JP7141027B2 - molding - Google Patents

Description

The present invention relates to molded articles.

A hydrogenated block copolymer composed of a polymer block composed of a monomer derived from an aromatic vinyl compound and a polymer block composed of a structural unit derived from a conjugated diene can be converted into a vulcanized rubber without further vulcanization. It exhibits the same characteristics as , and has excellent damping properties, flexibility, rubber elasticity, and weather resistance. Widely used.
Such a hydrogenated block copolymer can be obtained, for example, by hydrogenating a block copolymer obtained by sequentially polymerizing an aromatic vinyl compound and a conjugated diene such as isoprene or butadiene.

Patent Document 1 describes a hydrogenated block copolymer obtained by sequentially polymerizing an aromatic vinyl compound and a conjugated diene such as isoprene or butadiene. However, the peak top temperature of tan δ is relatively high, and there is a problem with flexibility at low temperatures.

JP 2010-090267 A

Conventionally, a molded article containing a hydrogenated block copolymer composed of a polymer block composed of a monomer derived from an aromatic vinyl compound and a polymer block composed of a structural unit derived from a conjugated diene has damping properties. It has been used as a material with excellent flexibility, rubber elasticity and weather resistance, but there is room for improvement in its physical properties. In particular, there is room for improvement in flexibility at low temperatures.
The present invention has been made in view of the above circumstances, and by using 1,3,7-octatriene, whose physical properties have not been clarified yet, exhibits high flexibility at low temperatures and has excellent vibration damping properties. It is an object to provide a molded article containing a compound, and to provide a laminate, film, fiber, nonwoven fabric, adhesive agent, elastic member, aqueous emulsion, sealant, and viscosity index improver using the compound. and

As a result of intensive studies by the present inventors, a polymer block (A) using 1,3,7-octatriene as a conjugated diene and mainly composed of structural units derived from 1,3,7-octatriene, A molded article containing a hydride of a block copolymer containing a polymer block (B) mainly composed of structural units derived from an aromatic vinyl compound is mainly composed of structural units derived from isoprene, butadiene, etc. as conjugated dienes. The present inventors have found that, compared with molded articles containing hydrides of block copolymers containing polymer blocks of the above, exhibit high flexibility at low temperatures and excellent vibration damping properties, leading to the completion of the present invention.

That is, the present invention provides the following [1] to [17].
[1] Hydrogenated block copolymer containing a polymer block (A) containing a structural unit derived from a conjugated diene and a polymer block (B) mainly containing a structural unit derived from an aromatic vinyl compound A molded body comprising
the conjugated diene comprises 1,3,7-octatriene;
The polymer block (A) is a molded article containing a hydrogenated block copolymer mainly composed of structural units derived from 1,3,7-octatriene.
[2] The molded article according to [1] above, wherein the polymer block (A) does not contain a structural unit derived from a conjugated diene having 12 or more carbon atoms.
[3] The molded article according to [1] or [2] above, which has a hardness of 1 to 40 measured at a temperature of 23° C. according to JIS K 6253-3 (2012) type A durometer method.
[4] The above [1] to [3], wherein the mass ratio [(B)/(A)] of the polymer block (B) to the polymer block (A) is 1/99 or more and 50/50 or less. ] The copolymer according to any one of the above.
[5] The above [1], wherein the block copolymer includes a triblock copolymer having blocks in the order of the polymer block (B), the polymer block (A), and the polymer block (B). The molded article according to any one of to [4].
[6] The copolymer according to any one of [1] to [5] above, wherein the block copolymer contains a structural unit derived from a coupling agent.
[7] In accordance with JIS K7244-10 (2005), a strain amount of 0.1%, a frequency of 1 Hz, a measurement temperature of -70 to 200 ° C., a heating rate of 3 ° C./min, and a test piece thickness of 1 mm. The copolymer according to any one of the above [1] to [6], which has a tan δ peak top of 1.50 or more as measured by .
[8] A laminate comprising a layer using the block copolymer hydride according to any one of [1] to [7] above.
[9] A film using the block copolymer hydride according to any one of [1] to [7] above.
[10] A fiber using the block copolymer hydride according to any one of [1] to [7] above.
[11] A nonwoven fabric using the block copolymer hydride according to any one of [1] to [7] above.
[12] A decorative molding material comprising the laminate described in [8] above, the film described in [9] above, the fiber described in [10] above, or the nonwoven fabric described in [11] above.
[13] A pressure-sensitive adhesive using the block copolymer hydride according to any one of [1] to [7] above.
[14] An elastic member using the block copolymer hydride according to any one of [1] to [7] above.
[15] An aqueous emulsion using the hydrogenated block copolymer according to any one of [1] to [7] above.
[16] A viscosity index improver using the block copolymer hydride according to any one of [1] to [7] above.
[17] A sealant using the block copolymer hydride according to any one of [1] to [7] above.

According to the present invention, it is possible to provide a molded article containing a hydride that exhibits high flexibility at low temperatures and has excellent damping properties. agents, elastic members, aqueous emulsions, viscosity index improvers, and sealants.

1 is a graph of tan δ of a molded article in Example 1 of the present invention. 5 is a graph of tan δ of a molded body in Comparative Example 1 of the present invention. 5 is a graph of tan δ of a compact in Comparative Example 2 of the present invention.

In the following description, the preferable definition can be arbitrarily selected, and the combination of preferable definitions can be arbitrarily combined.

[Molded body]
The molded article of the present invention is a block copolymer containing a polymer block (A) containing structural units derived from a conjugated diene and a polymer block (B) mainly containing structural units derived from an aromatic vinyl compound. A molded article containing a coalesced hydride, wherein the conjugated diene contains 1,3,7-octatriene, and the polymer block (A) has a structure derived from 1,3,7-octatriene It includes hydrides of block copolymers that are mainly composed of units. According to the molded article of the present invention, it is possible to provide a molded article that exhibits high flexibility at low temperatures and excellent vibration damping properties.
Examples of molded articles include films, sheets, injection-molded bottles, blow bottles, injection-molded cups, fibers, non-woven fabrics, elastic members, sealants, medical tubes, liquid packaging materials, interlayer films for laminated glass, and the like.

<Polymer block (A)>
Polymer block (A) contains structural units derived from a conjugated diene, which includes 1,3,7-octatriene. The polymer block (A) is mainly composed of a structural unit derived from 1,3,7-octatriene (hereinafter sometimes abbreviated as "1,3,7-octatriene unit"). . The term “mainly” used herein means that the content of structural units derived from 1,3,7-octatriene in the polymer block (A) is 40% by mass or more. The content of 1,3,7-octatriene units in the polymer block (A) is preferably 50% by mass or more, and preferably 70% by mass, from the viewpoint of flexibility and damping properties at low temperatures of molded articles. % or more, more preferably 90 mass % or more, even more preferably 95 mass % or more, and may be 100 mass %.

Representative bonding modes of 1,3,7-octatriene include 1,2-bond, 1,4-bond, 3,4-bond and 4,1-bond, and the bonding order and There is no particular restriction on the content ratio. In the present invention, the 1,4-bond is regarded as the same as the 4,1-bond.
Regarding the bonding mode of 1,3,7-octatriene, the content ratio of 1,2-bonds to the total bonding mode is preferably 35 to 65 mol %, more preferably 40 to 60 mol %. The content of 1,4-bonds relative to all bonding modes is preferably 20 to 65 mol%, more preferably 40 to 60 mol%, even more preferably 40 to 50 mol%. The content ratio of 3,4-bonds with respect to the total bonding mode is the balance of the content ratio of 1,2-bonds and 1,4-bonds. That is, the content ratio of 3,4-bonds with respect to all bonding modes is obtained from "100-(content ratio of 1,2-bonds+content ratio of 1,4-bonds)".
As the content of 3,4-bonds relative to all bonding modes decreases, the peak top temperature of tan δ, which will be described later, decreases, and flexibility is exhibited in a lower temperature range.

The polymer (A) contains structural units derived from a conjugated diene, and the conjugated diene contains 1,3,7-octatriene.
Conjugated diene compounds other than 1,3,7-octatriene include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 4,5-diethyl-1,3-butadiene, 2-phenyl-1, 3-butadiene, 2-hexyl-1,3-butadiene, 2-benzyl-1,3-butadiene, 2-p-toluyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl- 1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene, 2,3-diethyl-1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-hexadiene, 2, 3-diethyl-1,3-heptadiene, 3-butyl-1,3-octadiene, 2,3-dimethyl-1,3-octadiene, 4,5-diethyl-1,3-octadiene, 1,3-cyclohexadiene , 1,3,7-octatriene, myrcene (7-methyl-3-methyleneocta-1,6-diene), and at least one compound selected from the group consisting of springen, preferably butadiene and isoprene. , such as butadiene or isoprene.

A structural unit derived from a conjugated diene compound monomer other than 1,3,7-octatriene in the polymer block (A) (hereinafter referred to as "a conjugated diene compound monomer other than 1,3,7-octatriene (sometimes abbreviated as "unit") is preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 30% by mass or less, and 10% by mass. It is more preferably 5% by mass or less, and even more preferably 5% by mass or less.

The polymer block (A) may have a structural unit derived from a monomer other than the conjugated diene as long as it does not interfere with the object and effect of the present invention, but preferably does not. The content of structural units derived from monomers other than conjugated dienes in the polymer block (A) is preferably 20% by mass or less, more preferably 10% by mass or less, and 5% by mass or less. is more preferred.
The polymer block (A) has a tan δ peak temperature that is too low, and there is a risk that the sound insulation properties when used as a glass interlayer film, for example, will be reduced. preferably not included. For example, the polymer block (A) is preferably only structural units derived from conjugated dienes having less than 12 carbon atoms.
When the polymer block (A) has two or more types of structural units, their bonding forms are random, tapered, completely alternating, partly blocky, block, or a combination of two or more thereof. can be

The block copolymer should just have at least one said polymer block (A). When the block copolymer has two or more polymer blocks (A), the polymer blocks (A) may be the same or different. In the present specification, "polymer blocks are different" means the monomer units constituting the polymer blocks, the weight average molecular weight, the stereoregularity, and the ratio and covalentity of each monomer unit when there are multiple monomer units. It means that at least one of the forms of polymerization (random, tapered, completely alternating, partially blocky, block, etc.) is different.
In the present invention, the block copolymer preferably has one polymer block (A).

The total peak top molecular weight (Mp) of the polymer block (A) is preferably 1,000 to 350 in the state before hydrogenation, from the viewpoint of flexibility at low temperatures of molded articles, damping properties, etc. ,000, more preferably 3,000 to 200,000, still more preferably 5,000 to 150,000, particularly preferably 6,000 to 100,000, most preferably 6,500 ~72,000.

The total peak top molecular weight (Mp) of the polymer block (A) is the total peak top molecular weight when the block copolymer contains two or more polymer blocks (A1) and (A2). (Mp), and when the block copolymer (A) contains only one polymer block (A), it means the peak top molecular weight (Mp) of that polymer block (A).
The "peak top molecular weight (Mp)" and "molecular weight distribution (Mw/Mn)" described in this specification are all peak top molecular weights (Mp) in terms of standard polystyrene obtained by gel permeation chromatography (GPC) measurement. and molecular weight distribution (Mw/Mn), more specifically, values measured according to the method described in Examples.
The peak top molecular weight (Mp) of each polymer block in the block copolymer can be obtained by measuring a sampled polymer each time polymerization of each polymer block is completed in the production process. For example, when a triblock copolymer having an A1-B-A2 structure is synthesized by sequentially polymerizing A1, B, and A2 in that order, the peak top molecular weight (Mp) of the first polymer block A1 is the polymerization of A1. It can be determined by GPC measurement of the polymer sampled when is completed. Further, the peak top molecular weight (Mp) of the polymer block B is obtained by GPC measurement of the polymer sampled when the polymerization of B is completed, and the peak top molecular weight (Mp) of the diblock copolymer having the structure of A1-B. It can be obtained by subtracting the peak top molecular weight (Mp) of the polymer block A1 from the obtained value. Furthermore, the peak top molecular weight (Mp) of the polymer block A2 was determined by GPC measurement of the polymer sampled when the polymerization of A2 was completed, and the peak top molecular weight (Mp) of the triblock copolymer having the structure A1-B-A2. ) and subtracting the peak top molecular weight (Mp) of the diblock copolymer having the structure of A1-B from that value.
As another method, in the case of a triblock copolymer having an A1-B-A2 structure, the total peak top molecular weight (Mp) of the polymer block (A) is the peak top molecular weight of the block copolymer ( Mp) and the total content of the polymer block (A) confirmed by ¹ H-NMR measurement, and the peak top molecular weight (Mp) of the first deactivated polymer block A1 was calculated by GPC measurement. It is also possible to obtain the peak top molecular weight (Mp) of the second polymer block A2 by subtracting.

<Polymer block (B)>
The polymer block (B) is mainly composed of structural units derived from aromatic vinyl compounds (hereinafter sometimes abbreviated as "aromatic vinyl compound units"). The term "mainly" used herein means that the polymer block (B) contains 50% by mass or more of structural units derived from an aromatic vinyl compound. The content of the aromatic vinyl compound-derived structural unit in the polymer block (B) is preferably 70% by mass or more, and preferably 90% by mass, from the viewpoint of flexibility and damping properties at low temperatures of the molded article. It is more preferably 95% by mass or more, and even more preferably 95% by mass or more.
Examples of the aromatic vinyl compound include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, β-methylstyrene, 2,6-dimethylstyrene, 2,4-dimethylstyrene, α-methyl-o-methylstyrene, α-methyl-m-methylstyrene, α-methyl-p-methylstyrene, β-methyl-o-methylstyrene, β-methyl-m-methylstyrene, β-methyl-p -methylstyrene, 2,4,6-trimethylstyrene, α-methyl-2,6-dimethylstyrene, α-methyl-2,4-dimethylstyrene, β-methyl-2,6-dimethylstyrene, β-methyl- 2,4-dimethylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,6-dichlorostyrene, 2,4-dichlorostyrene, α-chloro-o-chlorostyrene, α-chloro-m -chlorostyrene, α-chloro-p-chlorostyrene, β-chloro-o-chlorostyrene, β-chloro-m-chlorostyrene, β-chloro-p-chlorostyrene, 2,4,6-trichlorostyrene, α -chloro-2,6-dichlorostyrene, α-chloro-2,4-dichlorostyrene, β-chloro-2,6-dichlorostyrene, β-chloro-2,4-dichlorostyrene, o-tert-butylstyrene, m-tert-butylstyrene, p-tert-butylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, o-bromo At least one compound selected from the group consisting of methylstyrene, m-bromomethylstyrene, p-bromomethylstyrene, styrene derivatives substituted with silyl groups, indene, vinylnaphthalene and the like can be mentioned. Among them, styrene, α-methylstyrene, p-methylstyrene and mixtures thereof are preferred, and styrene is more preferred, from the viewpoint of production cost and physical property balance.

However, the polymer block (B) is a structural unit derived from an unsaturated monomer other than the aromatic vinyl compound (hereinafter referred to as "other unsaturated monomer may be abbreviated as "unit"). Examples of other unsaturated monomers include butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, 1,3-hexadiene, isobutylene, methyl methacrylate, methyl vinyl ether, β-pinene, 8 ,9-p-mentene, dipentene, methylenenorbornene, 2-methylenetetrahydrofuran and the like. When the polymer block (B) contains the other unsaturated monomer units, the bonding form is not particularly limited, and may be random, tapered, completely alternating, partially blocky, block, or two or more thereof. It can consist of combinations.
When the polymer block (B) contains the other unsaturated monomer unit, the content thereof is preferably 20% by mass or less based on the total mass of the polymer block (B), and 10 mass % or less, more preferably 5% by mass or less, and particularly preferably 0% by mass.

The block copolymer should just have at least one said polymer block (B). When the block copolymer has two or more polymer blocks (B), the polymer blocks (B) may be the same or different.
In the present invention, the block copolymer preferably has one or two polymer blocks (B).

The total peak top molecular weight (Mp) of the polymer block (B) of the block copolymer is preferably in the state before hydrogenation, from the viewpoint of flexibility at low temperature of the molded product, vibration damping property, etc. is 3,000 to 15,000, more preferably 7,500 to 8,500.

<Block copolymer>
The block copolymer of the present invention contains a polymer block (A) mainly composed of 1,3,7-octatriene units and a polymer block (B) mainly composed of aromatic vinyl compound units.
Moreover, it is preferable that the polymer block (A) does not contain a structural unit derived from a conjugated diene having 12 or more carbon atoms.
The block copolymer of the present invention may contain a polymer block mainly composed of 1,3,7-octatriene units and a polymer block (B) mainly composed of aromatic vinyl compound units. In addition to the polymer block (A) and the polymer block (B), it may contain a polymer block (C) composed of other polymerizable monomers. Further, the copolymer of the present invention may be a block copolymer formed only from 1,3,7-octatriene units and aromatic vinyl compound units.
Examples of monomers constituting the polymer block (C) include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene and 1-undecene. , 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene and other unsaturated hydrocarbon compounds; 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-methylpropanesulfonic acid, vinylsulfonic acid, vinyl acetate, and unsaturated compounds containing a functional group such as methyl vinyl ether; These may be used singly or in combination of two or more.

The block copolymer of the present invention may contain structural units derived from a coupling agent. When the copolymer of the present invention contains a structural unit derived from a coupling agent, the content of the structural unit derived from the coupling agent is preferably 2.5 mol% or less in all structural units, It is more preferably 1.0 mol % or less.
Coupling agents include, for example, dichloromethane, dibromomethane, dichloroethane, dibromoethane, dibromobenzene, and phenyl benzoate. Among these, phenyl benzoate is preferred.

(Binding mode of polymer block (A) and polymer block (B))
In the block copolymer, as long as the polymer block (A) and the polymer block (B) are bonded, the form of bonding is not limited, and may be linear, branched, radial, or two of these. Any combination of the above binding modes may be used. Among them, it is preferable that the polymer block (A) and the polymer block (B) are bonded in a straight chain. When represented by B, a diblock copolymer represented by AB, a triblock copolymer represented by ABA or BAB, a tetrablock copolymer represented by ABAB Block copolymer, pentablock copolymer represented by ABA or BABAB, (AB) nX type copolymer (X is a coupling agent residue group, and n represents an integer of 2 or more). Among these, linear diblock copolymers or triblock copolymers are preferable, and AB type diblock copolymers or BAB type triblock copolymers are preferable. , BAB type triblock copolymers are more preferred.
Here, in the present specification, when polymer blocks of the same kind are linearly bonded via a bifunctional coupling agent or the like, the entire bonded polymer blocks are treated as one polymer block. be In accordance with this, the polymer block which should be strictly represented as YXY (X represents a coupling agent residue), including the above examples, should be distinguished from a single polymer block Y. It is denoted as Y as a whole, unless there is a Polymer blocks of this type containing coupling agent residues are treated as above herein, so for example, containing coupling agent residues, strictly speaking A—B—X—B—A ( X represents a coupling agent residue) is written as ABA and is treated as a triblock copolymer.
If it contains a coupling agent residue, it is preferably a linear triblock copolymer, more preferably of the BAXAB type (BAB type).
Further, the block copolymer may contain a polymer block ( C) may be present. In this case, when the polymer block (C) is represented by C, the structure of the block copolymer includes an ABC type triblock copolymer and an ABCA type tetrablock copolymer. , ABAC type tetrablock copolymers, and the like.

In the block copolymer, the mass ratio [(B)/(A)] of the polymer block (B) to the polymer block (A) is preferably 1/99 or more and 50/50 or less, more preferably 5/95. 40/60 or less, more preferably 10/90 or more and 35/65 or less.

In the block copolymer, the total content of polymer block (A) and polymer block (B) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably is 90% by weight or more, most preferably substantially 100% by weight. The value does not take into account the coupling agent residue, if the block copolymer contains the residue.

In the copolymer of the present invention, the content of the polymer block (A) with respect to the total amount of the polymer block (A), the polymer block (B), and optionally the polymer block (C) is Although not limited, it may be, for example, 1 to 99% by mass. The lower limit of the content of the polymer block (A) may be 3% by mass, 5% by mass, 30% by mass, or 50% by mass or more. , 70% by mass, 85% by mass, or 90% by mass. On the other hand, the upper limit of the content of the polymer block (A) may be 98% by mass or less, 95% by mass or less, 90% by mass or less, or 80% by mass or less. may be 70% by mass or less, 65% by mass or less, or 40% by mass or less. The lower limit and upper limit of the content of the polymer block (A) may be arbitrarily selected so as to maintain consistency.
Moreover, the content of the polymer block (B) with respect to the total amount of the polymer block (A), the polymer block (B), and the polymer block (C) used as necessary is not particularly limited. However, for example, it may be 1 to 99% by mass, may be 2 to 95% by mass, may be 5 to 95% by mass, may be 10 to 80% by mass, may be 20 to It may be 70% by mass, or 20 to 50% by mass.
When the copolymer of the present invention contains the polymer block (C) used as necessary, its content is the balance of the polymer block (A) and the polymer block (B).

The copolymer of the present invention may or may not be copolymerized with an anionically polymerizable compound.
The anionically polymerizable compound is not particularly limited as long as it is a compound other than 1,3,7-octatriene, styrene and other conjugated diene compounds and is anionically polymerizable. For example 2-chlorostyrene, 4-chlorostyrene, α-methylstyrene, α-methyl-4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,5 -dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 4-n-propylstyrene, 4-isopropylstyrene, 4-tert-butyl Styrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-(4-phenyl-n-butyl)styrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 1,1-diphenylethylene , N,N-dimethyl-p-aminoethylstyrene, N,N-diethyl-p-aminoethylstyrene, 1,2-divinylbenzene, 1,3-divinylbenzene, 1,4-divinylbenzene, 1,2- Divinyl-3,4-dimethylbenzene, 2,4-divinylbiphenyl, 1,3-divinylnaphthalene, 1,2,4-trivinylbenzene, 3,5,4'-trivinylbiphenyl, 1,3,5- aromatic vinyl compounds such as trivinylnaphthalene and 1,5,6-trivinyl-3,7-diethylnaphthalene; α,β-unsaturated nitriles such as acrylonitrile, methacrylonitrile and ethacrylonitrile; α,β-unsaturated carboxylic acids such as crotonic acid, 3-methylcrotonic acid, 3-butenoic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid; methyl acrylate, ethyl acrylate, propyl acrylate , butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, Isopropyl methacrylate, butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, dimethyl maleate, diethyl maleate, malein α,β-unsaturated carboxylic acid esters such as dibutyl acid, dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate; N - methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-octylacrylamide, N-phenylacrylamide, N-glycidylacrylamide, N,N'-ethylenebisacrylamide, N,N-dimethylacrylamide, N-ethyl-N-methylacrylamide, N,N-diethylacrylamide, N,N-dipropylacrylamide, N,N-dioctylacrylamide, N,N-diphenylacrylamide, N-ethyl-N-glycidylacrylamide, N,N - diglycidylacrylamide, N-methyl-N-(4-glycidyloxybutyl)acrylamide, N-methyl-N-(5-glycidyloxypentyl)acrylamide, N-methyl-N-(6-glycidyloxyhexyl)acrylamide, N-acryloylpyrrolidine, N-acryloyl-L-proline methyl ester, N-acryloylpiperidine, N-acryloylmorpholine, 1-acryloylimidazole, N,N'-diethyl-N,N'-ethylenebisacrylamide, N,N'-dimethyl-N,N'-hexamethylenebisacrylamide,di(N,N'-ethylene)bisacrylamide and the like. The anionic polymerizable compounds may be used singly or in combination of two or more.

<Hydride>
The molded article of the present invention contains a hydride of the block copolymer.
The hydrogenation rate of the hydride is not particularly limited, but in the block copolymer, 80.0 mol% or more of the carbon-carbon double bonds in the polymer block (A) are hydrogenated (also referred to as hydrogenation ), more preferably 85.0 mol% or more is hydrogenated, more preferably 90.0 mol% or more is hydrogenated, and 93.0 mol% or more is It is more preferably hydrogenated, and most preferably 95.0 mol % or more is hydrogenated. In addition, this value may be called a hydrogenation rate (hydrogenation rate). Although the upper limit of the hydrogenation rate is not particularly limited, it may be 99.0 mol % or less.
The degree of hydrogenation is determined by ¹ H-NMR measurement after hydrogenation of the content of carbon-carbon double bonds. More specifically, it can be obtained according to the method described in Examples.

The peak top molecular weight (Mp) of the hydrogenated block copolymer (referred to as a hydrogenated block copolymer) is preferably 20,000 from the viewpoint of flexibility at low temperatures of molded articles, vibration damping properties, and the like. ~500,000, more preferably 50,000 to 450,000, more preferably 80,000 to 400,000, even more preferably 100,000 to 350,000, most preferably 110,000 to 330,000 .
The molecular weight distribution (Mw/Mn) of the hydrogenated block copolymer is not particularly limited, but is preferably 1.0 to 3.0, more preferably 1.2 to 2.2.

<Method for producing hydrogenated block copolymer>
The hydrogenated block copolymer of the present invention can be obtained by, for example, a step of polymerizing by anionic polymerization and a step of hydrogenating the block copolymer obtained in the polymerization step. .
In the anionic polymerization, a monomer derived from the polymer block (A) and a monomer derived from the polymer block (B) are successively added in the presence of a solvent, an anionic polymerization initiator, and optionally a Lewis base to form a block. A copolymer can be obtained. Further, if necessary, a block copolymer containing a structural unit derived from a coupling agent can be obtained by further adding a coupling agent and reacting.
For example, in the presence of a solvent, an anionic polymerization initiator, and optionally a Lewis base, an aromatic vinyl compound, 1,3,7-octatriene, and optionally other than 1,3,7-octatriene A block copolymer can be obtained by sequentially adding a conjugated diene compound. Further, if necessary, a block copolymer containing a structural unit derived from a coupling agent can be obtained by further adding a coupling agent and reacting.
Then, by hydrogenating the block copolymer, a hydrogenated block copolymer can be obtained.

In the above method, the polymerization initiator for anionic polymerization is not limited to any type as long as it is a compound capable of initiating anionic polymerization, and an organic alkali metal compound generally used in the anionic polymerization of aromatic vinyl compounds and conjugated diene compounds. can be used. Examples of the organic alkali metal compounds include methyllithium, ethyllithium, propyllithium, isopropyllithium, butyllithium, sec-butyllithium, tert-butyllithium, isobutyllithium, pentyllithium, hexyllithium, butadienyllithium, cyclohexyl. Lithium, phenyllithium, benzyllithium, p-toluyllithium, styryllithium, trimethylsilyllithium, 1,4-dilithiobutane, 1,5-dilithiopentane, 1,6-dilithiohexane, 1,10-dilithiodecane, 1,1-dilithiodecane Thiodiphenylene, dilithiopolybutadiene, dilithiopolyisoprene, 1,4-dilithiobenzene, 1,2-dilithio-1,2-diphenylethane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5 -organolithium compounds such as trilithiobenzene, 1,3,5-trilithio-2,4,6-triethylbenzene; methyl sodium, ethyl sodium, n-propyl sodium, isopropyl sodium, n-butyl sodium, sec-butyl sodium , tert-butylsodium, isobutylsodium, phenylsodium, sodium naphthalene, cyclopentadienylsodium and other organic sodium compounds. Among them, n-butyllithium and sec-butyllithium are preferred. An organic alkali metal compound may be used individually by 1 type, and may use 2 or more types together.

The amount of the anionic polymerization initiator used is, for example, the total amount of raw material monomers/anionic polymerization initiator (molar ratio) is preferably 10 to 3,000, more preferably 50 to 2,500, more preferably 100 to It is more preferably 2,500, particularly preferably 100 to 2,000, and most preferably 100 to 1,500.

A Lewis base may also be used during the anionic polymerization. The type of the Lewis base is not particularly limited as long as it is an organic compound that does not substantially react with the anionic polymerization initiator and the growing terminal anion.
When a Lewis base is used, the molar ratio (Lewis base/polymerization initiator) between the Lewis base and the polymerization initiator (anionic polymerization initiator) used for anionic polymerization is preferably 0.01 to 1,000. , more preferably 0.01 to 400, more preferably 0.1 to 50, and particularly preferably 0.1 to 20. Within this range, it is easy to achieve a high conversion of 1,3,7-octatriene in a short time.

Examples of Lewis bases 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 tert; - alkali metal alkoxides such as butoxide; phosphine compounds and the like.

Although the copolymer of the present invention can be produced in the absence of a solvent, it is preferably carried out in the presence of a solvent for the purpose of efficiently removing the heat of polymerization.
The solvent is not particularly limited as long as it does not substantially react with the anionic polymerization initiator and the growing terminal anion, but hydrocarbon solvents are preferred.
Hydrocarbon solvents include, for example, isopentane (27.9°C; boiling point at 1 atm; hereinafter the same), pentane (36.1°C), cyclopentane (49.3°C), hexane (68°C), .7°C), cyclohexane (80.7°C), heptane (98.4°C), isoheptane (90°C), isooctane (99°C), 2,2,4-trimethylpentane (99°C), methylcyclohexane (101 .1°C), cycloheptane (118.1°C), octane (125.7°C), ethylcyclohexane (132°C), methylcycloheptane (135.8°C), nonane (150.8°C), decane (174 .1 ° C.) and other saturated aliphatic hydrocarbons; benzene (80.1 ° C.), toluene (110.6 ° C.), ethylbenzene (136.2 ° C.), p-xylene (138.4 ° C.), m-xylene ( 139.1°C), o-xylene (144.4°C), propylbenzene (159.2°C) and butylbenzene (183.4°C).
It is preferable to use a solvent having a boiling point lower than that of 1,3,7-octatriene (boiling point 125.5° C.), which is one of the raw material monomers, because the heat of polymerization can be efficiently removed by reflux condensation cooling of the solvent. From this point of view, solvents include isopentane (27.9°C), pentane (36.1°C), cyclopentane (49.3°C), hexane (68.7°C), cyclohexane (80.7°C), heptane (98.4°C), isoheptane (90°C), isooctane (99°C), 2,2,4-trimethylpentane (99°C), methylcyclohexane (101.1°C), cycloheptane (118.1°C), Benzene (80.1°C) and toluene (110.6°C) are preferred. From the same point of view, cyclohexane and n-hexane are more preferred.
A solvent may be used individually by 1 type, and may use 2 or more types together.

The polymerization temperature during anionic polymerization is not particularly limited, but it is preferable to carry out the anionic polymerization at a temperature above the freezing point of the chemical and below a temperature at which the chemical does not thermally decompose. Preferably -50 to 200°C, more preferably -20 to 120°C, and even more preferably 15 to 100°C, while shortening the polymerization time and maintaining a high conversion of 1,3,7-octatriene. It is possible to produce a copolymer excellent in mechanical properties by suppressing the formation of a low-molecular-weight polymer caused by partial thermal degradation of the growing terminal anion.

Polymerization in the present invention can be carried out favorably as long as contamination of substances that inhibit the polymerization reaction by reacting with growing terminal anions, such as air containing oxygen and water, is suppressed.
When using a solvent having a boiling point below the polymerization temperature, the temperature may be controlled by controlling the pressure with an inert gas to control the amount of solvent vapor generated. is used, the temperature may be controlled by reducing the pressure in the reaction system using an exhaust pump and controlling the amount of vapor generated from the solvent.
The polymerization pressure is not particularly limited, but if it is 0.01 to 10 MPaG, more preferably 0.1 to 1 MPaG, not only the amount of inert gas used can be reduced, but also the reactor with high pressure resistance and the inert gas can be removed from the system. Polymerization can be economically advantageous because a pump for exhausting the gas is not required.

The polymerization time is not particularly limited, but it is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours, in order to suppress the formation of low-molecular-weight polymers due to partial thermal degradation of growing terminal anions. It is easy to produce a copolymer having excellent mechanical properties.

After the anionic polymerization reaction, a coupling agent is then added for coupling reaction to obtain a block copolymer containing structural units derived from the coupling agent.
As the coupling agent, the coupling agents described above can be used.

After the polymerization is carried out by the method described above, an active hydrogen compound such as alcohols, carboxylic acids or water is added to terminate the polymerization reaction.
The conversion rate of 1,3,7-octatriene determined by gas chromatography after anionic polymerization is preferably 80.0% or more, more preferably 90.0% or more, and 95.0%. It is more preferably 97.0% or more, even more preferably 97.0% or more, and most preferably 98.0% or more.

A hydrogenated block copolymer is usually produced by adding a hydrogenation catalyst to a polymer solution obtained by terminating polymerization in the production of the copolymer or to a polymer solution diluted with the solvent as necessary. can be produced by reacting with hydrogen.
Hydrogenation catalysts include, for example, Raney nickel; heterogeneous catalysts in which metals such as Pt, Pd, Ru, Rh, and Ni are supported on simple substances such as carbon, alumina, and diatomaceous earth; transition metal compounds, alkylaluminum compounds, and alkyllithium Ziegler-type catalysts in combination with other compounds; metallocene-based catalysts; Specific examples include bis(2-ethylhexanoate)nickel(II) and triisobutylaluminum.

The temperature of the hydrogenation reaction is preferably −20 to 250° C., which is higher than the freezing point of the solvent and lower than the thermal decomposition temperature of the copolymer. ~150°C is more preferred. If the temperature is 30°C or higher, the hydrogenation reaction proceeds, and if the temperature is 150°C or lower, the hydrogenation reaction can be carried out with a small amount of the hydrogenation catalyst even if thermal decomposition of the hydrogenation catalyst occurs concurrently. From the viewpoint of reducing the amount of hydrogenation catalyst used, 60 to 100° C. is more preferable.
Hydrogen can be used in a gaseous state, and the pressure is not particularly limited as long as it is normal pressure or higher. If the pressure is 20 MPaG or less, the hydrogenation reaction can be carried out with a small amount of the hydrogenation catalyst even if the hydrogenation catalyst is concurrently hydrocracked. From the viewpoint of reducing the amount of hydrogenation catalyst used, 0.5 to 10 MPaG is more preferable.
The time required for the hydrogenation reaction can be appropriately selected depending on the conditions, but from the viewpoint of industrially advantageous production of the hydrogenated copolymer, it is preferably in the range of 10 minutes to 24 hours from the start of coexistence with the catalyst.
After completion of the hydrogenation reaction, the reaction mixture can be diluted or concentrated with the solvent, if necessary, and then washed with a basic aqueous solution or an acidic aqueous solution to remove the hydrogenation catalyst.

The polymer solution obtained after the polymerization reaction or the polymer solution obtained after the hydrogenation reaction may be concentrated and then supplied to an extruder to isolate the copolymer, or may be brought into contact with steam to remove a solvent, etc. may be isolated by removing the copolymer, or the copolymer may be isolated by contacting it with a heated inert gas to remove the solvent and the like.

<Hydrogenated block copolymer composition>
The hydrogenated block copolymer composition of the present invention contains the hydrogenated block copolymer of the present invention, a polymer other than the hydrogenated block copolymer of the present invention, and other materials such as various additives. It is a thing.
The molded article of the present invention may contain the hydrogenated block copolymer as a hydrogenated block copolymer composition.
Other materials include polyolefin resins, tackifying resins, softeners, heat shielding materials, UV absorbers, antioxidants, light stabilizers, and the like.
The content of the hydrogenated block copolymer in the hydrogenated block copolymer composition of the present invention is preferably 1 to 99% by mass from the viewpoint of moldability.

Examples of polyolefin resins include polyethylene, polypropylene, polybutene-1, polyhexene-1, poly-3-methyl-butene-1, poly-4-methyl-pentene-1, ethylene and an α-olefin having 3 to 20 carbon atoms. (For example, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene, 6-methyl-1- heptene, isooctene, isooctadiene, decadiene, etc.), ethylene/propylene/diene copolymer (EPDM), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer etc. are preferably used.
The polyolefin resin may be modified with maleic anhydride or the like.

The polyolefin resin may be a polar group-containing polyolefin polymer.
The polar group of the polar group-containing polyolefin polymer includes, for example, a polar group derived from vinyl acetate, vinyl chloride, ethylene oxide, propylene oxide, acrylamide, unsaturated carboxylic acid or its ester or acid anhydride.
Among them, a polar group derived from an unsaturated carboxylic acid or its ester or acid anhydride is preferred. Examples of unsaturated carboxylic acids or their esters or acid anhydrides include (meth)acrylic acid, (meth)acrylic acid esters, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, hymic acid, and anhydride. hymic acid and the like. The polar group-containing polyolefin polymer may have one or more of these polar groups.
The method of obtaining the polar group-containing polyolefin polymer is not particularly limited. Those obtained by random copolymerization, block copolymerization or graft copolymerization by known methods, those obtained by subjecting polyolefin resins to reactions such as oxidation or chlorination by known methods, etc. are used. can.
Examples of copolymers of olefins and polar group-containing copolymerizable monomers include ethylene-methyl (meth)acrylate copolymers, ethylene-ethyl (meth)acrylate copolymers, ethylene-(meth)acrylate copolymers, Acrylic acid copolymers, metal ion crosslinked resins (ionomers) of ethylene-(meth)acrylic acid copolymers, and the like.
In the hydrogenated block copolymer composition of the present invention, the mass ratio of the hydrogenated block copolymer to the polyolefin resin [hydrogenated block copolymer/polyolefin resin] is preferably 10/90 to 99/1, and 30/ 70 to 98/2 are more preferred, and 40/60 to 97/3 are even more preferred.

When the molded article of the present invention is a medical tube, the mass ratio of the hydrogenated block copolymer to the polyolefin resin [hydrogenated block copolymer/polyolefin resin] is preferably 10/90 to 95/5, and 30/ 70 to 85/15 is more preferred, and 40/60 to 80/20 is even more preferred.

When the molded article of the present invention is a liquid packaging material, the mass ratio of the hydrogenated block copolymer to the polyolefin resin [hydrogenated block copolymer/polyolefin resin] is preferably 10/90 to 99/1, and 30/ 70 to 98/2 are more preferred, and 40/60 to 97/3 are even more preferred.

When the molded article of the present invention is an interlayer film for laminated glass, the mass ratio of the hydrogenated block copolymer to the polyolefin resin [hydrogenated block copolymer/polyolefin resin] is preferably 80/20 to 97/3. 90/10 to 95/5 are more preferred. When the mass ratio of the hydrogenated block copolymer to the polyolefin resin exceeds 80, the haze of laminated glass is improved. As polyolefins having an adhesive functional group, among the above polyolefins, polypropylene containing a carboxyl group is preferable from the viewpoint of ease of availability, ease of adjustment of adhesiveness, and ease of adjustment of haze. is.

Examples of tackifying resins include rosin resins, terpene phenol resins, terpene resins, aromatic hydrocarbon-modified terpene resins, aliphatic petroleum resins, alicyclic petroleum resins, aromatic hydrocarbon resins, coumarone-indene resins, Phenolic resins, xylene resins, hydrogenated products thereof, and the like are included. These tackifying resins may be used alone or in combination of two or more.

Softening agents include, for example, hydrocarbon oils such as paraffinic, naphthenic, and aromatic oils; vegetable oils such as peanut oil and rosin; phosphate ester; low molecular weight polyethylene glycol; liquid paraffin; low molecular weight polyethylene, ethylene-α - Known softeners such as hydrocarbon-based synthetic oils such as olefin copolymer oligomer, liquid polybutene, liquid polyisoprene or its hydrogenated products, liquid polybutadiene or its hydrogenated products can be used. These may be used alone or in combination of two or more. Among them, paraffinic hydrocarbon oils and hydrocarbon synthetic oils such as ethylene-α-olefin copolymer oligomers are preferably used as softeners.

As heat shielding materials, tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), aluminum-doped zinc oxide (AZO), phthalocyanine compounds (NIOBP), naphthalocyanine compounds, compounds having an anthracyanine skeleton, general formula MmWOn (M represents a metal element, m is 0.01 or more and 1.0 or less, n is 2.2 or more and 3.0 or less), metal-doped tungsten oxide, zinc antimonate (ZnSbO), and lanthanum hexaboride. Among them, ITO, ATO, and metal-doped tungsten oxide are preferable from the viewpoint of infrared absorption, metal-doped tungsten oxide is more preferable, and cesium tungsten oxide is particularly preferable.

Examples of UV absorbers include, but are not limited to, 2-(5-chloro-2-benzotriazolyl)-6-tert-butyl-p-cresol, 2-(5-methyl-2-hydroxyphenyl). Benzotriazole, 2-[2-hydroxy-3,5-bis(α,α'-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl) Benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-tert-butyl-5-methyl-2-hydroxyphenyl) -benzotriazole such as 5-chlorobenzotriazole, 2-(3,5-di-tert-amyl-2-hydroxyphenyl)benzotriazole or 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole UV absorbers, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6, 6-pentamethyl-4-piperidyl)-2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonate, or 4-(3-(3,5-di-tert -butyl-4-hydroxyphenyl)propionyloxy)-1-(2-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy)ethyl)-2,2,6,6- Hindered amine UV absorbers such as tetramethylpiperidine, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, or hexadecyl-3,5-di-tert-butyl- Benzoate-based ultraviolet absorbers such as 4-hydroxybenzoate and the like are included. Other examples include triazine-based compounds, benzophenone-based compounds, malonic acid ester compounds, and oxalic acid anilide compounds.

Examples of the triazine-based compound include 6-(4-hydroxy-3,5-di-tert-butylanilino)-2,4-bis-octylthio-1,3,5-triazine, 6-(4-hydroxy- 3,5-dimethylanilino)-2,4-bis-octylthio-1,3,5-triazine, 6-(4-hydroxy-3-methyl-5-tert-butylanilino)-2,4-bis-octylthio -1,3,5-triazine or 2-octylthio-4,6-bis-(3,5-di-tert-butyl-4-oxyanilino)-1,3,5-triazine. In this specification, the triazine-based compound is treated as an ultraviolet absorber and not as an antioxidant.

Examples of the benzophenone compounds include 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2-carboxybenzophenone, 2-hydroxy-4-n - octoxybenzophenone and the like.
Examples of the malonic ester compound include dimethyl 2-(p-methoxybenzylidene)malonate, tetraethyl-2,2-(1,4-phenylenedimethylidene)bismalonate, 2-(p-methoxybenzylidene)-bis( 1,2,2,6,6-pentamethyl-4-piperidinyl)malonate and the like.

Examples of antioxidants include phenol antioxidants, phosphorus antioxidants, sulfur antioxidants, etc. Among these, phenol antioxidants are preferred, and alkyl-substituted phenol antioxidants are particularly preferred. preferable.

Examples of phenolic antioxidants include 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenylacrylate, 2,4-di-tert-amyl -Acrylate compounds such as 6-(1-(3,5-di-tert-amyl-2-hydroxyphenyl)ethyl)phenylacrylate, 2,6-di-tert-butyl-4-methylphenol, 2,6 -di-tert-butyl-4-ethylphenol, octadecyl-3-(3,5-)di-tert-butyl-4-hydroxyphenyl)propionate, 2,2′-methylene-bis(4-methyl-6- tert-butylphenol), 4,4′-butylidene-bis(4-methyl-6-tert-butylphenol), 4,4′-butylidene-bis(6-tert-butyl-m-cresol), 4,4′- thiobis(3-methyl-6-tert-butylphenol), bis(3-cyclohexyl-2-hydroxy-5-methylphenyl)methane, 3,9-bis(2-(3-(3-tert-butyl-4- Hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,1,3-tris(2-methyl-4 -hydroxy-5-tert-butylphenyl)butane, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4, 6-(1H,3H,5H)-trione, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tetrakis(methylene-3 -(3′,5′-di-tert-butyl-4′-hydroxyphenyl)propionate)methane, or triethylene glycol bis(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate) and alkyl-substituted phenolic compounds such as

Phosphorus antioxidants include, for example, tris(2,4-di-tert-butylphenyl) phosphate, triphenylphosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite, tris(nonylphenyl)phosphite, tris (Dinonylphenyl)phosphite, tris(2-tert-butyl-4-methylphenyl)phosphite, tris(cyclohexylphenyl)phosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl Phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-tert-butyl-4-hydroxybenzyl)-9,10-dihydro-9- Monophosphite compounds such as oxa-10-phosphaphenanthrene-10-oxide or 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene, 4,4′-butylidene-bis(3 -methyl-6-tert-butylphenyl-di-tridecylphosphite), 4,4'-isopropylidene-bis(phenyl-di-alkyl (C12 or more, C15 or less) phosphite) 4,4'-isopropylidene -bis (diphenyl monoalkyl (C12 or more, C15 or less) phosphite), 1,1,3-tris(2-methyl-4-di-tridecylphosphite-5-tert-butylphenyl)butane, or tetrakis ( Diphosphite compounds such as 2,4-di-tert-butylphenyl)-4,4′-biphenylene phosphite and the like are included. Among these, monophosphite compounds are preferred.

Examples of sulfur-based antioxidants include dilauryl 3,3'-thiodipropionate, distearyl 3,3-thiodipropionate, laurylstearyl 3,3'-thiodipropionate, pentaerythritol-tetrakis-( β-lauryl-thiopropionate), 3,9-bis(2-dodecylthioethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane and the like.

As the light stabilizer, the light stabilizer is a hindered amine type, for example, ADEKA Co., Ltd. "ADEKA STAB LA-57 (trade name)", Ciba Specialty Chemicals Co., Ltd. dimethyl succinate and 4-hydroxy -2,2,6,6-tetramethyl-1-piperidineethanol "Tinuvin-622SF (trade name)", which is a polymer, and the like.

The hydrogenated block copolymer composition of the present invention may contain other resins as long as the objects of the present invention are not impaired. Other resins include conjugated diene resins such as polyisoprene, polybutadiene, styrene-butadiene rubber, and styrene-isoprene rubber; styrene resins such as polystyrene, AS resin, and ABS resin; polyphenylene ether resins such as modified polyphenylene ether; Polyamide resins such as nylon 6 and nylon 66; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; polyurethane resins; acetal resins such as polyvinyl acetal, polyoxymethylene homopolymer and polyoxymethylene copolymer; Examples include acrylic resins such as resins.
In the hydrogenated block copolymer composition of the present invention, the mass ratio of the hydrogenated block copolymer to the other resin [hydrogenated block copolymer/other resin] is preferably 1/99 to 60/40. 3/97 to 40/60 is more preferable.

The hydrogenated block copolymer composition of the present invention may contain other hydrogenated block copolymers other than the hydrogenated block copolymer of the present invention.
Other hydrogenated block copolymers include, for example, a polymer block (B) mainly composed of structural units derived from the aromatic vinyl compound and a conjugated diene other than the 1,3,7-octatriene. A hydrogenated block copolymer obtained by hydrogenating a block copolymer containing a polymer block (C) mainly composed of structural units that Preferred aspects of the polymer block (B), the polymer block (C), and the hydrogenation rate in other hydrogenated block copolymers are the respective polymer blocks and It is the same as the preferred mode of the hydrogenation rate.

<Method for manufacturing molded body>
The method for producing the molded article is not particularly limited, and various conventional molding methods such as injection molding, blow molding, press molding, extrusion molding, calendar molding and the like can be used.
Examples of the shape of the molded body include pellets, sheets, plates, pipes, tubes, rods, granules, and various other shapes.

<Hardness>
The molded article of the present invention has a hardness (hereinafter also referred to as "A hardness") at a temperature of 23 ° C. measured by the type A durometer method of JIS K 6253-3 (2012), from the viewpoint of flexibility at low temperatures. Therefore, it is preferably 75 or less, more preferably 60 or less, still more preferably 40 or less, and is 1 or more from the viewpoint that the molded article has appropriate hardness. It should be noted that the lower the numerical value of the altitude, the more excellent the flexibility.
In another aspect, the hardness at a temperature of 23 ° C measured by the type D durometer method of JIS K 6253-3 (2012) (hereinafter also referred to as "D hardness") is the flexibility at low temperatures of the molded product. It is preferably 75 or less, more preferably 60 or less, still more preferably 53 or less from the viewpoint of hardness, and 1 or more from the viewpoint that the molded article has appropriate hardness.
In the present invention, the hardness can be measured using a molded article obtained by injection molding the hydrogenated block copolymer of the present invention or the hydrogenated block copolymer composition of the present invention. More details are as described in Examples.

<Peak top of tan δ and peak top temperature>
The molded article of the present invention conforms to JIS K7244-10 (2005) with a strain amount of 0.1%, a frequency of 1 Hz, a measurement temperature of -70 to 200 ° C., a heating rate of 3 ° C./min, and a test piece thickness. It is preferable that the peak top of tan δ measured under the condition of 1 mm is 1.5 or more.
The tan δ (loss tangent) is the ratio of loss elastic modulus/storage elastic modulus at a frequency of 1 Hz in dynamic viscoelasticity measurement, and the peak top of tan δ greatly contributes to damping properties and other physical properties. Here, the peak top of tan δ is the value of tan δ when the peak of tan δ is maximum.
In the present invention, the peak top of tan δ is measured by pressing the hydrogenated block copolymer of the present invention or the hydrogenated block copolymer composition of the present invention at a temperature of 230 ° C. and a pressure of 10 MPaG for 3 minutes. A single-layer sheet is prepared, and a compact obtained by cutting the single-layer sheet into a disc shape can be used.
In the present invention, the tan δ measuring device is not particularly limited, but a rotary rheometer "ARES-G2" (manufactured by TA Instruments) or the like is used, and the molded product is sandwiched between flat plates with a diameter of 8 mm for testing. can do. More details are as described in Examples.
The higher the peak top value of tan δ, the better the damping property at that temperature. From the viewpoint of damping properties, the molded article of the present invention preferably has a tan δ peak top of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. .
The peak top in the tan δ measurement conditions of the present invention can be controlled by methods such as optimizing the selection and content ratio of the monomers used in the block copolymer and suitably adjusting the amount of vinyl bonds. .

In the molded body of the present invention, in accordance with JIS K7244-10 (2005), strain amount 0.1%, frequency 1 Hz, measurement temperature -70 to 200 ° C., heating rate 3 ° C./min, thickness of test piece The peak top temperature of tan δ measured under the condition of 1 mm is preferably 40 ° C. or less, more preferably 20 ° C. or less, and 0 ° C. or less from the viewpoint of flexibility at low temperatures of the molded body. is more preferable, and -20° C. or lower is even more preferable. If the peak top temperature of tan δ is −50° C. or higher, it is possible to obtain sufficient damping properties in an actual use environment.
Incidentally, the peak top temperature of tan δ can be measured using the same shaped body as the shaped body used for measuring the peak top.

[Laminate]
The laminate of the present invention includes a layer using the molded article of the present invention.
The laminate of the present invention uses the hydrogenated block copolymer of the present invention or the hydrogenated block copolymer composition of the present invention.
The shape of the laminate is not particularly limited, and may be film-like, sheet-like, tube-like, etc. Among them, the film-like laminate is preferable.
The laminate of the present invention can be obtained, for example, by laminating the hydrogenated block copolymer of the present invention or a film using the hydrogenated block copolymer of the present invention and a layer made of another resin. .
Such other resins include polyolefin resins, polyester resins, polyamide resins, acrylic resins, polyoxymethylene resins, styrene resins, polycarbonate resins, natural rubbers, chloroprene rubbers, acrylic rubbers, butyl rubbers, acrylonitrile butadiene rubbers. , urethane rubber, and the like. Examples of polyolefin resins include polypropylene (homopropylene, block propylene, random propylene), propylene-ethylene copolymer, low-density polyethylene, linear low-density polyethylene, high-density polyethylene, and ethylene-α-olefin copolymer. mentioned. Examples of polyester-based resins include polyethylene terephthalate (PET).
The content of the hydrogenated block copolymer contained in the film is preferably 100% by mass.

The laminate of the present invention may be a layer of fabric and a layer using the hydrogenated block copolymer of the present invention or the hydrogenated block copolymer composition of the present invention. In this case, the method for producing the laminate of the present invention is not particularly limited, but for example, injection molding methods such as insert injection molding method, two-color injection molding method, sandwich injection molding method; method, extrusion molding method such as extrusion coating method; calendar molding method; press molding method; A method of combining and laminating by a compression molding method can be mentioned.

There are no particular restrictions on the type of fabric of the fabric, but examples thereof include woven fabrics, knitted fabrics, felts, and non-woven fabrics.
Further, the material of the cloth may be natural fibers, synthetic fibers, or a combination of natural fibers and synthetic fibers. Natural fibers include one or more selected from cotton, silk, hemp and wool.
The synthetic fiber is preferably at least one selected from polyester fiber, acrylic fiber (polyacrylonitrile), polyurethane fiber, polyamide fiber, polyolefin fiber and vinylon fiber. Polyamide fibers include nylon 6, nylon 6.6, and the like. Examples of polyolefin fibers include polyethylene fibers and polypropylene fibers.
However, from the viewpoint of further improving the adhesive strength, the content of natural fibers is preferably 10% by mass or more, more preferably 20% by mass or more, and more preferably 30% by mass or more. The content is more preferably 40% by mass or more, more preferably 70% by mass or more, particularly preferably 80% by mass or more, and most preferably 90% by mass or more.

The laminate of the present invention comprises a layer using the hydrogenated block copolymer of the present invention or the hydrogenated block copolymer composition of the present invention (hereinafter referred to as "layer (1)") and a fabric layer ( Hereinafter, it may also be referred to as "fabric (2)". In the case of three or more layers consisting of these, "layer (1) / fabric (2) / layer (1)", "layer (1) / layer (1) / fabric (2)" (however, two layers ( 1) consists of different components.) and the like.
Furthermore, the laminate of the present invention may have another layer (3) in addition to the layer (1) and the fabric (2). When another layer (3) is provided, the layer (3) may be provided on the layer (1) or on the fabric (2). From the viewpoint of the surface layer, the other layer (3) is on the layer (1), that is, it has a layer structure of "fabric (2) / layer (1) / layer (3)" is preferred.
The other layer (3) may consist of one layer, or may consist of two or more layers.
Other components of layer (3) are not particularly limited, but examples include thermoplastic resins, various metals, various leathers, various glasses, and various woods. Among them, thermoplastic resins and various leathers are preferably used.

In the laminate of the present invention, the layer (1) may be foamed by containing a foaming agent. Examples of foaming agents that can be used in this case include inorganic foaming agents such as ammonium carbonate, ammonium hydrogen carbonate, sodium hydrogen carbonate, ammonium nitrite, sodium borohydride, and azides; N-nitroso compounds such as methylenetetramine, N,N'-dimethyl-N,N'-dinitrosoterephthalamide, azo compounds such as azobisisobutyronitrile, azodicarbonamide, barium azodicarboxylate, trichloro Fluorinated alkanes such as monofluoromethane and dichloromonofluoromethane, p-toluenesulfonyl hydrazide, diphenylsulfone-3,3'-disulfonyl hydrazide, 4,4'-oxybis(benzenesulfonyl hydrazide), allyl bis(sulfonyl hydrazide) sulfonyl hydrazine compounds, sulfonyl semicarbazide compounds such as p-toluylenesulfonyl semicarbazide and 4,4′-oxybis(benzenesulfonyl semicarbazide), triazole compounds such as 5-morpholyl-1,2,3,4-thiatriazole, etc. organic foaming agent; heat-expandable compounds such as isobutane and pentane are heat-expandable fine particles encapsulated in microcapsules made of thermoplastic resins such as vinylidene chloride, acrylonitrile, acrylic acid esters, and methacrylic acid esters. be able to.

Commercially available thermally expandable fine particles include "Microsphere" (trade name, epoxy resin-encapsulated microcapsules) manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd., and "Philite" (trade name, inorganic microballoons) manufactured by Nippon Philite Co., Ltd. , and "EXPANCEL" (trade name, organic microballoon) manufactured by AKZO NOBEL. Among the foaming agents, inorganic foaming agents, azo compounds, and sulfonylhydrazine compounds are preferred from the viewpoint of safety to the human body. These may be used alone or in combination of two or more.

When a foaming agent is used, its content is preferably 0.1 to 3.0% by mass, more preferably 0.3 to 2.8% by mass, based on the mass of the entire hydrogenated block copolymer composition. If the content of the foaming agent is less than 0.1% by mass, the expansion ratio of the resulting foamed molded product may be insufficient and the rubber elasticity may be poor. There is a possibility that a laminate having adequate closed cells may not be obtained.

The foaming method when using a foaming agent is not particularly limited, but a chemical method for foaming by decomposition or reaction of the foaming agent, or a combination of the chemical method and a physical method such as supercritical foaming or water foaming may be used. good.

The laminate of the present invention is a laminate in which a layer comprising a hydrogenated block copolymer or the hydrogenated block copolymer composition of the present invention is used as an adhesive layer, and a layer comprising another resin is used as a substrate layer. can also be used as
The base material layer is not particularly limited, but polyolefin-based resins and polyester-based resins are preferable from the viewpoint of the performance and price of the laminate.
The structure of the substrate layer may be a single layer or a multi-layer structure of two or more layers. When it consists of two or more layers, two or more kinds of resins having different materials may be used.
The thickness of the substrate layer is preferably 500 µm or less, more preferably 200 µm or less, and even more preferably 100 µm or less.

Additives such as heat stabilizers, light stabilizers, ultraviolet absorbers, antioxidants, lubricants, colorants, Antistatic agent, flame retardant, water repellent, waterproof agent, hydrophilic agent, conductivity imparting agent, thermal conductivity imparting agent, electromagnetic wave shielding agent, translucency adjusting agent, fluorescent agent, slidability imparting agent , a transparency imparting agent, an antiblocking agent, a metal deactivator, an antibacterial agent, and the like may be further added.

The method for producing the laminate of the present invention is not particularly limited. Alternatively, a film molding method, a multilayer injection blow method such as a coin injection blow method, a blow molding method such as a multilayer direct blow method, a calender molding method, or the like can be employed. Further, the molded laminate can be used as it is, or after being uniaxially or biaxially stretched. That is, the hydrogenated block copolymer of the present invention or the hydrogenated block copolymer composition of the present invention is applied to a substrate layer by a coextrusion T-die method, an inflation method, a lamination method, a solvent coating method, or a calendar molding method. It can be obtained by a lamination method or the like.

As a method of extruding a hydrogenated block copolymer or a composition or substrate containing a hydrogenated block copolymer melted by heating from a T-die by a co-extrusion T-die method or a lamination method, there is a feed block method (single manifold method ), multi-manifold method, and the like.
In the case of producing a laminate by solvent coating, the hydrogenated block copolymer of the present invention or a composition containing the hydrogenated block copolymer of the present invention is dissolved in an organic solvent to prepare a solution. is applied to the substrate layer and then dried to obtain a laminate.

The organic solvent is not particularly limited, and examples thereof include cyclohexane, methylcyclohexane, n-hexane, n-heptane, benzene, toluene, toluene-ethanol mixed solvent, xylene, ethylbenzene, tetrahydrofuran and the like. These solvents may be used alone or in combination of two or more.
When a laminate is produced by solvent coating, the concentration in the solution of the hydrogenated block copolymer of the present invention or the composition containing the hydrogenated block copolymer of the present invention depends on the ease of coating and the production of the solution. From the viewpoint of easiness and easiness of drying, it is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and even more preferably 5 to 30% by mass.

[the film]
The film of the invention includes the molded article of the invention.
The film of the present invention uses the hydrogenated block copolymer of the present invention or a composition containing the hydrogenated block copolymer of the present invention, and consists of a single layer.
The film of the present invention may be composed only of the hydrogenated block copolymer of the present invention, or may contain other than the hydrogenated block copolymer, such as the copolymer composition of the present invention. , preferably composed only of the hydrogenated block copolymer of the present invention.
The film of the present invention can be formed by various methods, and its shape is not particularly limited. The molding method includes, for example, blow molding, press molding, extrusion molding, or the molding methods mentioned in the above-described laminate manufacturing method.
The films of the present invention also include protective films. The protective film of the present invention comprises the laminate of the present invention or the film of the present invention. The protective film is, if necessary, a form in which a release liner is attached to the adhesive surface for the purpose of protecting the adhesive surface (the surface of the adhesive layer that is attached to the adherend) (protective film with release liner form).
As the release liner, paper, synthetic resin film or the like can be used, and synthetic resin film is preferably used because of its excellent surface smoothness. The thickness of the release liner can be, for example, 5 μm to 200 μm, preferably 10 μm to 100 μm. The surface of the release liner to be bonded to the adhesive layer is coated with a conventionally known release agent (e.g., silicone-based, fluorine-based, long-chain alkyl-based, fatty acid amide-based, etc.) or silica powder, etc., to release or Antifouling treatment may be applied.

[Fibers, non-woven fabrics]
The fibers and nonwoven fabrics of the present invention use the hydrogenated block copolymer of the present invention or the hydrogenated block copolymer composition of the present invention.
The fiber and non-woven fabric of the present invention may be composed only of the hydrogenated block copolymer of the present invention, and may contain other than the hydrogenated block copolymer, such as the copolymer composition of the present invention. However, it is preferable that it is composed only of the hydrogenated block copolymer of the present invention.
The method for producing the fiber and nonwoven fabric of the present invention is not particularly limited, but from the viewpoint of the strength of the fiber and nonwoven fabric, the denseness of the nonwoven fabric, quality, and cost, the meltblowing method or the spunbond method is preferable, and the method is finer and thinner. , the melt blow method is more preferable from the viewpoint of the denseness of the nonwoven fabric.
Moreover, the spunbond method is preferable from the viewpoints of high uniformity (pattern density, openability), air permeability, little fluffiness, resistance to fraying of the cut surface, and productivity.

[Decorative molding materials]
The decorative molding material of the present invention includes the laminate, film, fiber or nonwoven fabric of the present invention.
The thickness of the decorative molding material of the present invention can be appropriately set, but is preferably 10 to 1000 μm from the viewpoint of the strength and adhesive strength of the decorative molding material.

Since the decorative molding material of the present invention is excellent in moldability, it is possible to easily produce a decorative molded product by molding using a known press molding machine, for example. As a method for producing a decorative molded product, for example, after heating the upper mold and lower mold of a molding machine to 80 to 180 ° C., the decorative molding material of the present invention and the thermosetting molding material are placed on the lower mold. are charged in a layered manner, the mold is closed, thermocompression molding is performed at a pressure of 10 to 120 kg/cm ² for 30 seconds to 20 minutes, the resin is cured, and the mold is removed to obtain a decorated molded product. method.
A decorated molded product can also be obtained by a method in which the decorative molding material of the present invention is preformed so as to conform to the shape inside the mold, is brought into close contact with the inside surface of the mold, and then injected resin is injected into the mold. be able to.

[Adhesive]
The pressure sensitive adhesive of the present invention uses the hydrogenated block copolymer of the present invention or the hydrogenated block copolymer composition of the present invention.
The amount of application to the adherend can be appropriately set according to various conditions such as the type of adherend and the bonding atmosphere (temperature, humidity, etc.). The method of applying the adhesive of the present invention to an adherend includes, for example, a method of applying a solution in which the adhesive is dissolved in an organic solvent with a brush or a roll (solution coating), is heated and melted and coated with a hot gun (hot melt coating).
When the adhesive contains a polyolefin resin, the mass ratio of the hydrogenated block copolymer to the polyolefin resin [hydrogenated block copolymer/polyolefin resin] is preferably from 40/60 to 95/5, and from 50/50 to 90/10 is more preferred.

[Elastic member]
The elastic member of the present invention includes the molded article of the present invention.
The stretchable member of the present invention is a stretchable member containing the hydrogenated block copolymer of the present invention.
The elastic member may contain optional components other than the hydrogenated block copolymer. Examples of such optional components include polystyrene resins and softening agents.
Softening agents include, for example, hydrocarbon oils such as paraffinic, naphthenic, and aromatic oils; vegetable oils such as peanut oil and rosin; phosphate ester; low molecular weight polyethylene glycol; liquid paraffin; low molecular weight polyethylene, ethylene-α - Known softeners such as hydrocarbon-based synthetic oils such as olefin copolymer oligomer, liquid polybutene, liquid polyisoprene or its hydrogenated products, liquid polybutadiene or its hydrogenated products can be used. These may be used alone or in combination of two or more. Among them, paraffinic hydrocarbon oils and hydrocarbon synthetic oils such as ethylene-α-olefin copolymer oligomers are preferably used as softeners.
When the elastic member contains a softening agent, the mass ratio of the hydrogenated block copolymer to the softening agent [hydrogenated block copolymer/polyolefin resin] is preferably 40/60 to 95/5, and 50/50 to 90. /10 is more preferred.

[Aqueous emulsion]
The aqueous emulsion of the present invention uses the hydrogenated block copolymer of the present invention or the hydrogenated block copolymer composition of the present invention.
The emulsion may contain optional components other than the hydrogenated block copolymer. Examples of such optional components include surfactants, stabilizers, neutralizers, cross-linking agents, and the like.
The content of the hydrogenated block copolymer in the emulsion is preferably 10 to 90% by mass, more preferably 20 to 80% by mass.
A thin-film molded article can be obtained by forming a coating film of the aqueous emulsion of the present invention on the surface of an object to be coated, such as a glass plate, and drying the film.

[Viscosity index improver]
The viscosity index improver of the present invention uses the hydrogenated block copolymer of the present invention or the hydrogenated block copolymer composition of the present invention.
A viscosity index improver has the effect of improving the viscosity index of an oil composition containing a base oil, such as a lubricating oil.
The content of the hydrogenated block copolymer of the present invention in the viscosity index improver is preferably 100% by mass.
The viscosity index content in the oil composition is preferably 0.1 to 20.0% by mass, more preferably 0.5 to 10.0% by mass.
The content of the base oil in the oil composition is preferably 80.0-99.9% by mass, more preferably 90.0-10.0% by mass.

[Sealant]
The sealant of the present invention uses the hydrogenated block copolymer of the present invention or the hydrogenated block copolymer composition of the present invention.
The sealant of the present invention may contain the hydrogenated block copolymer of the present invention, a softening agent, a tackifying resin, other resins, various additives, and the like.
Examples of softening agents include paraffinic, naphthenic and aromatic process oils; phthalic acid derivatives such as dioctyl phthalate and dibutyl phthalate; white oils; mineral oils; liquid co-oligomers of ethylene and α-olefin; Polybutene; low molecular weight polyisobutylene; liquid polydienes such as liquid polybutadiene, liquid polyisoprene, liquid polyisoprene/butadiene copolymer, liquid styrene/butadiene copolymer, liquid styrene/isoprene copolymer, and hydrogenated products thereof; be done.
Tackifier resins include, for example, gum rosin, tall oil rosin, wood rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, glycerol esters thereof, rosin esters such as pentaerythritol esters, and other rosin resins; α-pinene, Terpene resins such as β-pinene, dipentene, etc. as main constituents, aromatic modified terpene resins, hydrogenated terpene resins, terpene resins such as terpene phenolic resins; (hydrogenated) aliphatic (C5) petroleum resins, (hydrogenated ) Aromatic (C9) petroleum resin, (hydrogenated) copolymer (C5/C9) petroleum resin, (hydrogenated) dicyclopentadiene petroleum resin, hydrogenated alicyclic saturated hydrocarbon resin, etc. petroleum resins that may be used; poly α-methylstyrene, α-methylstyrene/styrene copolymer, styrene monomer/aliphatic monomer copolymer, styrene monomer/α-methylstyrene/aliphatic monomer copolymer Synthetic resins such as coalescence, styrene-based monomer copolymers, styrene-based monomers/aromatic monomer copolymers other than styrene-based monomers, coumarone-indene-based resins, phenolic resins, and xylene resins. be done.
The content of the hydrogenated block copolymer of the present invention in the sealant is preferably 1 to 50% by mass, more preferably 5 to 40% by mass.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples.
The production of 1,3,7-octatriene was carried out under an inert gas atmosphere such as nitrogen and argon, unless otherwise specified.
Unless otherwise specified, all chemical solutions were used after replacing the dissolved gas with an inert gas and removing the antioxidant and water.
2,7-octadien-1-ol with a purity of 99.54% manufactured by Kuraray Co., Ltd. was used as the starting material for the production of 1,3,7-octatriene.

[Production Example 1] Production of 1,3,7-octatriene <Acetylation reaction of 2,7-octadien-1-ol>
A pressure vessel equipped with a thermometer, a nitrogen inlet, a dropping funnel and a stirrer was prepared. After replacing the inside with nitrogen, 75.04 kg of 2,7-octadien-1-ol, 90.32 kg of triethylamine, and 3.63 kg of 4-dimethylaminopyridine were sequentially charged, and then a dry ice acetone bath was used while stirring at 140 rpm. Then, the mixture was cooled to -40°C to obtain a mixed liquid. On the other hand, a dropping funnel was charged with 91.08 kg of acetic anhydride, and the acetic anhydride was added dropwise over 1 hour so that the liquid temperature of the mixture was maintained at -50 to -30°C.
After completion of dropping, the reaction was continued for 1 hour, and 35.00 kg of distilled water was added to stop the reaction. The organic phase was collected and washed successively with 1 L of 5% hydrochloric acid twice, 1 L of saturated sodium bicarbonate solution twice, 50 L of distilled water once, and 50 L of saturated sodium chloride solution once. After dehydration by adding 8.50 kg of anhydrous sodium sulfate to the organic phase thus obtained, the anhydrous sodium sulfate was filtered off to recover the organic phase.
92.56 kg (92.5% yield) of 1-acetoxy-2,7-octadiene was obtained from the organic phase.

<Dereaction of 1-acetoxy-2,7-octadiene>
1-acetoxy-2,7-octadiene obtained by the above method was replaced with nitrogen in a vacuum distillation apparatus equipped with a Claisen tube distillation head, a stirrer and a thermometer connected to a receiver via a Liebig condenser60. 29 kg, 1.33 kg of palladium acetate and 6.24 kg of triphenylphosphine were charged. While stirring at 200 rpm, the internal pressure was controlled to 1.52 to 1.35 kPaA using a constant pressure reduction device, and the distillate was recovered while heating the liquid temperature to 90°C. After removing 0.21 kg at the initial stage of distillation, 39.99 kg distilled thereafter was recovered.
The recovered fraction was washed with 25 L of 0.2 mol/L aqueous sodium hydroxide solution three times, once with 25 L of distilled water, and once with 25 L of saturated sodium chloride aqueous solution, in this order. After 2.5 kg of anhydrous sodium sulfate was added to the organic phase to dry it, the anhydrous sodium sulfate was removed by filtration to recover the organic layer.
31.85 kg of the organic layer was charged into a distillation apparatus having an inner diameter of 150 mm and a height of 2 m filled with McMahon packing. A fraction was collected at a reflux ratio of 2 at 79.1 to 60.3° C. under the condition of 22.1 to 13.0 kPaA to obtain 1,3,7-octatriene.

Hereinafter, the production of copolymers was carried out under an inert gas atmosphere such as nitrogen and argon, unless otherwise specified.
In addition, the following reagents were used in Examples and Comparative Examples.
Styrene used was obtained by removing moisture and a polymerization inhibitor from styrene (containing a stabilizer) manufactured by Wako Pure Chemical Industries, Ltd. with neutral activated alumina, and replacing the dissolved gas with argon gas.
The butadiene used was obtained by purifying butadiene manufactured by JSR Corporation with molecular sieves 3A and neutral activated alumina, and further bubbling with nitrogen gas.
The isoprene used was obtained by purifying isoprene (containing a stabilizer) manufactured by Wako Pure Chemical Industries, Ltd. with molecular sieves 3A and neutral activated alumina, and further bubbling with nitrogen gas.
Cyclohexane used was obtained by dehydrating cyclohexane (not containing a stabilizer) manufactured by Wako Pure Chemical Industries, Ltd. with Molecular Sieves 3A and further bubbling with nitrogen gas.
As sec-butyllithium, a cyclohexane solution of sec-butyllithium manufactured by Asia Lithium Co., Ltd. was adjusted to a concentration of 1.26 mmol/g using the above cyclohexane.
Tetrahydrofuran and N,N,N',N'-tetramethylethylenediamine used were those manufactured by Wako Pure Chemical Industries, Ltd., dehydrated with neutral activated alumina, and further bubbled with argon gas.

Further, the conversion rate and binding mode of 1,3,7-octatriene were determined by the following measurements.

<Measurement of conversion rate>
1.00 g of ethylene glycol dimethyl ether was added to 5.00 g of the polymerization start liquid and 5.00 g of the polymerization termination liquid obtained after the polymerization reaction was completed, and the mixture was analyzed by gas chromatography under the following measurement conditions. did.
In addition, "relative area ratio of 1,3,7-octatriene and ethylene glycol dimethyl ether at 0 hours from the start of the polymerization reaction" and "relative ratio of unreacted 1,3,7-octatriene and ethylene glycol dimethyl ether after completion of the polymerization reaction From the area ratio”, the conversion rate (%) of 1,3,7-octatriene was calculated based on the following formula 1 and was 99.9%.

(Gas chromatography measurement conditions)
Apparatus: "GC-14B" manufactured by Shimadzu Corporation
Column: “Rxi-5ms” manufactured by Restek Corporation (inner diameter 0.25 mm, length 30 m, film thickness 0.25 μm)
Carrier gas: Helium (140.0 kPaG) was passed at a flow rate of 1.50 mL/min.
Sample injection volume: 0.1 μL of drug solution was injected at a split ratio of 50/1.
Detector: FID
Detector temperature: 280°C
Vaporization chamber temperature: 280°C
Temperature rising conditions: After holding at 40° C. for 10 minutes, the temperature was raised to 250° C. at 20° C./min and held for 5 minutes.

[Example 1]
<Production of block copolymer>
(Manufacture of styrene block)
After purging the inside of a 200 L capacity SUS316 (registered trademark) autoclave equipped with a thermometer, an electric heater, an electromagnetic induction stirrer, a chemical inlet, and a sampling inlet, with argon, 62.4 kg of cyclohexane was charged. Subsequently, after the internal pressure was adjusted to 0.1 MPaG with argon, the temperature was raised to 50° C. over 30 minutes while stirring at 250 rpm. 0.1520 kg of a cyclohexane solution containing 10.5% by mass of sec-butyllithium was charged under an argon stream. Subsequently, 1.556 kg of styrene (1) was charged in less than 0.1 hour, and the internal pressure was adjusted to 0.15 MPaG with argon. The time point at which the charging was started was defined as 0 hour of the start of the polymerization reaction, and the reaction was carried out for 1 hour while controlling the liquid temperature to be 50±2°C. This produced a styrene block.

(Production of diblock copolymer)
Subsequently, 14.038 kg of 1,3,7-octatriene obtained in Production Example 1 was charged as a diene-based monomer into the autoclave in which the styrene block was produced in less than 0.1 hour, and the internal pressure was reduced to 0 with argon. .20 MPaG.
The diene polymerization reaction was started at 0 hours, and the reaction was continued for 5 hours while controlling the liquid temperature to 50°C. As a result, a diblock copolymer in which the diene block was bonded to the styrene block was produced.

(Production of triblock copolymer)
Subsequently, 0.67 kg of a cyclohexane solution containing 0.019 kg of phenyl benzoate as a coupling agent was charged into the autoclave in which the diblock copolymer was produced in less than 0.1 hour, and the internal pressure was reduced to 0.00 by argon. 3 MPaG. The time point at which the charging was started was defined as 0 hour from the start of the polymerization reaction, and the reaction was carried out for 2 hours while controlling the liquid temperature to be 50°C. As a result, the end of the diene block was bound to the coupling agent to produce a triblock copolymer having a BAB structure (referred to as copolymer (I-1)).
<Production of hydride>
(Preparation of hydrogenation catalyst)
4.47 kg of bis(2-ethylhexanoic acid) nickel (II) 2-ethylhexanoic acid solution (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 50.7 kg of cyclohexane in a 100 L nitrogen-substituted SUS reactor. After that, 5.6 kg of triisobutylaluminum (manufactured by Nippon Alkyl Aluminum Co., Ltd.) was added over 30 minutes and stirred for 30 minutes to prepare a hydrogenation catalyst, which was used in the following hydrogenation reaction.

(Hydrogenation reaction)
First, the inside of the autoclave containing the cyclohexane solution containing the copolymer (I-1) was replaced with hydrogen gas, pressurized to 0.2 MPaG with hydrogen gas, and then heated to a liquid temperature of 75°C. .
Thereafter, a hydrogenation catalyst corresponding to 150 ppm by mass of nickel metal was added to the copolymer to adjust the internal pressure to 0.98 MPaG. The time when the hydrogenation catalyst was first charged is 0 hours, 150 mass ppm as nickel metal at 0 hours, 150 mass ppm as nickel metal at 2 hours, 150 mass ppm as nickel metal at 4 hours, 6 hours as nickel metal. 150 ppm by mass, further reacted in 2 hours after the catalyst was charged in the 6th hour to obtain a hydride. The total amount of hydrogenation catalyst was 600 ppm by mass, and the hydrogenation reaction time was 8 hours after the introduction of the first hydrogenation catalyst.
After allowing the reaction solution to cool and release pressure, distilled water containing 30% by mass of hydrogen peroxide and citric acid monohydrate was added, and the mixture was stirred at 50° C. to remove the hydrogenation catalyst. 100 kg of methanol was added to a cyclohexane solution containing the obtained copolymer (referred to as copolymer (i-1)) to precipitate copolymer (i-1). Then, it was dried in a vacuum dryer under 0.1 kPaA while heating at 50° C. for 12 hours to obtain a solid copolymer (i-1). Table 1 shows the amount of each reagent used.

The obtained styrene block, the peak top molecular weight (Mp) of the diblock copolymer, and the obtained copolymer (i-1) peak top molecular weight (Mp) and molecular weight distribution (Mw / Mn), and hydrogenation Percentages were determined according to the following measurements.
From the peak top molecular weights (Mp) of the styrene block and diblock copolymers, polymer block (A) (1,3,7-octatriene block: diene block) and polymer block (B) (styrene block) The peak top molecular weight (Mp) of was obtained. As a result, the peak top molecular weight (Mp) of polymer block (A) was 69,000, and the peak top molecular weight (Mp) of polymer block (B) was 7,900.
Table 1 shows the peak top molecular weight (Mp) and hydrogenation rate of the copolymer (i-1). The molecular weight distribution (Mw/Mn) of copolymer (i-1) was 1.38.

<Measurement of peak top molecular weight (Mp) and molecular weight distribution (Mw/Mn)>
60.0 g of tetrahydrofuran was added to 0.10 g of the obtained styrene block, 0.10 g of the diblock copolymer, 0.10 g of the triblock copolymer, and 0.10 g of the copolymer (i-1), and the mixture was uniformly mixed. A solution is prepared, and this solution is analyzed by gel permeation chromatography under the following measurement conditions, and the peak top molecular weight (Mp), weight average molecular weight number (Mw), and number average molecular weight (Mn) are obtained in terms of standard polystyrene. , the molecular weight distribution (Mw/Mn) was calculated.

(Gel permeation chromatography measurement conditions)
Apparatus: "HLC-8320GPC EcoSEC" manufactured by Tosoh Corporation
Column: Two "TSKgel Super Multipore HZ-M" manufactured by Tosoh Corporation (inner diameter 4.6 mm, length 150 mm) were used by connecting them in series.
Eluent: Tetrahydrofuran was passed at a flow rate of 0.35 mL/min.
Sample injection volume: 10 μL
Detector: RI
Detector temperature: 40°C

<Measurement of hydrogenation rate>
To 150 mg of the unhydrogenated block copolymer (copolymer (I-1)) and 150 mg of the hydrogenated block copolymer (copolymer (i-1)), 1.00 g of deuterated chloroform was added to obtain a uniform mixture. A solution was prepared, and this solution was subjected to ¹ H-NMR measurement under the following measurement conditions.
( ¹ H-NMR measurement conditions)
Device: "JNM-LA500" manufactured by JEOL Ltd.
Reference substance: Tetramethylsilane Measurement temperature: 25°C
Accumulated times: 254 times

The number of moles of double bonds of non-hydrogenated 1,3,7-octatriene with respect to the total number of moles of styrene forming the styrene block in the block copolymer before hydrogenation, and the hydrogenated block copolymer after hydrogenation Derived from 1,3,7-octatriene from the number of moles of double bonds in unhydrogenated 1,3,7-octatriene relative to the total number of moles of styrene forming the styrene block in the polymer (hydride) The percent hydrogenation was calculated as the percentage of hydrogenated double bonds. Table 1 shows the results.

<Preparation of compact>
In order to measure the peak top of tan δ, peak top temperature, and hardness of the molded body, press molding equipment "NF-50T" (manufactured by Shindo Kinzoku Kogyo Co., Ltd.) at a temperature of 230 ° C. and a pressure of 10 MPaG for 3 minutes. A sheet of a hydrogenated block copolymer having a thickness of 1.0 mm was prepared, and the sheet was cut into a disc shape having a diameter of 8 mm to prepare a compact (I-1), and tan δ was measured.
Under the same conditions, a 2.0 mm-thick sheet-like formed body (I-1) of the hydrogenated block copolymer was produced and used for hardness measurement.

[Example 2]
<Production of block copolymer>
(Manufacture of styrene block body)
After purging the inside of a 200 L capacity SUS316 (registered trademark) autoclave equipped with a thermometer, an electric heater, an electromagnetic induction stirrer, a chemical inlet, and a sampling inlet, with argon, 62.4 kg of cyclohexane was charged. Subsequently, after the internal pressure was adjusted to 0.1 MPaG with argon, the temperature was raised to 50° C. over 30 minutes while stirring at 250 rpm. 0.0549 kg of a cyclohexane solution containing 10.5% by mass of sec-butyllithium was charged under an argon stream. Subsequently, 0.465 kg of styrene (1) was charged in a time shorter than 0.1 hour, and the internal pressure was adjusted to 0.15 MPaG with argon. The time point at which the charging was started was defined as 0 hour of the start of the polymerization reaction, and the reaction was carried out for 1 hour while controlling the liquid temperature to be 50±2°C. This produced a styrene block.

(Production of diblock copolymer)
0.0271 kg of tetrahydrofuran (THF) was charged into the autoclave in which the styrene block was produced. Immediately thereafter, 13.700 kg of 1,3,7-octatriene obtained in Production Example 1 was charged as a diene-based monomer in less than 0.1 hour, and the internal pressure was adjusted to 0.20 MPaG with argon.
The diene polymerization reaction was started at 0 hours, and the reaction was continued for 5 hours while controlling the liquid temperature to 50°C. As a result, a diblock copolymer having a diene block bonded to a styrene block was produced.

(Production of triblock copolymer)
Subsequently, 1.398 kg of styrene (2) was charged in less than 0.1 hour, and the internal pressure was adjusted to 0.15 MPaG with argon. The time point at which the charging was started was defined as 0 hour from the start of the polymerization reaction, and the reaction was carried out for 2 hours while controlling the liquid temperature to be 50°C. As a result, the first styrene block, the diene-based block and the second styrene block were combined to produce a triblock copolymer having a BAB structure.
Thereafter, 0.030 kgg (0.075 mol as ethanol) of a cyclohexane solution containing 2.50 mmol/g of ethanol was added to terminate the polymerization reaction, resulting in a triblock copolymer (referred to as copolymer (I-2)). ) was obtained.

<Production of hydride>
In Example 1, except that the copolymer (I-2) was used instead of the copolymer (I-1), a hydrogenation reaction was carried out in the same manner to obtain a hydride (copolymer (i-2) ) was obtained. The peak top molecular weight (Mp), molecular weight distribution (Mw/Mn), and hydrogenation rate of the obtained copolymer (i-2) were determined in the same manner as in Example 1. Table 1 shows the amount of each reagent used, the degree of hydrogenation, and the peak top molecular weight (Mp) of the hydride. The molecular weight distribution (Mw/Mn) of the hydride was 2.04.

<Preparation of compact>
Molded article (I-2) was obtained in the same manner as in Example 1 except that copolymer (i-2) was used instead of copolymer (i-1).

[Examples 3 and 4]
In the production of the triblock copolymer of Example 2, the procedure was the same except that 1,3,7-octatriene obtained in Production Example 1 and butadiene or isoprene were charged as shown in Table 1 as conjugated diene monomers. Then, hydrides (Example 3: copolymer (i-3), Example 4: copolymer (i-4)) were obtained.
The peak top molecular weight (Mp), molecular weight distribution (Mw/Mn), and hydrogenation rate of the resulting copolymer (i-3) and copolymer (i-4) were determined in the same manner as in Example 1. Table 1 shows the amount of each reagent used, the degree of hydrogenation, and the peak top molecular weight (Mp) of the hydride. The molecular weight distribution (Mw/Mn) of the hydride was 1.64 in the copolymer (i-3) of Example 3, and 1.64 in the copolymer (i-4) of Example 4. was 45.
In terms of the hydrogenation rate, the ratio of non-hydrogenated 1,3,7-octatriene and diene such as butadiene and isoprene to the total number of moles of styrene forming the styrene block in the block copolymer before hydrogenation. Unhydrogenated 1,3,7-octatriene, butadiene and isoprene relative to the number of moles of heavy bonds and the total number of moles of styrene forming styrene blocks in the hydrogenated block copolymer (hydride) after hydrogenation From the number of moles of double bonds in dienes such as Calculated.
Next, molded article (I-3) was obtained in the same manner as in Example 2 except that copolymer (i-3) and copolymer (i-4) were used instead of copolymer (i-2). And a compact (I-4) was obtained.

[Comparative Example 1]
<Production of styrene block body>
After purging the inside of a 200 L capacity SUS316 (registered trademark) autoclave equipped with a thermometer, an electric heater, an electromagnetic induction stirrer, a chemical feed port, and a sampling port, with argon, 62.4 kg of cyclohexane and sec-butyllithium were added. 0.1631 kg (0.267 mol as sec-butyllithium) of cyclohexane solution containing 10.5% by mass was charged.
After heating the inside of the vessel to 50° C., 2.080 kg of styrene (1) was added and reacted for 30 minutes. This produced a styrene block.

<Production of diblock copolymer>
The temperature inside the autoclave in which the styrene blocks were produced was lowered to 40° C., 0.3603 kg of tetrahydrofuran was added, and then 16.64 kg of isoprene was added over 5 hours and reacted for 1 hour. As a result, a diblock copolymer having a diene block bonded to a styrene block was produced.

<Production of triblock copolymer>
Subsequently, the inside of the container was heated to 50° C., 2.080 kg of styrene (2) was added and polymerized for 30 minutes, and methanol was added to stop the reaction, thereby forming the first styrene block and the diene block. A triblock copolymer (referred to as copolymer (II-1)) having a BAB structure was produced by bonding with the second styrene block.
Thereafter, 0.118 kg (0.294 mol as ethanol) of a cyclohexane solution containing 2.50 mmol/g of ethanol was added to terminate the polymerization reaction, thereby obtaining a cyclohexane solution containing copolymer (II-1).

<Production of hydride>
After heating the cyclohexane solution containing the copolymer (II-1) to 50° C. and pressurizing it to a hydrogen pressure of 1 MPaA, a Ziegler catalyst (hydrogenation catalyst) formed from nickel octylate and trimethylaluminum was placed in a hydrogen atmosphere. The temperature was raised to 80° C. by the heat of reaction, and the reaction was continued until no more hydrogen was absorbed.
After allowing the reaction solution to cool and release pressure, distilled water containing 30% by mass of hydrogen peroxide and citric acid monohydrate was added, and the mixture was stirred at 50° C. to remove the hydrogenation catalyst. 50 kg of methanol was added to a cyclohexane solution containing the obtained copolymer (referred to as copolymer (ii-1)) to precipitate copolymer (ii-1). Then, it was dried in a vacuum dryer for 12 hours while heating at 50° C. under 0.1 kPaA to obtain a solid copolymer (ii-1). Table 1 shows the amount of each reagent used.
Table 1 shows the amount of each reagent used, the degree of hydrogenation, and the peak top molecular weight (Mp) of the hydride.
In the hydrogenation rate, the number of moles of double bonds of dienes such as non-hydrogenated butadiene and isoprene with respect to the total number of moles of styrene forming the styrene block in the block copolymer before hydrogenation, and the hydrogenation Conjugated dienes such as butadiene and isoprene from the number of moles of double bonds in dienes such as unhydrogenated butadiene and isoprene relative to the total number of moles of styrene forming the styrene block in the subsequent hydrogenated block copolymer (hydride) The hydrogenation rate was calculated as the percentage of hydrogenated double bonds derived from the compound.

<Preparation of compact>
Molded article (II-1) was obtained in the same manner as in Example 1, except that copolymer (ii-1) was used instead of copolymer (i-1).

[Comparative Examples 2 to 4]
Comparative Example 2 was carried out in the same manner as in Comparative Example 1, except that butadiene was added together with isoprene during the production of the diblock copolymer, and the amount of each reagent used was changed as shown in Table 1. A compact (II-2) was obtained.
For Comparative Example 3, in the production of the diblock copolymer, tetrahydrofuran was not used, butadiene was added together with isoprene, and the amount of each reagent used was changed as shown in Table 1. A compact (II-3) was obtained in the same manner as above.
Comparative Example 4 was carried out in the same manner as in Comparative Example 1 except that butadiene was added instead of isoprene and the amount of each reagent used was changed as shown in Table 1, to obtain molded article (II-4). rice field.
The hydrogenation rates and the peak top molecular weights (Mp) of the hydrides in Comparative Examples 2 to 4 were obtained in the same manner as in Comparative Example 1.
Table 1 shows the amount of each reagent used, the degree of hydrogenation, and the peak top molecular weight (Mp) of the hydride.

[Example 5]
<Production of block copolymer and production of hydride>
A copolymer (i-1) was obtained in the same manner as in Example 1.
<Production of resin composition>
70 parts by mass of the obtained copolymer (i-1) and 30 parts by mass of homopolypropylene "Novatec EA7A" (manufactured by Japan Polypropylene Co., Ltd.) as a polyolefin resin were placed in a "laboplastomill" ( R60 type mixer, roller type blade, manufactured by Toyo Seiki), and after 1 minute, change the rotation speed to 100 rpm, knead for 3 minutes, and make a resin composition (I -5) was obtained.
<Preparation of compact>
The obtained resin composition (I-5) is pressurized for 3 minutes at a temperature of 230° C. and a pressure of 10 MPaG using a press molding apparatus “NF-50T” (manufactured by Shindo Metal Industry Co., Ltd.) to form a sheet. A compact (I-5) (length 150.0 mm, width 150.0 mm, thickness 2.0 mm) was obtained.

[Example 6]
A molding (I-6) was obtained in the same manner as in Example 5 except that the copolymer (i-2) obtained in Example 2 was used.

[Comparative Examples 5 to 8]
Using the copolymers obtained in Comparative Examples 1 to 4 (Comparative Example 5: Copolymer (ii-1), Comparative Example 6: Copolymer (ii-2), Comparative Example 7: Copolymer ( ii-3), Comparative Example 8: Copolymer (ii-4)) was performed in the same manner as in Example 5, and a molded article (Comparative Example 5: molded article (II-5), Comparative Example 6: molded article ( II-6), Comparative Example 7: molded article (II-7), Comparative Example 8: molded article (II-8)).

[Example 7]
<Production of block copolymer and production of hydride>
A copolymer (i-1) was obtained in the same manner as in Example 1.
<Preparation of Molded Body for Medical Tubing>
65 parts by mass of the obtained copolymer (i-1) and 35 parts by mass of a propylene-based random copolymer "Purell RP373R" (manufactured by Lyondell Basel Co., Ltd.) as a polypropylene-based resin were melted at a resin temperature of 230 ° C. A resin composition (I-7) was prepared by axial kneading. Subsequently, the obtained resin composition (I-7) was molded at 220° C. using a single screw extruder and a tube die, and after confirming the moldability, it was rapidly cooled in a cooling bath at a water temperature of 25° C. A compact (I-7) (medical tube) having a diameter of 3.0 mm and an outer diameter of 4.0 mm was obtained.

[Example 8]
<Production of block copolymer and production of hydride>
A copolymer (i-1) was obtained in the same manner as in Example 1.
<Preparation of compact for liquid packaging material>
As materials for the inner layer, 100 parts by mass of propylene-butene random copolymer "SFC-750D" (manufactured by LOTTE CHEMICAL), 43 parts by mass of the obtained copolymer (i-1), and as materials for the intermediate layer, 100 parts by mass of propylene-ethylene random copolymer "SB-520Y" (manufactured by LOTTE CHEMICAL), 54 parts by mass of obtained copolymer (i-1), homopolypropylene "PT-100" as material for outer layer (manufactured by LCY CHEMICAL)) 100 parts by mass, 5 parts by mass of the obtained copolymer (i-1), respectively, using a water-cooled downward inflation molding machine, resin temperature 200 ° C., cooling water temperature 20 ° C., Molding was performed at a line speed of 10 m/min to obtain a laminate (film) having a thickness of 200 μm. The thickness of each layer was 20 μm for the inner layer, 130 μm for the intermediate layer, and 50 μm for the outer layer.
The laminate was cut into a size of 15 cm × 9 cm, two of which were used to overlap the inner layers, and three of the four sides were heated under the conditions of a temperature of 140 ° C., a pressure of 0.4 MPaG, and a heating time of 1 second. After heat-sealing, 100 ml of water is injected from one side where the mouth is open, and then the one side is heat-sealed under the same conditions as above to form a liquid packaging container with an internal capacity of 100 ml. body (I-8) was obtained.

[Example 9]
<Production of block copolymer and production of hydride>
A copolymer (i-1) was obtained in the same manner as in Example 1.
<Production of sealant>
100 parts by mass of the resulting copolymer (i-1), 300 parts by mass of a softening agent "Diana Process Oil PW-90" (hydrogenated paraffinic oil, manufactured by Idemitsu Kosan Co., Ltd.), and a hydrogenated alicyclic ring as a tackifying resin A sealant (resin composition) is produced by mixing 120 parts by mass of a group-based hydrocarbon resin "Escoretz ECR-227E" (manufactured by Exxon Mobil) at a temperature of 200 to 230 ° C. for 2 hours using a sigma blade type kneader. did.
<Preparation of compact>
The obtained sealant is compression molded at a temperature of 200° C. and a pressure of 10 MPaG for 2 minutes with a press molding machine “NF-50T” (manufactured by Shindo Metal Industry Co., Ltd.), and then cooled at 1 MPaG for 1.5 minutes. A sheet-like compact (I-9) (length 150.0 mm, width 150.0 mm, thickness 1.0 mm) was obtained.

[Example 10]
<Production of block copolymer and production of hydride>
A copolymer (i-1) was obtained in the same manner as in Example 1.
<Production of composition>
The obtained copolymer (i-1) was premixed with a super mixer "SMV-100" (manufactured by Kawata Co., Ltd.), and then a twin-screw extruder "TEM-35B" (manufactured by Toshiba Machine Co., Ltd.) was used. The mixture was melt-kneaded under conditions of a temperature of 230° C. and a screw rotation of 200 rpm, extruded into strands, and cut to obtain a thermoplastic polymer composition in the form of pellets.
<Production of laminate>
The obtained pellets of the thermoplastic polymer composition are compression molded using a compression molding machine at a temperature of 190° C. and a pressure of 1.0 MPaG for 3 minutes to form a sheet of the thermoplastic polymer composition (longitudinal 110 0 mm, width 110.0 mm, thickness 4.0 mm). The sheet and fabric (100% cotton, weight per unit area: 216 g/m ² , thickness: 0.70 mm) were compression molded for 3 minutes by a compression molding machine at a temperature of 140°C and a pressure of 1.0 MPaG to obtain a laminate. .

[Example 11]
<Production of block copolymer and production of hydride>
A copolymer (i-1) was obtained in the same manner as in Example 1.
<Production of interlayer film for laminated glass>
(Production of composition for X layer)
In the obtained copolymer (i-1), cesium tungsten oxide (manufactured by Sumitomo Metal Mining Co., Ltd., hereinafter referred to as CWO) as a heat shielding material, Tinuvin 326 as an ultraviolet absorber, and Cyanox 2777 as an antioxidant. and Tinuvin 622SF as a light stabilizer to obtain a composition constituting the X layer. The heat shield material has a surface density of 0.25 g/m ² in the X layer, the ultraviolet absorber has a surface density in the X layer of 1.0 g/m ² , and the antioxidant has a surface density in the X layer. The density was adjusted to 0.20 g/m ² , and the light stabilizer was adjusted so that the surface density in the X layer was 1.6 g/m ² .

Incidentally, Tinuvin326 used as an ultraviolet absorber is 2-(5-chloro-2-benzotriazolyl)-6-tert-butyl-p-cresol (manufactured by Ciba Specialty Chemicals Co., Ltd.). Cyanox 2777 used as an antioxidant is 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-( It is a mixture of 1H,3H,5H)-trione and tris(2,4-di-tert-butylphenyl)phosphate (manufactured by CYTEC). Tinuvin 622SF used as a light stabilizer is a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol (manufactured by Ciba Specialty Chemicals Co., Ltd.).

Furthermore, to 100 parts by mass of TPE-1, 5 parts by mass of maleic anhydride-modified polypropylene "Umex 1010" (manufactured by Sanyo Chemical Industries, Ltd.) is added as an adhesive force adjuster with the Y layer, and the TPE is -1 was obtained as a main component for the X layer. Here, the main component means the component with the largest mass in the composition, and when a plasticizer is contained, the main component is called the main component including the plasticizer.

(Preparation of composition for Y layer)
The main components of the Y layer include a viscosity average polymerization degree of about 1100, a degree of acetalization of 68.7 mol%, a vinyl acetate unit content of 0.8 mol%, and a vinyl alcohol unit content of 30.5 mol%. Polyvinyl butyral (PVB) was used.

The above PVB-1 was mixed with Tinuvin 326 as an ultraviolet absorber to obtain a composition constituting the Y layer. The blending amount of the ultraviolet absorber was adjusted so that the surface density of the Y layer was 5.1 g/m ² . __

<Preparation of intermediate film>
The composition for the X layer is introduced into a T die (multi-manifold type: width 500 mm) at 205 ° C. using a 50 mmφ vented single screw extruder at a temperature of 210 ° C. and a discharge rate of 4 kg / h. The composition was introduced into the T-die using a 65 mmφ vented single-screw extruder under conditions of 205° C. and a discharge rate of 24 kg/h. The molded product coextruded from the T die is nipped by two metal mirror surface rolls, one of which is set at 50 ° C. and the other at 60 ° C., and is taken up at a take-up speed of 1.2 m / min, Y layer / X layer / Y layer An intermediate film (thickness: 760 μm) having a three-layer structure (thickness: 330 μm/thickness: 100 μm/thickness: 330 μm) was molded. The molded intermediate film was passed through a metal embossing roll (45 degrees tilt angle with respect to the flow direction of the laminate, 150 μm pitch, 50 μm width of the top of the convex portion, 30 μm width of the bottom of the concave portion, height from the bottom of the concave portion to the top of the convex portion. 100 μm) and an elastic rubber roll to form embossments on one side, and then again to form embossments on the opposite side. At that time, the surface temperature of the embossing roll was set to 80° C., the surface temperature of the elastic rubber roll was set to 30° C., the linear pressure between the embossing roll and the elastic rubber roll was set to 0.1 MPaG, and the line speed was 0.5 m/min. An intermediate film was obtained.

<Production of laminated glass>
The obtained interlayer film for laminated glass is sandwiched between two sheets of commercially available green glass (length 50.0 mm x width 50.0 mm x thickness 1.6 mm), and a vacuum laminator "1522N" (manufactured by Nisshinbo Mechatronics Co., Ltd.) is used. , hot plate temperature of 165° C., evacuation time of 12 minutes, pressing pressure of 50 kPaG, and pressing time of 17 minutes to obtain a laminated glass.

[Example 12]
<Production of block copolymer and production of hydride>
A copolymer (i-1) was obtained in the same manner as in Example 1.
<Production of film>
The resulting copolymer (i-1) was added to toluene to prepare a toluene solution having a resin concentration of 30 mass %. Using a doctor blade, this toluene solution was applied to a polyethylene terephthalate (PET) film "Teijin Tetron Film G2" (manufactured by Teijin DuPont Films Ltd.) with a thickness of 50 μm, and then dried at a temperature of 110° C. for 5 minutes. A film was obtained in which an adhesive layer composed of copolymer (i-1) was formed on a PET film as a base layer. The thickness of the adhesive layer in this film was 12 µm.

[Example 13]
<Production of block copolymer, production of hydride and production of film>
A film was obtained in the same manner as in Example 12.
<Production of protective film>
The resulting film is attached to a smooth acrylic resin plate "Comoglass P" (thickness 3 mm, manufactured by Kuraray Co., Ltd.) so that the adhesive layer is in contact with the acrylic resin plate, cut to a width of 25 mm, and protected. got the film.

[Example 14]
<Production of block copolymer and production of hydride>
A copolymer (i-1) was obtained in the same manner as in Example 1.
<Production of resin composition>
Polypropylene “Prime Polypro F327” (MFR [230° C., load 2.16 kg (21 N)]: 7 g/10 min, manufactured by Prime Polymer Co., Ltd.) 42 g, maleic anhydride 160 mg, 2,5-dimethyl-2,5-dimethyl 42 mg of (tert-butylperoxy)hexane was melt-kneaded using a batch mixer at 180° C. and a screw rotation speed of 40 rpm to obtain polypropylene containing maleic anhydride groups.
Subsequently, 100 parts by mass of the obtained copolymer (i-1) and 25 parts by mass of polypropylene containing maleic anhydride groups were melt-kneaded using a batch mixer under conditions of 230° C. and a screw rotation speed of 200 rpm. , to prepare a thermoplastic elastomer composition (resin composition).
<Preparation of resin composition sheet>
The resulting thermoplastic elastomer composition was molded at a temperature of 230 using a compression press molding machine "NF-37" (manufactured by Shindo Metal Industry Co., Ltd.) using a "Teflon (registered trademark)" coated metal frame as a spacer. After compression press molding at a temperature of 18° C. and a pressure of 1.0 MPaG for 5 minutes, compression press molding was performed at a temperature of 18° C. and a pressure of 15 kgf/cm ² for 1 minute to obtain a resin composition sheet with a thickness of 1 mm. .

<Production of laminate>
Both surfaces of an aluminum plate measuring 75.0 mm long×25.0 mm wide×1.0 mm thick were washed with an aqueous surfactant solution and distilled water in this order as washing liquids, and dried. The aluminum plate, the obtained resin composition sheet, and a polyethylene terephthalate (PET) sheet having a thickness of 50.0 μm were stacked in this order to form a laminate having outer dimensions of 200.0 mm×200.0 mm and inner dimensions of 150.0 mm×150 mm. It was placed in the center of a metal spacer of 0 mm and 2.0 mm thick.
The stacked sheets and metal spacers ^were sandwiched between polytetrafluoroethylene sheets, and then sandwiched between metal plates from the outside. ² ), compression molding was performed for 3 minutes to obtain a laminate composed of PET/resin composition/aluminum plate. The copolymer (i-1) contained in the resin composition is used for the purpose of imparting the function of improving the adhesion between the PET and the aluminum plate.

[Example 15]
<Production of block copolymer and production of hydride>
A copolymer (i-1) was obtained in the same manner as in Example 1.
<Production of resin composition>
100 parts by mass of block copolymer (i-1) and 30 parts by mass of hydrogenated paraffinic process oil "Diana Process Oil PW-90" (manufactured by Idemitsu Kosan Co., Ltd.) as a softening agent were mixed at a temperature of 230 ° C. and 230 ° C. using a batch mixer. The resin composition was obtained by melt-kneading under conditions of a screw rotation speed of 200 rpm.
<Production of elastic member>
The obtained resin composition was compression molded at a temperature of 240° C. and a pressure of 10 MPaG for 3 minutes to obtain an elastic member having a thickness of about 0.5 mm.

[Example 16]
<Production of block copolymer and production of hydride>
A copolymer (i-1) was obtained in the same manner as in Example 1.
<Production of aqueous emulsion>
Protective colloid: ammonium salt of acrylic acid ester-unsaturated carboxylic acid copolymer (acrylic acid: methacrylic acid: methyl methacrylate: butyl acrylate: butyl 200 g of a 30% by mass concentration toluene solution containing 13 parts by mass of methacrylate (8:8:11:11:11 (mass ratio), weight average molecular weight: 5,000) was prepared, then 400 g of distilled water was added, and a homomixer was added. The mixture was added to a stirring tank and stirred at 10,000 rpm for 10 minutes, and then the contents were transferred to a pressurized homogenizer for further emulsification. Next, toluene and distilled water were distilled off with a rotary evaporator under conditions of 0.8 kPaA and a temperature of 60° C. to obtain an aqueous emulsion (solid concentration: 40% by mass).
<Preparation of thin compact>
A glass plate as an object to be coated was immersed in the resulting aqueous emulsion to form a coating film having a thickness of 2.4 mm on the surface of the glass plate. gone. Subsequently, this was cooled, cut into a size of 10.0 cm×10.0 cm with a cutter knife, and separated from the glass plate to obtain a thin molded product having a thickness of 100.0 μm. The process of forming and drying the above coating film was repeated 7 to 10 times, and finally, vacuum drying heat treatment was performed at 120° C. and a pressure of 0.67 kPaA for 24 hours to obtain a thin compact with a thickness of 1.0 mm.

[Example 17]
<Production of block copolymer and production of hydride>
A copolymer (i-1) was obtained in the same manner as in Example 1.
<Preparation of compact>
As a resin modifier, after dry blending 10 parts by mass of the obtained copolymer (i-1) and 90 parts by mass of modified polyphenylene ether "PPO534" (manufactured by SABIC), a twin-screw extruder "TEX-44XCT (manufactured by Japan Steel Works, Ltd.), the mixture was melt-kneaded at a cylinder temperature of 310° C. and a screw rotation speed of 200 rpm, extruded into strands, and cut to obtain a molded body containing the modified polyphenylene ether resin.

[Example 18]
<Production of block copolymer and production of hydride>
A copolymer (i-1) was obtained in the same manner as in Example 1.
<Production of oil composition>
Using the obtained copolymer (i-1) as a viscosity index improver, using a paraffin oil "Dianafresia S-32" (manufactured by Idemitsu Kosan Co., Ltd.) as a base oil, with respect to 99% by mass of these base oils 1% by mass of the copolymer (i-1) was blended. Subsequently, an oil composition was obtained by mixing for 6 hours at a temperature of 120° C. and a rotational speed of 350 rpm in a nitrogen-substituted pressure vessel.

[Example 19]
<Production of block copolymer and production of hydride>
A copolymer (i-1) was obtained in the same manner as in Example 1.
<Production of nonwoven fabric>
The obtained block copolymer (i-1) was put into an extruder and melted at a temperature of 310° C. to obtain an extruder with a pore size of 0.1. The molten resin was discharged from meltblown nozzles arranged in a row with 3mm holes at a pitch of 0.75mm, and at the same time hot air at 310°C was jetted to the molten resin, and the meltblown fibers were collected on a molding conveyor to obtain a meltblown nonwoven fabric.

[evaluation]
<Peak top of tan δ and peak top temperature>
The peak top of tan δ and the peak top temperature of the molded body were measured to evaluate the flexibility and damping property.
As a measurement device, based on JIS K7244-10 (2005), a strain-controlled dynamic viscoelasticity device "ARES-G2" (manufactured by TA Instruments) is used, and a flat plate with a diameter of 1 mm is formed. Body (I-1) to (I-4) (thickness: 1.0 mm) and molded body (II-1) to (II-4) (thickness: 1.0 mm) sandwiched, strain amount 0.1% , vibration was applied at a frequency of 1 Hz, and the temperature was raised from -70°C to 200°C at a rate of 3°C/min.
By the above test, the peak top of tan δ and the peak top temperature were obtained. The results obtained in Examples 1-4 and Comparative Examples 1-4 are shown in Table 1, and the tan δ graphs of Example 1, Comparative Example 1 and Comparative Example 2 are shown in FIGS.
The larger the peak top value of tan δ of the molded body, the more excellent the vibration damping property, and the lower the peak top temperature, the more flexibility is exhibited in the low temperature range.

<Hardness>
(1) Examples 1-4 and Comparative Examples 1-4
Three molded articles (I-1) (thickness: 2.0 mm) obtained in Example 1 were stacked to obtain a test piece having a thickness of 6 mm. For the test piece, A hardness was measured at a temperature of 23° C. in accordance with JIS K 6253-3 (2012) using a type A durometer indenter.
For Examples 2 to 4 and Comparative Examples 1 to 4, the A hardness was measured in the same manner as in Example 1.
These results are shown in Table 1.
It should be noted that the lower the hardness value, the more excellent the flexibility.
(2) Examples 5-6 and Comparative Examples 5-8
Three molded articles (I-5) (thickness: 2.0 mm) obtained in Example 5 were stacked to obtain a test piece having a thickness of 6 mm. For the test piece, using a type D durometer indenter, D hardness was measured at a temperature of 23° C. in accordance with JIS K 6253-3 (2012).
For Example 6 and Comparative Examples 5 to 8, D hardness was measured in the same manner as in Example 5.
These results are shown in Table 2.
It should be noted that the lower the hardness value, the more excellent the flexibility.

<Adhesive residue evaluation>
After rolling the protective film from the substrate layer side at a rate of 20 mm/min using a 2 kg rubber roller, the film was allowed to stand in an atmosphere of 80° C.±1° C. and humidity of 50±5% for 1 hour. Subsequently, after cooling in an environment of 25 ° C. for 0.5 hours, in accordance with JIS Z 0237 (2009), it was peeled at a peeling speed of 300 mm / min, and the adhesive residue remaining on the surface of the acrylic resin plate ( resin composition component) was visually evaluated according to the following evaluation criteria. The less adhesive residue, the more excellent the adhesive residue resistance of the resulting protective film.
A: No adhesive residue B: Less than 10% of the peeled area C: More than 10% of the peeled area

<Kinematic viscosity, viscosity index>
The kinematic viscosity and viscosity index of the oil composition were measured according to JISK2283 (2000).

From Table 1, it can be seen that the molded bodies of Examples 1 to 4 exhibit high flexibility at low temperatures because the tan δ peak top temperature is lower and the hardness is lower than that of the molded bodies of Comparative Examples 1 and 2. .
In addition, the molded bodies of Examples 1 to 4 have a higher tan δ peak top and a lower hardness than the molded bodies of Comparative Examples 3 and 4, so that they exhibit high flexibility at low temperatures and also have damping properties. I know it's good.
Furthermore, the molded bodies of Examples 5 and 6 have lower hardness than the molded bodies of Comparative Examples 5-8, indicating that they exhibit high flexibility.

Claims (17)

Molding containing a hydride of a block copolymer containing a polymer block (A) containing structural units derived from a conjugated diene and a polymer block (B) mainly containing structural units derived from an aromatic vinyl compound being a body,
the conjugated diene comprises 1,3,7-octatriene;
The polymer block (A) is a molded article containing a hydrogenated block copolymer mainly composed of structural units derived from 1,3,7-octatriene. 2. The molded article according to claim 1, wherein the polymer block (A) does not contain a structural unit derived from a conjugated diene having 12 or more carbon atoms. 3. The molded article according to claim 1, which has a hardness of 1 to 40 measured at a temperature of 23° C. according to JIS K 6253-3 (2012) type A durometer method. The mass ratio (B)/(A) of the polymer block (B) to the polymer block (A) is 1/99 or more and 50/50 or less, according to any one of claims 1 to 3. molding. Any one of claims 1 to 4, wherein the block copolymer comprises a triblock copolymer having blocks in the order of the polymer block (B), the polymer block (A), and the polymer block (B). The molded article according to k. The molded article according to any one of claims 1 to 5, wherein the block copolymer contains a structural unit derived from a coupling agent. In accordance with JIS K7244-10 (2005), strain amount 0.1%, frequency 1 Hz, measurement temperature -70 to 200 ° C., heating rate 3 ° C./min, test piece thickness 1 mm. The molded article according to any one of claims 1 to 6, which has a tan δ peak top of 1.50 or more. A laminate comprising a layer using the block copolymer hydride according to any one of claims 1 , 2, and 4 to 6 . A film using the hydride of the block copolymer according to any one of claims 1 , 2, and 4 to 6 . A fiber using the block copolymer hydride according to any one of claims 1 , 2, and 4 to 6 . A nonwoven fabric using the block copolymer hydride according to any one of claims 1 , 2, and 4 to 6 . A decorative molding material comprising the laminate according to claim 8, the film according to claim 9, the fiber according to claim 10, or the nonwoven fabric according to claim 11. A pressure-sensitive adhesive using the hydrogenated block copolymer according to any one of claims 1 , 2, and 4 to 6 . An elastic member using the hydrogenated block copolymer according to any one of claims 1 , 2, and 4 to 6 . An aqueous emulsion using the block copolymer hydride according to any one of claims 1 , 2, and 4 to 6 . A viscosity index improver using the hydrogenated block copolymer according to any one of claims 1 , 2, and 4 to 6 . A sealant using the block copolymer hydride according to any one of claims 1 , 2, and 4 to 6 .

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