JP5236417B2 - Hydrogenated block copolymer composition - Google Patents

Description

  The present invention relates to a hydrogenated block copolymer composition, which is a combination of a hydrogenated block copolymer and a rubber softener, having excellent transparency, low hardness and low rebound resilience.

  Block copolymers consisting of conjugated dienes and vinyl aromatic hydrocarbons have the same elasticity at room temperature as vulcanized natural and synthetic rubbers without vulcanization, when there are relatively few vinyl aromatic hydrocarbons. In addition, since it has the same processability as a thermoplastic resin at high temperatures, it is widely used in the fields of footwear, plastic modification, asphalt modification, adhesives and the like.

  However, block copolymers with relatively few vinyl aromatic hydrocarbons have the drawback of being poor in low resilience, although they are good in flexibility, and this is a limitation for use in applications that require impact buffering properties. Yes.

In Patent Document 1, as a flexible material, a vinyl aromatic hydrocarbon content is a random copolymer having a content of 3 to 50% by mass, a molecular weight distribution (Mw / Mn) is 10 or less, and A composition of a hydrogenated diene copolymer obtained by hydrogenating a copolymer having a vinyl bond content of 10 to 90% in the diene part in the copolymer and a polypropylene resin is disclosed.
Patent Document 2 discloses a random copolymer having a vinyl aromatic hydrocarbon content of 5 to 60% by mass, and a copolymer having a vinyl bond content of a diene portion in the copolymer of 60% or more. A composition of a hydrogenated diene copolymer obtained by hydrogenation of a polypropylene resin and a polypropylene resin is disclosed.

  Patent Document 3 discloses a thermoplastic elastomer composition having little oil bleeding and having excellent mechanical strength, transparency and flexibility.

  In Patent Document 4, an attempt is made to obtain a flexible material in a block copolymer having a relatively high vinyl aromatic hydrocarbon content. A block mainly composed of styrene and a block mainly composed of butadiene / styrene. There is disclosed a molding material based on a hydrogenated block copolymer comprising a copolymer containing.

Japanese Patent Laid-Open No. 2-158463 JP-A-6-287365 Japanese Laid-Open Patent Publication No. 2005-281489 International Publication No. 98/012240 Pamphlet

  However, the compositions disclosed in Patent Documents 1 and 2 are not sufficiently flexible, and are also insufficient in terms of impact buffering properties.

  The thermoplastic elastomer composition disclosed in Patent Document 3 is excellent in flexibility and transparency, has few oil bleeds and is excellent in moldability, but is inferior in low resilience and inferior in impact buffering properties. It is enough.

  Furthermore, although the hydrogenated copolymer disclosed in Patent Document 4 is excellent in low resilience, it is poor in flexibility and has insufficient shock buffering properties. Further, when a rubber softener is added for the purpose of imparting flexibility, although flexibility is improved, there is a problem that oil bleeding occurs and low resilience is impaired.

  We have first developed a composition comprising a hydrogenated block copolymer, a hydrogenated block copolymer, and a rubber softener that can be used as a material having both excellent flexibility and low resilience and excellent shock buffering properties. (See International Publication No. 06/088187 pamphlet). However, the present situation is that there is a demand for the appearance of a flexible material that has no bleeding of a rubber softener and is excellent in low resilience.

  In view of the above circumstances, the problem to be solved by the present invention is water that is excellent as transparency, flexibility, low resilience, and suitable as a soft material that requires impact buffering and appearance (color development, transparency). It is to provide an additive block copolymer composition.

  As a result of intensive studies to solve the above problems, the present inventors have found that a composition containing a hydrogenated block copolymer having specific characteristics and structure and a rubber softener in a specific ratio is the above. The present inventors have found that the problem can be effectively solved, and have completed the present invention.

That is, the present invention is as follows.
[1]
(I) having at least one polymer block of the following (a), (b) and (c),
(A) Vinyl aromatic compound polymer block A
(B) Hydrogenated copolymer block B comprising conjugated diene and vinyl aromatic compound
(C) Hydrogenated polymer block C of conjugated diene polymer having a vinyl bond content of 40% or more
In the viscoelasticity measurement chart, at least one peak of tan δ (loss tangent) exists at 10 ° C. to 50 ° C. and −70 ° C. to −20 ° C., respectively, 100 parts by mass of a hydrogenated block copolymer;
(II) 100 to 150 parts by mass of a rubber softener;
A hydrogenated block copolymer composition comprising:
A hydrogenated block copolymer composition having a hardness of 5 to 25 and a rebound resilience of less than 50%.
[2]
The hydrogenated block copolymer composition according to the above [1], wherein the hydrogenated block copolymer satisfies the following (1) to (6).
(1) It has at least one polymer block of the following (a), (b) and (c) respectively (a) Vinyl aromatic compound polymer block A
(B) Hydrogenated copolymer block B comprising conjugated diene and vinyl aromatic compound
(C) Hydrogenated polymer block C of conjugated diene polymer having a vinyl bond content of 40% or more
(2) The content of the vinyl aromatic compound in the hydrogenated block copolymer is more than 40% by mass and less than 70% by mass. (3) The weight average molecular weight is 50,000 to 500,000. The vinyl bond content of the conjugated diene monomer unit constituting the pre-hydrogenated copolymer of the combined block B is 10% or more and less than 20%. (5) The hydrogenation rate of the double bond of the conjugated diene monomer unit is 50. (6) The content of the vinyl aromatic compound polymer block A in the hydrogenated block copolymer is 5% by mass to 30% by mass, and the content of the hydrogenated copolymer block B is 30% by mass. % To 50% by mass, and the content of the hydrogenated polymer block C is more than 35% by mass and 50% by mass or less.
[3]
The hydrogenated block copolymer composition according to the above [1] or [2], wherein the hydrogenated block copolymer has at least two vinyl aromatic compound polymer blocks A.
[4]
The hydrogenated block copolymer according to [1] to [3], wherein the hydrogenated block copolymer has the vinyl aromatic compound polymer block A at both ends of the polymer.
[5]
The hydrogenated block copolymer composition according to any one of [1] to [4], wherein the hydrogenated block copolymer is bonded to an atomic group having a functional group.
[6]
The hydrogenated block copolymer composition according to any one of the above [1] to [5], wherein at least one tan δ (loss tangent) peak is present at 0 ° C. to 40 ° C. in the viscoelasticity measurement chart.
[7]
The molded article obtained by bridge | crosslinking the hydrogenated block copolymer composition in any one of said [1]-[6].
[8]
The molded article according to the above [7], further comprising a urethane film coated on the surface of the molded article.

  The hydrogenated block copolymer composition of the present invention has excellent transparency, flexibility, low resilience, surface feel (no softener bleed), impact buffering and appearance (color development, transparency). As a material to have, it can use suitably for various uses.

  Hereinafter, the best mode for carrying out the present invention (hereinafter referred to as the present embodiment) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

The hydrogenated block copolymer composition of the present embodiment is
(I) having at least one polymer block of the following (a), (b) and (c),
(A) Vinyl aromatic compound polymer block A
(B) Hydrogenated copolymer block B comprising conjugated diene and vinyl aromatic compound
(C) Hydrogenated polymer block C of conjugated diene polymer having a vinyl bond content of 40% or more
In the viscoelasticity measurement chart, at least one peak of tan δ (loss tangent) exists at 10 ° C. to 50 ° C. and −70 ° C. to −20 ° C., respectively, 100 parts by mass of a hydrogenated block copolymer;
(II) 100 to 150 parts by mass of a rubber softener;
A hydrogenated block copolymer composition comprising:
Hardness is 5-25, and impact resilience is less than 50%.

[(I) Hydrogenated block copolymer]
The (I) hydrogenated block copolymer of the present embodiment is
Each having at least one polymer block of the following (a), (b) and (c):
(A) Vinyl aromatic compound polymer block A
(B) Hydrogenated copolymer block B comprising conjugated diene and vinyl aromatic compound
(C) Hydrogenated polymer block C of conjugated diene polymer having a vinyl bond content of 40% or more
In the viscoelasticity measurement chart, at least one tan δ (loss tangent) peak exists at 10 ° C. to 50 ° C. and −70 ° C. to −20 ° C., respectively.

  In the obtained viscoelasticity measurement chart, the hydrogenated block copolymer has at least one tan δ (loss tangent) peak at 10 ° C. to 50 ° C. and −70 ° C. to −20 ° C., respectively. Furthermore, it is recommended that at least one be present at 0 ° C to 40 ° C, preferably 5 ° C to 35 ° C, more preferably 10 ° C to 30 ° C.

  The peak existing at 10 ° C. to 50 ° C. of tan δ is a peak due to the hydrogenated polymer block B composed of a conjugated diene and a vinyl aromatic compound in the hydrogenated block copolymer. By having at least one peak in the range of 10 ° C. to 50 ° C., the balance between the low resilience and flexibility of the hydrogenated block copolymer composition is improved.

  Moreover, the peak which exists in -70 degreeC--20 degreeC of tan-delta is a peak resulting from the hydrogenated polymer block C of the conjugated diene polymer whose vinyl bond amount in a hydrogenated block copolymer is 40% or more. . The presence of at least one peak in the range of −70 ° C. to −20 ° C. improves the rubber softener absorbability of the hydrogenated block copolymer composition. Here, the rubber softener absorbability means the holding power of the rubber softener of the hydrogenated block copolymer composition. If this is inferior, bleeding out of the rubber softener occurs.

  In the present embodiment, the position of the tan δ peak due to the vinyl aromatic compound polymer block A bonded in the hydrogenated block copolymer is not particularly limited, but usually 80 ° C. It exists in the temperature range of over 150 degreeC.

  The (I) hydrogenated block copolymer of the present embodiment comprises (a) at least one vinyl aromatic compound polymer block A (hereinafter sometimes referred to as “polymer block A”), preferably 2 (B) a hydrogenated copolymer block B comprising a conjugated diene and a vinyl aromatic compound (hereinafter sometimes referred to as “polymer block B”), and (c) a vinyl bond content of 40%. Each has at least one hydrogenated polymer block C of the conjugated diene polymer (hereinafter also referred to as “polymer block C”).

  The conjugated diene in the present embodiment is a diolefin having a pair of conjugated double bonds, such as 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl- 1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene and the like are mentioned, and particularly common examples include 1,3-butadiene and isoprene. . These compounds can be used individually by 1 type or in combination of 2 or more types.

  Examples of the vinyl aromatic compound in the present embodiment include styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene and the like can be mentioned, and styrene is preferable. These compounds can be used individually by 1 type or in combination of 2 or more types.

  The hydrogenated block copolymer of the present embodiment has (a) at least one vinyl aromatic compound polymer block A, preferably two.

  In the hydrogenated block copolymer composition of the present embodiment, the polymer block A of the hydrogenated block copolymer is an important component from the viewpoints of mechanical strength and surface feel (no stickiness). The content of the polymer block A in the hydrogenated block copolymer is 5% by mass or more from the viewpoint of mechanical strength and surface feel, and preferably 30% by mass or less from the viewpoint of flexibility. In particular, when obtaining a hydrogenated block copolymer composition having good mechanical strength, the content of the polymer block A is preferably 15% by mass or more and 30% by mass or less. Moreover, when obtaining a hydrogenated block copolymer composition with particularly good flexibility, the content of the polymer block A is preferably 5% by mass or more and 15% by mass or less.

  The content of the polymer block A is determined by a method in which osmium tetroxide is used as a catalyst to oxidatively decompose the copolymer before hydrogenation with tertiary butyl hydroperoxide (IM KOLTHOFF, et al., J. Polym. Sci. 1, 429 (1946), hereinafter referred to as osmium tetroxide method). The content of the polymer block A is determined using a nuclear magnetic resonance apparatus (NMR) (Y. Tanaka, et al., RUBBER) using a copolymer before hydrogenation or a copolymer after hydrogenation as a specimen. CHEMISTRY and TECHNOLOGY 54, 685 (1981) (hereinafter referred to as NMR method).

In this case, the content (referred to as Os) of the polymer block A measured using the copolymer before hydrogenation by the osmium tetroxide method and the copolymer after hydrogenation by the NMR method. The measured content (referred to as Ns) of the polymer block A has a correlation represented by the following formula (F).
(Os) = − 0.012 (Ns) ² +1.8 (Ns) -13.0 Formula (F)
Accordingly, when the content of the polymer block A in the block copolymer after hydrogenation is determined by NMR method, the polymer block that defines the value of (Os) determined by the above formula (F) in this embodiment. A content.

  The (I) hydrogenated block copolymer of the present embodiment has (b) at least one hydrogenated copolymer block B composed of a conjugated diene and a vinyl aromatic compound.

  In the hydrogenated block copolymer of the present embodiment, in the differential scanning calorimetry (DSC) chart, a crystallization peak due to the hydrogenated copolymer block B substantially exists in the range of −20 ° C. to 80 ° C. It is preferable that the hydrogenated product does not. Here, “the crystallization peak due to the hydrogenated polymer block B does not substantially exist in the range of −20 ° C. to 80 ° C.” means that the crystallization of the hydrogenated copolymer block B portion in this temperature range. Even when a peak due to crystallization does not appear or a peak due to crystallization is observed, the heat of crystallization peak due to crystallization is less than 3 J / g, preferably less than 2 J / g, more preferably less than 1 J / g Particularly preferably means that there is no crystallization peak heat.

  A hydrogenated block copolymer having no crystallization peak due to the hydrogenated copolymer block B in the range of −20 ° C. to 80 ° C. tends to have good flexibility of the composition. In order to obtain a hydrogenated block copolymer substantially free from the crystallization peak due to the hydrogenated copolymer block B in the range of −20 ° C. to 80 ° C. as described above, Hydrogenation using a non-hydrogenated copolymer obtained by conducting a polymerization reaction under the conditions described below, using a regulator that adjusts or adjusts the random copolymerizability between the conjugated diene compound and the vinyl aromatic compound A reaction may be performed.

  The content of the hydrogenated copolymer block B in the hydrogenated block copolymer is preferably 30% by mass or more and 50% by mass or less, more preferably 35% by mass or more and 50% by mass or less, from the viewpoint of low resilience. More preferably, it is 40 mass% or more and 50 mass% or less.

  The mass ratio of the conjugated diene and the vinyl aromatic compound (conjugated diene / vinyl aromatic compound) in the random copolymer constituting the hydrogenated copolymer block B is preferably 50/50 to 10/90, more preferably 40. / 60 to 15/85, more preferably 35/65 to 20/80.

  The microstructure (ratio of cis, trans, vinyl) of the conjugated diene monomer unit constituting the pre-hydrogenation polymer of the hydrogenated copolymer block B can be arbitrarily changed by using a polar compound described later. . The vinyl bond amount of the conjugated diene monomer unit is preferably 10% or more and less than 20%, more preferably 10% or more and 15% or less. When the vinyl bond amount is within the above range, low resilience tends to be good.

  In this embodiment, the “vinyl bond amount” means the total amount of 1,2-vinyl bond and 3,4-vinyl bond (provided that 1,3-butadiene is used as the conjugated diene). Represents the amount of 1,2-vinyl bonds, and the amount of 3,4-vinyl bonds when isoprene is used as the conjugated diene). The amount of vinyl bonds can be measured by measurement with an infrared spectrophotometer using a copolymer before hydrogenation as a specimen (for example, the Hampton method).

  The (I) hydrogenated block copolymer of the present embodiment has (c) at least one hydrogenated polymer block C of a conjugated diene polymer having a vinyl bond content of 40% or more.

  The amount of vinyl bond of the conjugated diene before hydrogenation of the hydrogenated polymer block C is preferably 40% or more, more preferably 45% to from the viewpoint of flexibility and surface feel (no softener bleed etc.). 80%, more preferably 45% to 75%, particularly preferably 45% to 70%.

  The content of the hydrogenated polymer block C in the hydrogenated block copolymer of the present embodiment is more than 35% by mass and 50% by mass or less, more preferably 40% from the viewpoint of rubber softener absorbability. It is 50 mass% or less.

  The content of the vinyl aromatic compound in the hydrogenated block copolymer of the present embodiment is more than 40% by mass and less than 70% by mass from the viewpoint of flexibility, surface feel, etc. of the hydrogenated block copolymer composition. Preferably, it is 40 mass% or more and less than 60 mass%, More preferably, it is 40 mass% or more and 50 mass%. Here, the content of the vinyl aromatic compound in the hydrogenated block copolymer is measured using an ultraviolet spectrophotometer using the block copolymer before hydrogenation or the block copolymer after hydrogenation as a specimen. be able to.

  The weight average molecular weight of the hydrogenated block copolymer of the present embodiment is 50,000 to 500,000, preferably 100,000 to 150,000, from the viewpoint of balance between heat resistance, mechanical strength and molding processability. More preferably, it is 100,000-130,000. Here, the weight average molecular weight of the hydrogenated block copolymer is measured by gel permeation chromatography (GPC), and a calibration curve obtained from measurement of commercially available standard polystyrene (the peak molecular weight of standard polystyrene is used. The molecular weight of the chromatogram determined using

  The molecular weight distribution of the hydrogenated block copolymer of the present embodiment is preferably 10 or less, more preferably 1 to 8, and still more preferably 1.01 to 5. Here, the molecular weight distribution of the hydrogenated block copolymer can be determined from the measurement by GPC in the same manner as described above, and is calculated by the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight).

  The hydrogenated block copolymer of the present embodiment is a hydrogenated product of a copolymer comprising a conjugated diene and a vinyl aromatic compound, and has a viewpoint of a balance between heat resistance and weather resistance and moldability of the composition. Therefore, the hydrogenation rate of the double bond of the conjugated diene monomer unit in the copolymer is 50% or more, preferably 70% or more, more preferably 90% or more. The hydrogenation rate of the aromatic double bond of the vinyl aromatic hydrocarbon monomer unit in the hydrogenated block copolymer is not particularly limited, but is preferably 50% or less, more preferably 30% or less. More preferably, it is 20% or less. The hydrogenation rate of the hydrogenated block copolymer can be measured using a nuclear magnetic resonance apparatus (NMR) or the like.

  The structure of the hydrogenated block copolymer in the present embodiment is not particularly limited, and any structure can be used. As the structure of the hydrogenated block copolymer comprising at least one polymer block A, preferably two, at least one hydrogenated copolymer block B, and at least one hydrogenated polymer block C, For example, what has a structure represented by the following general formula is mentioned.

C- (B-A) _n , C- (A-B) _n , C- (A-B-A) _l ,
C- (B-A-B) _n , A-C- (B-A) _l , A-C- (A-B) _l ,
A-C- (B-A) ₁ -B, [(A-B-C) ₁ ] _m -X, [A- (B-C) ₁ ] _m -X,
[(A-B) _l -C] _m -X, [(A-B-A) _l -C] _m -X,
[(B-A-B) _l -C] _m -X, [(C-B-A) _l ] _m -X,
[C- (BA) _l ] _m -X, [C- (ABA) _l ] _m -X,
[C- (BAB) _l ] _m -X

  In the above general formula, A, B and C represent polymer blocks A, B and C in the present embodiment, respectively. Here, the boundary of each block does not necessarily need to be clearly distinguished. The vinyl aromatic hydrocarbons in the polymer block B may be distributed uniformly or in a tapered shape. In the polymer block B, a plurality of portions where vinyl aromatic hydrocarbons are uniformly distributed and / or a portion where tapes are distributed may coexist. In the polymer block B, a plurality of segments having different vinyl aromatic hydrocarbon contents may coexist.

  Moreover, in the said general formula, l is 1 or more, Preferably it is an integer of 1-5, n is 2 or more, Preferably it is an integer of 2-5. m is 2 or more, preferably an integer of 2 to 11. X represents a residue of a coupling agent or a residue of a polyfunctional initiator.

  When a plurality of polymer blocks A, polymer blocks B, and polymer blocks C are present in the hydrogenated block copolymer, the structures such as molecular weight and composition may be the same or different. Further, the structure of the polymer chain bonded to X may be the same or different.

Among the structures represented by the above general formula, from the viewpoint of surface feel and mechanical strength, a copolymer having a structure having a block A at both ends is preferable, and an AC— (BA) _l structure is particularly preferable. .

  The hydrogenated block copolymer of the present embodiment may be any mixture of copolymers having a structure represented by the above general formula. In addition, a vinyl aromatic compound polymer, a copolymer having an AB structure, or a BAB structure may be mixed with the hydrogenated block copolymer.

  The copolymer before hydrogenation of the hydrogenated block copolymer of the present embodiment can be obtained, for example, by conducting anion living polymerization using an initiator such as an organic alkali metal compound in a hydrocarbon solvent. it can.

  Examples of the hydrocarbon solvent used for polymerization include aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, and n-octane; cyclohexane, cycloheptane, methylcycloheptane, and the like. And alicyclic hydrocarbons; and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene.

  In addition, as an initiator used for polymerization, an aliphatic hydrocarbon alkali metal compound or an aromatic hydrocarbon alkali metal compound generally known to have anionic polymerization activity with respect to a conjugated diene compound and a vinyl aromatic compound And organic amino alkali metal compounds, and examples of the alkali metal contained therein include lithium, sodium, and potassium.

  Suitable organic alkali metal compounds include aliphatic and aromatic hydrocarbon lithium compounds having 1 to 20 carbon atoms. For example, a compound containing one lithium in one molecule, and a plurality of lithium in one molecule. Examples thereof include dilithium compounds, trilithium compounds, and tetralithium compounds. More specifically, n-propyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, n-pentyl lithium, n-hexyl lithium, benzyl lithium, phenyl lithium, tolyl lithium, diisopropenylbenzene and Examples thereof include a reaction product of sec-butyllithium, a reaction product of divinylbenzene, sec-butyllithium, and a small amount of 1,3-butadiene.

  Furthermore, organic alkali metal compounds disclosed in US Pat. No. 5,708,092, British Patent 2,241,239, US Pat. No. 5,527,753, etc. are also used. be able to.

  Moreover, when the conjugated diene compound and the vinyl aromatic compound are copolymerized using the above-described organic alkali metal compound as a polymerization initiator, a vinyl bond (1, 2- or 3, resulting from the conjugated diene compound incorporated into the polymer) For the purpose of adjusting the amount of 4-bond) and adjusting the random copolymerizability between the conjugated diene compound and the vinyl aromatic compound, a regulator such as a tertiary amine compound or an ether compound can be added.

The tertiary amine compound is a general formula R ¹ R ² R ³ N (where R ¹ , R ² and R ³ are hydrocarbon groups having 1 to 20 carbon atoms or a tertiary amino group) It is a compound represented by. Examples of the tertiary amine compound include trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N-ethylpiperidine, N-methylpyrrolidine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetraethylethylenediamine, 1,2-dipiperidinoethane, trimethylaminoethylpiperazine, N, N, N ′, N ″, N ″ -pentamethylethylenetriamine, N, N′-dioctyl -P-phenylenediamine and the like.

  The ether compound is selected from linear ether compounds and cyclic ether compounds. Examples of the linear ether compound include dimethyl ether, diethyl ether, diphenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether. And dialkyl ether compounds of ethylene glycol such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol dibutyl ether. Examples of the cyclic ether compound include tetrahydrofuran, dioxane, 2,5-dimethyloxolane, 2,2,5,5-tetramethyloxolane, 2,2-bis (2-oxolanyl) propane, and furfuryl alcohol. And alkyl ethers.

  In the present embodiment, the method of copolymerizing a conjugated diene compound and a vinyl aromatic compound using an organic alkali metal compound as a polymerization initiator is batch polymerization, continuous polymerization, or a combination thereof. Also good. In particular, a batch polymerization method is preferred to obtain a copolymer having excellent heat resistance.

  The polymerization temperature is usually 0 ° C to 180 ° C, preferably 30 ° C to 150 ° C. The time required for polymerization varies depending on the conditions, but is usually within 48 hours, preferably 0.1 to 10 hours.

  The polymerization atmosphere is preferably an inert gas atmosphere such as nitrogen gas. The polymerization pressure is not particularly limited as long as the polymerization pressure is in a range sufficient to maintain the monomer and solvent in a liquid phase within the above polymerization temperature range. Furthermore, it is necessary to pay attention so that impurities that inactivate the catalyst and the living polymer, for example, water, oxygen, carbon dioxide gas, and the like are not mixed in the polymerization system.

  In the present embodiment, a coupling reaction can be performed by adding a necessary amount of a bifunctional or higher functional coupling agent at the end of the polymerization. A known bifunctional coupling agent can be used, and is not particularly limited. Specific examples include dihalogen compounds such as dimethyldichlorosilane and dimethyldibromosilane, and acid esters such as methyl benzoate, ethyl benzoate, phenyl benzoate, and phthalates.

Moreover, a well-known thing can be used as a polyfunctional coupling agent more than trifunctional, It does not specifically limit. Specifically, for example, polyalcohols having three or more valences, polyepoxy compounds such as epoxidized soybean oil, diglycidyl bisphenol A, general formula R _4-n SiX _n (where R is 1 to 20 carbon atoms) A halogenated silicon compound such as methylsilyl trichloride, t-butylsilyl trichloride, silicon tetrachloride, and bromides thereof. A tin halide compound represented by the general formula R _4-n SnX _n (where R represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen, and n represents an integer of 3 to 4), for example, And polyvalent halogen compounds such as methyltin trichloride, t-butyltin trichloride, and tin tetrachloride. Moreover, dimethyl carbonate, diethyl carbonate, etc. can also be used.

  The hydrogenated block copolymer of the present embodiment can be obtained by hydrogenating the block copolymer obtained above.

  The hydrogenation catalyst used for the hydrogenation is not particularly limited, and is conventionally known (1) A support in which a metal such as Ni, Pt, Pd, or Ru is supported on carbon, silica, alumina, diatomaceous earth, or the like. Type heterogeneous hydrogenation catalyst, (2) so-called Ziegler type hydrogenation catalyst using an organic acid salt such as Ni, Co, Fe, Cr or a transition metal salt such as acetylacetone salt and a reducing agent such as organic aluminum, 3) A homogeneous hydrogenation catalyst such as a so-called organometallic complex such as an organometallic compound such as Ti, Ru, Rh, or Zr is used.

  Specific examples of the hydrogenation catalyst include Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-337970, and Japanese Patent Publication No. 1-35381. The hydrogenation catalyst described in JP-B-2-9041 and the like can be used.

  Preferred hydrogenation catalysts include mixtures with titanocene compounds and / or reducing organometallic compounds. As the titanocene compound, for example, a compound described in JP-A-8-109219 can be used. Specifically, biscyclopentadienyl titanium dichloride, monopentamethylcyclopentadienyl titanium trichloride, and the like can be used. (Substituted) A compound having at least one ligand having a cyclopentadienyl skeleton, an indenyl skeleton, or a fluorenyl skeleton is exemplified. Examples of the reducing organometallic compound include organic alkali metal compounds such as organolithium, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds.

  In the present embodiment, the hydrogenation reaction is usually performed in a temperature range of 0 ° C to 200 ° C, preferably 30 ° C to 150 ° C. The pressure of hydrogen used for the hydrogenation reaction is usually 0.1 MPa to 15 MPa, preferably 0.2 MPa to 10 MPa, more preferably 0.3 MPa to 5 MPa. The hydrogenation reaction time is usually 3 minutes to 10 hours, preferably 10 minutes to 5 hours. The hydrogenation reaction can be any of a batch process, a continuous process, or a combination thereof.

  The hydrogenated block copolymer solution obtained as described above can be separated from the solution by removing the catalyst residue as necessary. As a method for separating the hydrogenated block copolymer from the solution, for example, a polar solvent that is a poor solvent for the hydrogenated block copolymer such as acetone or alcohol is added to the reaction solution after the hydrogenation reaction and polymerized. A method for precipitating and recovering the coal, a method in which the reaction solution is poured into hot water with stirring and removing the solvent by steam stripping, or a method in which the solvent is distilled off by directly heating the polymer solution, etc. Can be mentioned.

  Stabilizers such as various phenol stabilizers, phosphorus stabilizers, sulfur stabilizers and amine stabilizers can be added to the hydrogenated block copolymer of the present embodiment.

  Further, the hydrogenated block copolymer of the present embodiment includes a modified hydrogenated copolymer in which an atomic group having a functional group is bonded to the hydrogenated copolymer described above. Examples of the atomic group having a functional group include a hydroxyl group, a carbonyl group, a thiocarbonyl group, an acid halide group, an acid anhydride group, a carboxyl group, a thiocarboxylate group, an aldehyde group, a thioaldehyde group, a carboxylate group, Amide group, sulfonic acid group, sulfonic acid ester group, phosphoric acid group, phosphoric acid ester group, amino group, imino group, nitrile group, pyridyl group, quinoline group, epoxy group, thioepoxy group, sulfide group, isocyanate group, isothiocyanate And an atomic group containing at least one functional group selected from a group, a silicon halide group, a silanol group, an alkoxysilicon group, a tin halide group, an alkoxytin group, a phenyltin group, and the like. Among these, a modified hydrogenated block copolymer to which an atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group is bonded is preferable.

  Examples of the modifying agent for bonding the atomic group having a functional group to the hydrogenated block copolymer include tetraglycidylmetaxylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, ε-caprolactone, and δ-valero. Lactone, 4-methoxybenzophenone, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyldimethylphenoxysilane, bis (γ-glycidoxypropyl) methylpropoxysilane, Examples include 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N, N′-dimethylpropylene urea, N-methylpyrrolidone and the like.

  A modified hydrogenated block copolymer to which an atomic group having a functional group is bonded, for example, has a functional group-containing atomic group at the living terminal of the block copolymer obtained by the above-described method using an organolithium compound as a polymerization catalyst. The modification | denaturant to produce | generate can be addition-reacted to obtain a modified block copolymer, and further can be obtained by carrying out the hydrogenation reaction described above.

  The reaction temperature when the modifier is reacted is preferably 0 ° C to 150 ° C, more preferably 20 ° C to 120 ° C. The reaction time when the modifier is reacted varies depending on other conditions, but is preferably within 24 hours, more preferably 0.1 to 10 hours.

  Further, the hydrogenated block copolymer of the present embodiment has a functional group obtained by graft-modifying with an α, β-unsaturated carboxylic acid or a derivative thereof, for example, an anhydride, esterified product, amidated product or imidized product thereof. You may combine with the atomic group which has.

  Specific examples of α, β-unsaturated carboxylic acid or derivatives thereof include maleic anhydride, maleic anhydride imide, acrylic acid or ester thereof, methacrylic acid or ester thereof, endo-cis-bicyclo [2,2,1 ] -5-heptene-2,3-dicarboxylic acid or an anhydride thereof.

  The addition amount of the α, β-unsaturated carboxylic acid or derivative thereof is usually 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the hydrogenated block copolymer.

  The reaction temperature at the time of graft modification is preferably 100 to 300 ° C, more preferably 120 to 280 ° C.

  For details of the graft modification method, reference can be made to, for example, JP-A No. 62-79211.

  In the present embodiment, the above-mentioned (I) hydrogenated block copolymer (hereinafter also referred to as component (I)) and (II) rubber softener (hereinafter also referred to as component (II)), By combining at specific ratios, hydrogenated block copolymer compositions suitable for various molding materials can be obtained.

  Combining the hydrogenated block copolymer with a rubber softener at a specific ratio can soften the composition and provide good processability. Examples of the softening material for rubber include mineral oil and liquid or low molecular weight synthetic softening agents. Among them, naphthenic and / or paraffinic process oil or extender oil is preferable.

  Mineral oil-based rubber softener is a mixture of aromatic ring, naphthene ring and paraffin chain. Paraffin chain occupies 50% or more of total carbon is called paraffinic, and carbon of naphthene ring Those having a number of 30 to 45% are called naphthenes, and those having an aromatic carbon number exceeding 30% are called aromatics.

  Synthetic softeners such as polybutene, low molecular weight polybutadiene, and liquid paraffin may be used in the hydrogenated block copolymer composition, but it is more preferable to use the mineral oil rubber softener described above.

  The compounding amount of the rubber softener in the hydrogenated block copolymer composition of the present embodiment is 100 to 150 parts by mass, preferably 100 to 130 parts by mass with respect to 100 parts by mass of the hydrogenated block copolymer. is there. If the amount of the rubber softening agent exceeds 150 parts by mass, the rubber softening agent tends to bleed out and the surface feel is deteriorated. Moreover, since the hardness of a hydrogenated block polymer composition becomes high that the softening agent for rubbers is less than 100 mass parts, it is not preferable.

  In the hydrogenated block copolymer composition containing the hydrogenated block copolymer and the rubber softener in the present embodiment, the tan δ (loss tangent) peak is 0 ° C. to 40 ° C. in the obtained viscoelasticity measurement chart. It is desirable that at least one be present at 0 ° C., preferably 5 ° C. to 35 ° C., more preferably 10 ° C. to 30 ° C. The tan δ peak is a peak attributed to the hydrogenated polymer block B comprising a conjugated diene and a vinyl aromatic compound and a rubber softener in the hydrogenated block copolymer. When at least one peak exists in the range of 0 ° C. to 40 ° C., the balance between the low resilience and flexibility of the hydrogenated block copolymer composition is improved. The position of the peak of tan δ attributed to the vinyl aromatic compound polymer block A in the hydrogenated block copolymer is not particularly limited, but usually exists within a temperature range of more than 80 ° C. and 150 ° C. or less. To do.

  The hydrogenated block copolymer (component (I)) of the present embodiment is at least one selected from the group consisting of a thermoplastic resin and a rubbery polymer in addition to the rubber softener (component (II)). It is also possible to combine hydrogenated block copolymer compositions suitable for various molding materials by further combining seed components (hereinafter also referred to as component (III)).

  The amount of component (III) is preferably 5 to 100 parts by weight, more preferably 10 to 80 parts by weight, and still more preferably 20 to 60 parts by weight with respect to 100 parts by weight of component (I). When the compounding amount of the component (III) is larger than the above range, the flexibility of the composition may be lowered or the transparency may be deteriorated.

  When a thermoplastic resin such as polypropylene is blended in the hydrogenated block copolymer composition of the present embodiment, a composition excellent in mechanical properties, heat resistance, and the like can be obtained.

  As the thermoplastic resin, a block copolymer resin of a conjugated diene compound and a vinyl aromatic compound and a hydrogenated product thereof (but different from the hydrogenated block copolymer of the present embodiment), the vinyl aromatic compound described above Polymers of the above, vinyl aromatic compounds mentioned above and other vinyl monomers, for example, ethylene, propylene, butylene, vinyl chloride, vinylidene chloride, vinyl acetate, acrylic acid esters such as acrylic acid and acrylic methyl, methacrylic acid and methyl methacrylate Copolymer resins with methacrylic esters, acrylonitrile, methacrylonitrile, etc., rubber-modified styrene resins (HIPS), acrylonitrile-butadiene-styrene copolymer resins (ABS), methacrylate ester-butadiene-styrene copolymer resins ( MBS).

  Further, as a thermoplastic resin, polyethylene, a copolymer of ethylene containing 50% by mass or more of ethylene and another monomer copolymerizable therewith, for example, an ethylene-propylene copolymer, an ethylene-butylene copolymer, 50% by mass or more of ethylene-hexene copolymer, ethylene-octene copolymer, ethylene-vinyl acetate copolymer and its hydrolyzate, polyethylene resins such as ethylene-acrylic acid ionomer and chlorinated polyethylene, polypropylene and propylene Copolymers of contained propylene and other monomers copolymerizable therewith, for example, propylene-ethylene copolymers, polypropylene resins such as propylene-ethyl acrylate copolymers and chlorinated polypropylene, ethylene-norbornene resins Cyclic olefin resin such as polybutene tree It may be used polyvinyl chloride resin, polyvinyl acetate resin and a hydrolyzate thereof or the like.

  Further, as thermoplastic resins, acrylic acid and its ester and amide polymers, polyacrylate resins, acrylonitrile and / or methacrylonitrile polymers, and other copolymers containing 50% by mass or more of these acrylonitrile monomers. Polyamides such as nitrile resin, nylon-46, nylon-6, nylon-66, nylon-610, nylon-11, nylon-12, nylon-6 nylon-12 copolymer, which are copolymers with possible monomers Resins, polyester resins, thermoplastic polyurethane resins, polycarbonate polymers such as poly-4,4′-dioxydiphenyl-2,2′-propane carbonate, thermoplastic polysulfones such as polyethersulfone and polyallylsulfone, Polyoxymethylene resin, poly (2,6-dimethyl) Poly-1,4-phenylene) ether, polyphenylene ether resins, polyphenylene sulfide, polyphenylene sulfide resins such as poly 4,4′-diphenylene sulfide, polyarylate resins, polyether ketone polymers or copolymers, Polybutadiene resins such as polyketone resins, fluorine resins, polyoxybenzoyl polymers, polyimide resins, 1,2-polybutadiene, and transpolybutadiene may be used.

  Among the above-mentioned thermoplastic resins (component (III)), particularly preferred are styrene resins such as polystyrene and rubber-modified styrene resins, polyethylene, ethylene-propylene copolymers, ethylene-propylene-butylene copolymers, Ethylene-butylene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid ester copolymer, etc. Polyethylene resins, polypropylene resins such as polypropylene and propylene-ethylene copolymers, polyamide resins, polyester resins, and polycarbonate resins. The number average molecular weight of these thermoplastic resins is generally 1000 or more, preferably 5000 to 5 million, and more preferably 10,000 to 1 million.

  Further, when a rubber-like polymer is blended into the hydrogenated block copolymer composition of the present embodiment, a composition having excellent elongation characteristics and the like can be obtained.

  Examples of the rubber-like polymer include butadiene rubber and its hydrogenated product, styrene-butadiene rubber and its hydrogenated product (however, different from the hydrogenated block copolymer of the present embodiment), isoprene rubber, acrylonitrile-butadiene rubber. And hydrogenated products thereof, 1,2-polybutadiene, chloroprene rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber (EPDM), ethylene-butene-diene rubber, ethylene-butene rubber, ethylene-hexene rubber, ethylene-octene rubber, and other olefins Elastomer, butyl rubber, acrylic rubber, fluorine rubber, silicone rubber, chlorinated polyethylene rubber and the like can be mentioned.

  In addition, as rubbery polymers, epichlorohydrin rubber, α, β-unsaturated nitrile-acrylate ester-conjugated diene copolymer rubber, urethane rubber, polysulfide rubber, styrene-butadiene block copolymer and hydrogenated product thereof, styrene -Styrene elastomers such as isoprene block copolymers and hydrogenated products thereof, natural rubber, etc. may be used.

  Of the above-mentioned rubbery polymers (component (III)), particularly preferred are styrene elastomers such as styrene-butadiene block copolymers and hydrogenated products thereof, styrene-isoprene block copolymers and hydrogenated products thereof. 1,2-polybutadiene, ethylene-butene rubber, ethylene-octene rubber, ethylene-propylene-diene rubber (EPDM) and other olefin elastomers and butyl rubber. Further, these rubbery polymers may be modified rubbers provided with functional groups.

  The number average molecular weight of the rubber-like polymer is preferably 10,000 or more, more preferably 20,000 to 1,000,000, still more preferably 30,000 to 800,000.

  Moreover, these thermoplastic resins and rubber-like polymers may be used in combination of two or more as required. When two or more types are used in combination, the thermoplastic resin components may be used together, the rubber-like polymer components may be used together, or the thermoplastic resin and the rubber-like polymer may be used in combination.

  Arbitrary additives can be mix | blended with the hydrogenated block copolymer composition of this Embodiment as needed. The type of additive is not particularly limited as long as it is generally used for blending thermoplastic resins and rubber-like polymers.

  Examples of additives include pigments and colorants such as carbon black and titanium oxide, lubricants such as stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, and ethylene bisstearamide, mold release agents, phthalates Fatty acid esters such as acid ester compounds, adipic acid ester compounds, azelaic acid ester compounds, plasticizers such as mineral oil, hindered phenol antioxidants, antioxidants such as phosphorus heat stabilizers, hindered amine light stabilizers , Benzotriazole ultraviolet absorbers, antistatic agents, organic fibers, glass fibers, carbon fibers, reinforcing agents such as metal whiskers, other additives or mixtures thereof.

  In the hydrogenated block copolymer composition of the present embodiment, an optional filler and a flame retardant can be blended as necessary. The filler and the flame retardant are not particularly limited as long as they are materials generally used for blending thermoplastic resins and rubber-like polymers.

  Examples of the filler include silica, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, calcium sulfate, barium sulfate, carbon black, glass fiber, glass beads, glass balloon, glass flake, graphite, titanium oxide, and titanium. Potassium acid whisker, carbon fiber, alumina, kaolin clay, silicic acid, calcium silicate, quartz, mica, talc, clay, zirconia, potassium titanate, alumina, metal particles and other inorganic fillers, wooden chips, wooden powder, pulp And organic fillers such as The shape of the filler is not particularly limited, and those having a scale shape, a spherical shape, a granular shape, a powder shape, an indefinite shape, and the like can be used. These fillers can be used alone or in combination.

  Examples of the flame retardant include flame retardants such as halogen compounds, which are mainly bromine compounds, phosphorus compounds, which are mainly aromatic compounds, and inorganic materials, which are mainly metal hydroxides. In recent years, however, inorganic flame retardants are mainly used due to environmental problems. This is preferable. Examples of the inorganic flame retardant include metal hydroxides such as magnesium hydroxide, aluminum hydroxide and calcium hydroxide, metal oxides such as zinc borate and barium borate, other calcium carbonate, clay, basic magnesium carbonate, hydrotalc. Mainly hydrous metal compounds such as sites are listed. Among the above flame retardants, metal hydroxides such as magnesium hydroxide are preferable from the viewpoint of improving flame retardancy. In addition, the flame retardant includes a so-called flame retardant auxiliary that exhibits a low flame retardancy effect itself but exhibits a synergistically superior effect when used in combination with other flame retardants.

  As the filler and the flame retardant, a type in which a surface treatment is performed in advance with a surface treatment agent such as a silane coupling agent may be used.

  These fillers and flame retardants may be used in combination of two or more as required. When two or more kinds are used in combination, the filler components may be commensurate with each other, the flame retardant component comrades, or a filler and a flame retardant in combination.

  The hydrogenated block copolymer composition of the present embodiment may be added with other additives described in “Rubber / Plastic Compounding Chemicals” (edited by Rubber Digest Co., Ltd.) or a mixture thereof as necessary. May be.

  The hydrogenated block copolymer composition of this Embodiment can be bridge | crosslinked as needed. As a crosslinking method, a chemical method by adding a crosslinking agent such as peroxide and sulfur and, if necessary, a co-crosslinking agent, radiation crosslinking, and the like can be used. As the crosslinking process, a static method, a dynamic vulcanization method, or the like can be used.

  Examples of the crosslinking agent include organic peroxides, sulfur, phenolic, isocyanate-based, thiuram-based, morpholine disulfide, etc., and these include crosslinking aids such as stearic acid, oleic acid, zinc stearate, and zinc oxide. , Co-crosslinking agents, vulcanization accelerators and the like can be used in combination.

  Examples of the organic peroxide crosslinking agent include hydroperoxide, dialkyl peroxide, diallyl peroxide, diacyl peroxide, peroxyester, and ketone peroxide. Further, a physical crosslinking method using an electron beam, radiation or the like can also be used.

  The method for producing the hydrogenated block copolymer composition of the present embodiment is not particularly limited, and known methods can be used. For example, a melt kneading method using a general blender such as a Banbury mixer, a single screw extruder, a twin screw extruder, a kneader, a multi-screw extruder, etc., each component is dissolved or dispersed and mixed, and then the solvent is heated A removal method or the like can be used. In the present embodiment, a melt mixing method using an extruder is preferable from the viewpoints of productivity and good kneading properties. Although it does not specifically limit as a shape of the obtained hydrogenated copolymer composition, A pellet form, a sheet form, a strand form, a chip form, etc. are mentioned. Moreover, it can also be directly molded after melt-kneading.

  Examples of a method applicable when obtaining a foamed molded product of the hydrogenated block copolymer composition of the present embodiment include a chemical method and a physical method, and an inorganic foaming agent and an organic foaming respectively. Bubbles can be distributed inside the material by adding a foaming agent such as a chemical foaming agent or a physical foaming agent. By using a hydrogenated block copolymer composition as a foam material, weight reduction, flexibility improvement, design improvement, etc. can be achieved.

  Here, examples of the inorganic foaming agent include sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, ammonium nitrite, an azide compound, sodium borohydride, metal powder, and the like.

  Organic foaming agents include azodicarbonamide, azobisformamide, azobisisobutyronitrile, barium azodicarboxylate, N, N′-dinitrosopentamethylenetetramine, N, N′-dinitroso-N, N′- Examples thereof include dimethyl terephthalamide, benzenesulfonyl hydrazide, p-toluenesulfonyl hydrazide, p, p′-oxybisbenzenesulfonyl hydrazide, p-toluenesulfonyl semicarbazide and the like.

  Physical blowing agents include hydrocarbons such as pentane, butane and hexane, halogenated hydrocarbons such as methyl chloride and methylene chloride, gases such as nitrogen and air, trichlorofluoromethane, dichlorodifluoromethane, trichlorotrifluoroethane, chloro Examples thereof include fluorinated hydrocarbons such as difluoroethane and hydrofluorocarbon.

  The molded product of the hydrogenated block copolymer composition of the present embodiment is formed on the surface of the molded product, if necessary, for the purpose of improving the appearance, weather resistance, scratch resistance, etc. Decoration such as coating and embossing can be performed.

  As the coating agent, a two-component curing type, a moisture curing type, and a solvent volatilization curing type urethane coating agent are preferable, and a urethane film can be provided on the surface of the molded product using these coating agents. When surface treatment is performed for the purpose of improving printability, paintability, coating properties, etc., the surface treatment method is not particularly limited, and physical methods, chemical methods, and the like can be used. For example, corona discharge Treatment, ozone treatment, plasma treatment, flame treatment, acid / alkali treatment, and the like. Among these, corona discharge treatment is preferable from the viewpoints of ease of implementation, cost, and continuous treatment.

  The hydrogenated block copolymer composition of the present embodiment can be used for various applications by blending various additives as necessary. Regarding specific aspects of the hydrogenated copolymer composition of the present embodiment, (i) reinforcing filler compound, (ii) crosslinked product, (iii) foam, (iv) multilayer film and multilayer sheet, etc. (V) building materials, (vi) vibration damping and soundproofing materials, (vii) wire coating materials, (viii) high frequency fusible compositions, (ix) slush molding materials, (x) adhesive properties It can be suitably used for compositions, (xi) asphalt compositions, (xii) medical device materials, (xiii) automobile materials, and the like.

  The hydrogenated block copolymer composition of the present embodiment can be used for various applications as described above, but as a molding method when used as a molded product, extrusion molding, injection molding, hollow molding, pressure molding Vacuum molding, foam molding, multilayer extrusion molding, multilayer injection molding, high-frequency fusion molding, slush molding, calendar molding, and the like can be used. Specific examples of the molded product include a sheet, a film, a tube, a nonwoven fabric or a fibrous molded product, and synthetic leather.

Hereinafter, the present embodiment will be specifically described by way of examples. However, the present embodiment is not limited to these examples.
In the following examples, the methods for measuring the properties and physical properties of the polymers are as follows.

(1) Properties of hydrogenated block copolymer (1-1) Styrene content in hydrogenated block copolymer Ultraviolet spectrophotometer (UV-2450, manufactured by Shimadzu Corporation) using the copolymer before hydrogenation It measured using.
(1-2) Content of vinyl aromatic compound polymer A in hydrogenated block copolymer M.M. Kolthoff, et al. J. et al. Polym. Sci. 1, 429 (1946). For decomposition of the copolymer, an osmic acid 0.1 g / 125 ml tertiary butanol solution was used.
(1-3) Vinyl Bond Amount of Hydrogenated Block Copolymer The copolymer before hydrogenation was used and measured using an infrared spectrophotometer (FT / IR-230, manufactured by JASCO Corporation). The vinyl bond amount of the copolymer was calculated by the Hampton method.
(1-4) Weight average molecular weight and molecular weight distribution of hydrogenated block copolymer: GPC [Equipment: HLC-8120 GPC manufactured by Tosoh Corporation] was used. Tetrahydrofuran was used as the solvent, and the measurement was performed at a temperature of 35 ° C.
The weight average molecular weight was calculated | required using the analytical curve created using the commercially available standard polystyrene whose weight average molecular weight and number average molecular weight are known.
The molecular weight distribution was calculated from the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn).
(1-5) Hydrogenation rate (hydrogenation rate) of double bond of conjugated diene monomer unit of hydrogenated block copolymer
The hydrogenated copolymer after hydrogenation was used and measured with a nuclear magnetic resonance apparatus (device name: DPX-400; manufactured by BRUKER, Germany).
(1-6) Modification rate The modified hydrogenated block copolymer adsorbs on the silica gel column but does not adsorb on the polystyrene gel column. Measurement was performed using this characteristic. That is, for a sample solution containing a sample and a low molecular weight internal standard polystyrene, both GPC of a standard polystyrene gel column and GPC of a silica gel column (Zorbax, DuPont, USA) performed in the same manner as in (1-5) above. Gram was measured, and the amount of the modified hydrogenated block copolymer adsorbed onto the silica gel column was measured from the difference between them, and the modification rate was determined.

(2) Properties of hydrogenated block copolymer composition (2-1) Processability: flowability <melt flow rate (MFR)>
According to JIS K6758, MFR of 130 ° C. and a load of 2.16 kg was measured.
(2-2) Flexibility: Hardness The value after 10 seconds was measured with a durometer type A according to JIS K6253.
(2-3) Mechanical strength: Breaking strength, breaking elongation Measured according to JIS K6251 with a No. 3 dumbbell and a crosshead speed of 500 mm / min. When the breaking strength is less than 10 kg / cm 2, the strength is insufficient, which causes a practical problem.
(2-4) Transparency A press sheet having a thickness of 2 mm was prepared, and five sheets were stacked and placed on a newspaper. The degree to which the printed characters could be read was visually confirmed, and judged according to the following criteria.
○: The type can be clearly read.
Δ: The image is unclear but the type can be read.
X: The type cannot be read.
(2-5) Rebound resilience: Dunlop repulsion Measured at 23 ° C. according to BS903. If it is 50% or more, the impact resilience is too high, which causes a practical problem.
(2-6) Surface feel A press sheet having a thickness of 2 mm was prepared and evaluated by the following method.
-Stickiness: The surface of the sheet was touched with a finger to check for stickiness.
Oil bleed: Paper was sandwiched between sheets, and after 24 hours, the presence or absence of oil transfer to the paper was confirmed. When there is either stickiness or oil bleed, it becomes a practical problem.
(2-7) Peak temperature of tan δ (loss tangent) Viscoelasticity spectrum was measured and determined using a viscoelasticity measuring and analyzing apparatus (Model DVE-V4, manufactured by Rheology Co., Ltd.). The measurement frequency was 10 Hz.
(2-8) Adhesiveness Adhesiveness was evaluated from the measurement of adhesive strength by a T-type peel test. (The greater the adhesion strength, the better the adhesion.) The adhesion conditions and peel test conditions are as follows.
[Adhesion conditions]
The hydrogenated block copolymer composition was press-molded into a 2 mm thick sheet at 200 ° C., and then the surface of the sheet was surface-treated with a 3% ethyl acetate solution of triallyl isocyanurate containing hypochlorous acid. A sample sheet having a urethane coating on the surface was prepared by immersing the product in a butyl acetate solution of polyurethane, and adhered to a 2 mm thick sheet made of urethane elastomer with a two-component curable urethane adhesive. Sheets were cut into strips with a width of 2 cm and measurements were taken.
[Peel test]
Peeling speed: 200 mm / min. The peel strength was measured in units of kg / 2 cm.
The higher the peel strength, the better. Peeling when the adhesiveness is not sufficient occurs on the adhesive surface of the urethane coating layer and the hydrogenated block copolymer composition, but when the adhesiveness is excellent, the inside of the sheet made of the hydrogenated block copolymer composition is broken. Occurs, and the peel strength is improved.

<Preparation of hydrogenation catalyst>
In the following examples and comparative examples, the hydrogenation catalyst used for the hydrogenation reaction of the copolymer was prepared by the following method.
Charge 1 L of dried and purified cyclohexane to a nitrogen-substituted reaction vessel, add 100 mmol of bis (η5-cyclopentadienyl) titanium dichloride, and add n-hexane solution containing 200 mmol of trimethylaluminum with sufficient stirring. The reaction was allowed to proceed at room temperature for about 3 days.

<Preparation of hydrogenated block copolymer>
(Polymer 1)
Batch polymerization was carried out using a stirring device having an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration 20% by mass) containing 10 parts by mass of styrene was added. Next, 0.06 parts by mass of n-butyllithium with respect to 100 parts by mass of all monomers and N, N, N ′, N′-tetramethylethylenediamine (hereinafter abbreviated as TMEDA) with respect to 1 mol of n-butyllithium. 0.85 mol was added and polymerized at 70 ° C. for 1 hour. Thereafter, a cyclohexane solution (concentration: 20% by mass) containing 40 parts by mass of butadiene was added and polymerized at 70 ° C. for 1 hour. The vinyl bond content of the polybutadiene portion of the polymer sampled at this time was measured and found to be 60%.
Next, a cyclohexane solution (concentration: 20% by mass) containing 14 parts by mass of butadiene and 28 parts by mass of styrene was added and polymerized at 70 ° C. for 1 hour. The vinyl bond content of the polymer sampled at this time was measured and found to be 48%.
Finally, a cyclohexane solution containing 8 parts by mass of styrene was charged and polymerized at 70 ° C. for 1 hour.
The obtained polymer had a styrene content of 46% by mass, a polystyrene block content of 18% by mass, a vinyl bond content of the polybutadiene block part of 48% by mass, a molecular weight of 121,000, and a molecular weight distribution of 1.1.

Next, 100 ppm of the hydrogenation catalyst as titanium was added to 100 parts by mass of the polymer to the obtained polymer, and a hydrogenation reaction was performed at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. Thereafter, methanol was added, and then 0.3 parts by mass of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by mass of the polymer.
The hydrogenation rate of the obtained hydrogenated block copolymer (Polymer 1) was 70%.

(Polymer 2)
Polymer 2 was prepared in the same manner as Polymer 1.
After adding a cyclohexane solution containing 10 parts by mass of styrene, 0.06 parts by mass of n-butyllithium with respect to 100 parts by mass of all monomers and 0.85 mol of TMEDA with respect to 1 mol of n-butyllithium were added, Polymerization was performed at 70 ° C. for 1 hour. Thereafter, a cyclohexane solution containing 27 parts by mass of butadiene was added and polymerized at 70 ° C. for 1 hour. The vinyl bond content of the polybutadiene portion of the polymer sampled at this time was measured and found to be 59%.
Next, a cyclohexane solution containing 14 parts by mass of butadiene and 33 parts by mass of styrene was added and polymerized at 70 ° C. for 1 hour.
Finally, a cyclohexane solution containing 16 parts by mass of styrene was charged and polymerized at 70 ° C. for 1 hour.
The obtained polymer had a styrene content of 59% by mass, a polystyrene block content of 26% by mass, a vinyl bond content of the polybutadiene block part of 47% by mass, a molecular weight of 11,000,000 and a molecular weight distribution of 1.1.
Next, the obtained polymer was subjected to a hydrogenation reaction in the same manner as for polymer 1 to obtain a hydrogenated block copolymer (polymer 2).
The hydrogenation rate of the obtained hydrogenated block copolymer (Polymer 2) was 68%.

(Polymer 3)
Batch polymerization was carried out using a stirring device having an internal volume of 10 L and a jacketed tank reactor. First, a cyclohexane solution (concentration 20% by mass) containing 10 parts by mass of styrene was added. Next, 0.06 parts by mass of n-butyllithium with respect to 100 parts by mass of all monomers and 0.85 mol of TMEDA with respect to 1 mol of n-butyllithium were added and polymerized at 70 ° C. for 1 hour.
Thereafter, a cyclohexane solution (concentration: 20% by mass) containing 40 parts by mass of butadiene was added and polymerized at 70 ° C. for 1 hour. The vinyl bond content of the polybutadiene portion of the polymer sampled at this time was measured and found to be 60%.
Next, a cyclohexane solution (concentration: 20% by mass) containing 14 parts by mass of butadiene and 28 parts by mass of styrene was added and polymerized at 70 ° C. for 1 hour. The vinyl bond content of the polymer sampled at this time was measured and found to be 48%.
Next, a cyclohexane solution containing 8 parts by mass of styrene was charged and polymerized at 70 ° C. for 1 hour.
Further, 1,3-dimethyl-2-imidazolidinone as a modifier was added in an equimolar amount with n-butyllithium used for polymerization, and reacted at 70 ° C. for 20 minutes to obtain a modified block copolymer.
The obtained polymer had a styrene content of 46% by mass, a polystyrene block content of 18% by mass, a vinyl bond content of the polybutadiene block part of 48% by mass, a molecular weight of 121,000, and a molecular weight distribution of 1.1.

Next, 100 ppm of the hydrogenation catalyst as titanium was added to 100 parts by mass of the polymer to the obtained polymer, and a hydrogenation reaction was performed at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. Methanol was then added, and then 0.3 parts by weight of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by weight of the polymer.
The hydrogenation rate of the obtained hydrogenated copolymer (Polymer 3) was 70%. Further, when DSC of the obtained hydrogenated copolymer was measured, no crystallization peak was present.

  The properties of the obtained hydrogenated block copolymers (Polymers 1 to 3) are summarized in Table 1.

[Examples 1 to 4]
After the obtained hydrogenated block copolymer (Polymers 1 to 3) is pelletized, a rubber softener (oil) having the composition shown in Table 2 is added and kneaded with a twin screw extruder (PCM30) to form a pellet. By doing so, a hydrogenated block copolymer composition was obtained.
The extrusion conditions were a cylinder temperature of 130 ° C. and a screw rotation speed of 300 rpm.
The obtained composition was compression molded at 160 ° C. to prepare a sheet having a thickness of 2 mm, and a physical property measurement piece was obtained. Paraffin oil (PW-90: manufactured by Idemitsu Kosan Co., Ltd.) was used as the rubber softener.

[Comparative Examples 1-4]
Using polymer 1, a composition was obtained in the same manner as in Example, a molded sheet was prepared, and physical properties were measured.

  The physical properties of each test piece were measured, and the results are summarized in Table 2.

  As is clear from the results in Table 2, the hydrogenated block copolymer composition of the present embodiment is excellent in transparency, flexibility, low resilience, surface feel (no softener bleed), and shock buffering. The material is suitable as a material that requires the properties and the appearance (color development and transparency).

The composition containing the hydrogenated block copolymer of the present invention has excellent transparency, flexibility, low resilience, surface feel (no softener bleed), and appearance (color development, transparency). As a buffer material, it can be used suitably for various uses.
Taking advantage of these characteristics, it can be processed into molded products of various shapes by injection molding, extrusion molding, etc., and has industrial applicability to medical device materials, household appliances, industrial parts, sports equipment, toys and the like.

Claims (7)

(I) The following (1) to (6) are satisfied,
(1) below (a), (b) and the polymer block chromatic least one each of (c) (a) a vinyl aromatic compound polymer block A
(B) Hydrogenated copolymer block B comprising conjugated diene and vinyl aromatic compound
(C) Hydrogenated polymer block C of conjugated diene polymer having a vinyl bond content of 40% or more
(2) The content of the vinyl aromatic compound in the hydrogenated block copolymer is more than 40% by mass and less than 70% by mass.
(3) Weight average molecular weight is 50,000 to 500,000
(4) The vinyl bond content of the conjugated diene monomer unit constituting the pre-hydrogenation copolymer of the hydrogenated copolymer block B is 10% or more and less than 20%.
(5) The hydrogenation rate of the double bond of the conjugated diene monomer unit is 50% or more.
(6) The content of the vinyl aromatic compound polymer block A in the hydrogenated block copolymer is 5% by mass or more and 30% by mass or less, and the content of the hydrogenated copolymer block B is 30% by mass or more. 50% by mass or less, the content of the hydrogenated polymer block C is more than 35% by mass and 50% by mass or less, and the tan δ (loss tangent) peak is 10 ° C. to 50 ° C., −70 ° C. At least one hydrogenated block copolymer each present at -20 ° C,
(II) 100 to 150 parts by mass of a rubber softener;
A hydrogenated block copolymer composition comprising:
A hydrogenated block copolymer composition having a hardness measured with a durometer type A according to JIS K6253 of 5 to 25 and a rebound resilience measured at 23 ° C. according to BS903 of less than 50%. The hydrogenated block copolymer, wherein at least two have a vinyl aromatic compound polymer block A, according to claim 1 Symbol placement hydrogenated block copolymer composition. The hydrogenated block copolymer composition according to claim 1 or 2 , wherein the hydrogenated block copolymer has the vinyl aromatic compound polymer block A at both ends of the polymer. The hydrogenated block copolymer composition according to any one of claims 1 to 3 , wherein the hydrogenated block copolymer is bonded to an atomic group having a functional group. The peak of tan [delta (loss tangent) in viscoelasticity measurement chart is present at least one in 0 ° C. to 40 ° C., the hydrogenated block copolymer composition according to any one of claims 1-4. The molded article obtained by bridge | crosslinking the hydrogenated block copolymer composition of any one of Claims 1-5 . The molded article according to claim 6 , further comprising a urethane film coated on a surface of the molded article.