In a pressure-resistant container purged with nitrogen and dried, 50.0 kg of cyclohexane as a solvent and 16.9 g of sec-butyllithium (10.5 mass% cyclohexane solution) as an anionic polymerization initiator were charged and heated to 50 ° C., By adding 2.22 kg of styrene (1) and conducting polymerization for 1 hour, subsequently adding 1.11 kg of β-farnesene and polymerizing for 2 hours, and further adding 2.22 kg of styrene (2) and conducting polymerization for 1 hour. Then, a reaction liquid containing polystyrene-poly (β-farnesene) -polystyrene triblock copolymer (hereinafter referred to as “block copolymer (P′1)”) was obtained. To this reaction solution, 5% by mass of palladium carbon (palladium supported amount: 5% by mass) as a hydrogenation catalyst was added to the block copolymer (P′1), and the hydrogen pressure was 10 MPa under the conditions of 2 MPa and 150 ° C. Time reaction was performed. After allowing to cool and release, palladium carbon is removed by filtration, the filtrate is concentrated, and further dried under vacuum to obtain a hydrogenated polystyrene-poly (β-farnesene) -polystyrene triblock copolymer (hereinafter, “ Hydrogenated block copolymer (I'-1) ") was obtained. Said physical property was measured about the obtained hydrogenated block copolymer (I'-1). The results are shown in Table 2.

[Production Example 9]
The hydrogenated block copolymer (I′-2) (hereinafter referred to as “hydrogenated block copolymer (I′-2)”) was prepared in the same manner as in Production Example 5 except that the hydrogenation reaction time was changed to 2 hours. It was obtained. Said physical property was measured about the obtained hydrogenated block copolymer (I'-2). The results are shown in Table 2.

[Production Examples 10-12]
Instead of β-farnesene, only a mixture of isoprene and butadiene or butadiene was blended, tetrahydrofuran was added as a Lewis base as needed, and the same procedure as in Production Example 8 was followed except that the blending described in Table 2 was followed. The block copolymers (P′3) to (P′5) were obtained and then hydrogenated to produce hydrogenated block copolymers (I′-3) to (I′-5). The obtained hydrogenated block copolymers (I′-3) to (I′-5) were evaluated as described above. The results are shown in Table 2.

In addition, each notation in Table 1 and Table 2 is as follows.
(* 1): (A1) / (B1) represents a mass ratio between the content of the polymer block (A1) and the content of the polymer block (B1).
(* 2): (A1) / ((B1) + (C1)) is the sum of the contents of the polymer block (A1) and the respective contents of the polymer block (B1) and the polymer block (C1). And the mass ratio. However, it shows only when it has a polymer block (C1).
(* 3): (b1) / (B1) represents the content of the structural unit (b1) derived from farnesene in the polymer block (B1).
(* 4): ((b1) + (c1)) / ((B1) + (C1)) is the structural unit (b1) and structure relative to the total amount of the polymer block (B1) and the polymer block (C1) The total content of the unit (c1) is shown. However, it displays only when it has a polymer block (C1).
(* 5): St-F-St represents a polystyrene-poly (β-farnesene) -polystyrene triblock copolymer.
St- (F / Bd) -St represents a polystyrene-poly (β-farnesene / butadiene) -polystyrene triblock copolymer.
F-St-Bd-St-F represents a poly (β-farnesene) -polystyrene-polybutadiene-polystyrene-poly (β-farnesene) pentablock copolymer.
F-St-Ip-St-F represents a poly (β-farnesene) -polystyrene-polyisoprene-polystyrene-poly (β-farnesene) pentablock copolymer.
St- (Ip / Bd) -St represents a polystyrene-poly (isoprene / butadiene) -polystyrene triblock copolymer.
St-Bd-St represents a polystyrene-polybutadiene-polystyrene triblock copolymer.
(* 6): The hydrogenation rate indicates the hydrogenation rate of the carbon-carbon double bond in the polymer block (B1). However, when it has a polymer block (C1), the hydrogenation rate of the carbon-carbon double bond in a polymer block (B1) and a polymer block (C1) is shown.

[Production Example 13]
Hydrogenated product (SEEPS-OH) of a triblock copolymer having a hydroxyl group at one end of a molecule composed of polystyrene-poly (isoprene / butadiene) -polystyrene (number average molecular weight 65,000, styrene content = 29 mass%, poly (Isoprene / Butadiene) block hydrogenation rate = 98%, glass transition point = −58 ° C., average number of hydroxyl groups = 0.9 / molecule) 100 parts by mass, thermoplastic polyurethane [Kuraray Co., Ltd. “Kuramylon 1180” (Product name); Polyester polyurethane elastomer having polybutylene adipate as soft segment] 100 parts by mass of dry blend, and using a twin screw extruder (Coperion “ZSK26Mc”; number of cylinders 14) cylinder temperature 230 ° C. and Melt-kneading under the condition of screw speed 200rpm After, extruded into strands and cut to obtain pellets.
The unreacted polyurethane was extracted and removed from the obtained pellets using dimethylformamide, and then unreacted SEEPS-OH was extracted and removed using cyclohexane, and the remaining solid was dried to obtain a triblock copolymer. A polar group-containing polymer (III-1), which is a polyurethane block copolymer in which the coalesced (SEEPS) and thermoplastic polyurethane (“Clamylon 1180”) were bonded, was obtained.

[Production Example 14]
Hydrogenated product (SEBS) of triblock copolymer consisting of polystyrene-polybutadiene-polystyrene (number average molecular weight 70,000, styrene content = 30% by mass, hydrogenation rate in polybutadiene block = 99%, glass transition point = −56 ° C) 100 parts by mass, maleic anhydride 2.5 parts by mass, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane 0.3 parts by mass, and a twin-screw extruder ( After melt reaction under the conditions of a cylinder temperature of 210 ° C. and a screw speed of 300 rpm using “ZSK26Mc” (Cylinder number 14) manufactured by Coperion, the polymer was extruded into a strand shape, cut and pelletized into a polar group-containing polymer (III -2) was obtained.

[Examples 1 to 22 and Comparative Examples 1 to 11]
<Preparation of thermoplastic elastomer composition>
A composition prepared by premixing the components shown in Tables 3 and 4 at the ratios shown in Tables 3 and 4 was 230 ° C. and screwed using a twin-screw extruder (“ZSK26Mc” manufactured by Coperion; cylinder number 14). The mixture was melt-kneaded under a rotation speed of 200 rpm to obtain a thermoplastic elastomer composition. About the obtained thermoplastic elastomer composition, the following physical property was measured. The results are shown in Tables 5-7.
<Production of laminated structure>
Using the following adherend (length 100 mm × width 35 mm × thickness 1 mm) as an insert part, a laminated structure was produced by an injection insert molding method.
When the insert part is made of various polar resins, wipe both surfaces of the insert part with gauze impregnated with methanol, degrease and dry naturally. When the insert part is made of various metals, both surfaces of the insert part are washed with an aqueous surfactant solution and distilled water in this order, and dried at 100 ° C. Each insert part pretreated as described above was fixed in the mold by a vacuum line. A laminate structure is obtained by filling the obtained thermoplastic elastomer composition in a mold under conditions of a mold temperature of 40 ° C. and a cylinder temperature of 260 ° C., and cooling the surface temperature of the adherend to 40 ° C. It was. The peel strength of the thermoplastic elastomer composition of the obtained laminated structure was measured.

The details of the adherend used for the production of the laminated structure are as follows.
・ Polycarbonate (PC) board: Trade name “Iupilon S-3000R”, manufactured by Mitsubishi Engineering Plastics Co., Ltd. ・ Acrylonitrile-butadiene-styrene resin (ABS) board: Trade name “Toyolac 700-314”, manufactured by Toray Industries, Inc. Methyl methacrylate resin (PMMA) plate: trade name “PLEXIGLAS 6N”, manufactured by Daicel Evonik Co., Ltd., nylon 6 plate: trade name “UBE Nylon 6 1013B”, Ube Industries, Ltd., aluminum alloy plate: material “A5052P”
・ Magnesium alloy plate: Material "AZ31B"

(1) Hardness (1-1) Production of Sheet of Thermoplastic Elastomer Composition The thermoplastic elastomer composition obtained in each example and comparative example was injected into an injection molding machine (“EC75SX; 75 tons” manufactured by Toshiba Machine Co., Ltd.). ) Was injection molded under the conditions of a cylinder temperature of 260 ° C. and a mold temperature of 40 ° C. to produce a sheet having a length of 100 mm, a width of 35 mm, and a thickness of 2 mm.
(1-2) Measurement of hardness A dumbbell No. 3 test piece was obtained from the sheet of the thermoplastic elastomer composition obtained above using a punching blade according to JIS K 6251: 2010.
Three test pieces obtained were stacked and the hardness of 6 mm in thickness was measured according to JIS K 6253-3: 2012 using a type A durometer indenter. In addition, it is excellent in a softness | flexibility, so that the numerical value of hardness is low, 75 or less are preferable and 70 or less are more preferable.

(2) Measurement of tensile breaking strength, tensile breaking elongation and 100% modulus The dumbbell No. 3 type test piece obtained above was measured for tensile breaking strength, tensile breaking elongation and 100% modulus according to JIS K 6251: 2010. did. The higher the values of tensile strength at break and tensile elongation at break, the better the tensile properties. The tensile strength at break is preferably 2.0 MPa or more, more preferably 3.5 MPa or more. Further, the tensile elongation at break is preferably 100% or more, and more preferably 150% or more.

(3) Formability The surface of the sheet obtained above was visually observed, and the presence or absence of a flow mark was evaluated according to the following criteria.
A: There is no flow mark.
B: There are few flow marks.
C: Many flow marks.

(4) Heat resistance and weather resistance After the sheet obtained above was left in an atmosphere of 200 ° C. for 30 minutes to conduct a heat resistance test, Suntest CPS + (light source: xenon, irradiation intensity manufactured by Toyo Seiki Seisakusho Co., Ltd.) : 550 W / m ² ) for 12 hours. The color change before and after the test was observed visually and with a finger, and the heat resistance and weather resistance were evaluated according to the following criteria. If the following evaluation criteria is 2 or less, it can be put to practical use.
1: No change 2: Slight yellowing is observed.
3: Yellowing is observed.
4: The yellowing is severe and the tackiness of the sheet surface is increased.

(5) Peel strength For the laminated structure produced above, using “Instron 5566” manufactured by Instron, the conditions of a peel angle of 180 ° and a tensile speed of 50 mm / min according to JIS K6854-2: 1999 The peel adhesion strength test was performed, the peel strength was measured, and the average value was calculated four times in total. The higher the peel strength value, the higher the adhesion to the adherend, and the value is preferably 20 N / 25 mm or more, and more preferably 35 N / 25 mm or more. For Examples 6, 13 to 15, and 20, 21, standard deviation values were also obtained.

In Table 5, when Examples 1-7 which differ only in the kind of hydrogenated block copolymer and Comparative Examples 1-5 are compared, Examples 1-7 have a structural unit (b1) derived from farnesene. The mass ratio [(A1) / (B1)] of the block (A1) to the polymer block (B1) is 1/99 to 70/30, and the carbon-carbon double in the polymer block (B1) The hydrogenated block copolymer (I) having a hydrogenation rate of 50 mol% or more is used, and the hardness is lower than in Comparative Examples 1 to 5, and the flexibility, tensile properties, and moldability are also low. It turns out that it is excellent and the peel strength is high.
In Table 6, when Example 9 and Comparative Examples 7, 8, and 10 are compared, Example 9 has low hardness, excellent flexibility and molding processability, despite containing no softener. It can be seen that the peel strength against metal is high.
In Table 6, when compared with Example 8 in which the hydrogenated block copolymer (I) is a triblock copolymer and Example 9 in which it is a pentatriblock copolymer, Example 9 In comparison, it can be seen that the moldability is superior and the peel strength against metal is higher.
In Table 7, when comparing the standard deviation of the peel strengths of Examples 6, 13 to 15, and 20, 21, Examples 6, 14, 15, 20, and 21 containing a polar group-containing polymer contain polar groups. It can be seen that the value of the standard deviation is small compared with Example 13 which does not contain a polymer, and a high peel strength can be obtained stably.

Claims (18)

A thermoplastic elastomer composition comprising a hydrogenated block copolymer (I) and a thermoplastic elastomer (II),
The content of the thermoplastic elastomer (II) is 100 to 300 parts by mass with respect to 100 parts by mass of the hydrogenated block copolymer (I),
The hydrogenated block copolymer (I) contains 1 to 100% by mass of a polymer block (A1) containing a structural unit derived from an aromatic vinyl compound and a structural unit (b1) derived from farnesene, other than farnesene A polymer block (B1) containing 99 to 0% by mass of a structural unit (b2) derived from conjugated diene of
A hydrogenated block copolymer (P) having a mass ratio [(A1) / (B1)] of the polymer block (A1) to the polymer block (B1) of 1/99 to 70/30. Yes,
The hydrogenation rate of the carbon-carbon double bond in the polymer block (B1) is 50 mol% or more,
The thermoplastic elastomer composition, wherein the thermoplastic elastomer (II) is at least one selected from the group consisting of a thermoplastic polyurethane elastomer and a thermoplastic polyester elastomer.   The thermoplastic elastomer composition according to claim 1, further comprising 1 to 200 parts by mass of the polar group-containing polymer (III) with respect to 100 parts by mass of the hydrogenated block copolymer (I).   Furthermore, 1-100 mass parts of softening agents (IV) are contained with respect to 100 mass parts of said hydrogenated block copolymers (I), The thermoplastic-elastomer composition of Claim 1 or 2.   The thermoplastic-elastomer composition in any one of Claims 1-3 whose hydrogenation rate of the carbon-carbon double bond in the said polymer block (B1) is 70 mol% or more.   The thermoplastic elastomer composition according to any one of claims 1 to 4, wherein the aromatic vinyl compound is at least one selected from the group consisting of styrene, α-methylstyrene, and 4-methylstyrene.   The thermoplastic elastomer composition according to any one of claims 1 to 5, wherein the farnesene is β-farnesene.   The thermoplastic elastomer composition according to any one of claims 1 to 6, wherein the conjugated diene other than farnesene is at least one selected from the group consisting of isoprene, butadiene and myrcene.   The peak top molecular weight (Mp) calculated | required by gel permeation chromatography of the said hydrogenated block copolymer (I) in standard polystyrene conversion is 4,000-1,500,000, Any one of Claims 1-7. The thermoplastic elastomer composition described in 1.   The hydrogenated block copolymer (I) is a hydrogenated product of a triblock copolymer having blocks in the order of the polymer block (A1), the polymer block (B1), and the polymer block (A1). The thermoplastic elastomer composition according to any one of claims 1 to 8. The hydrogenated block copolymer (I) is a hydrogenated product of the block copolymer (P) containing the polymer block (A1), the polymer block (B1) and the polymer block (C1),
In the polymer block (C1), the content of the structural unit (c1) derived from farnesene is less than 1% by mass, and the content of the structural unit (c2) derived from conjugated diene other than farnesene is 1 to 100% by mass. A polymer block,
The mass ratio [(A1) / ((B1) + (C1))] of the polymer block (A1) and the total amount of the polymer block (B1) and the polymer block (C1) is 1/99. ~ 70/30,
The block copolymer (P) comprises at least two polymer blocks (A1), at least one polymer block (B1), and at least one polymer block (C1); and Having at least one polymer block (B1) at its end;
The thermoplastic elastomer composition according to any one of claims 1 to 8, wherein a hydrogenation rate of a carbon-carbon double bond in the polymer block (B1) and the polymer block (C1) is 50 mol% or more. object.   The block in which the polar group-containing polymer (III) has a polymer block (A2) containing a structural unit derived from an aromatic vinyl compound and a polymer block (B2) containing a structural unit derived from a conjugated diene other than farnesene The polymer block (D) containing a copolymer or a hydrogenated product thereof and the block copolymer (III-a) containing a thermoplastic polyurethane elastomer block (E), according to any one of claims 1 to 10. A thermoplastic elastomer composition.   The polar group-containing polymer (III) is a polymer (III-b) having a functional group derived from an α, β-unsaturated carboxylic acid or a derivative thereof, according to any one of claims 1 to 10. Thermoplastic elastomer composition.   The polar group-containing polymer (III-b) is an ethylene- (meth) acrylic acid alkyl ester copolymer containing a structural unit derived from ethylene and a structural unit derived from a (meth) acrylic acid alkyl ester. 12. The thermoplastic elastomer composition according to 12.   The thermoplastic elastomer composition according to claim 12, wherein the polar group-containing polymer (III-b) is an acid-modified polymer obtained by grafting maleic anhydride to a side chain.   The polymer constituting the acid-modified polymer includes a polymer block (A3) containing a structural unit derived from an aromatic vinyl compound and a polymer block (B3) containing a structural unit derived from a conjugated diene compound other than farnesene. It is at least one selected from the group consisting of a block copolymer (III-b1) containing a block copolymer or a polymer block (F) containing a hydrogenated product thereof, and a polyolefin (III-b2) Item 15. The thermoplastic elastomer composition according to Item 14.   A laminated structure having a layer formed of the thermoplastic elastomer composition according to any one of claims 1 to 15 and a layer formed of a material other than the thermoplastic elastomer composition.   The laminated structure according to claim 16, wherein the other material is at least one selected from the group consisting of a synthetic resin and a metal.   The manufacturing method of a laminated structure which melt-laminate-molds the thermoplastic elastomer composition in any one of Claims 1-15 with respect to materials other than this thermoplastic elastomer composition.