JP5731767B2 - Modified hydrogenated block copolymer composition and molded article - Google Patents

Description

  The present invention relates to a modified hydrogenated block copolymer composition in which a modified hydrogenated block copolymer and a rubber softener are combined, and a molded article using the modified hydrogenated block copolymer composition.

  A block copolymer composed of a conjugated diene compound and a vinyl aromatic hydrocarbon compound is a natural rubber or synthetic rubber vulcanized without vulcanization when the proportion of the vinyl aromatic hydrocarbon compound is relatively small. Since it exhibits the same elasticity at room temperature and has the same workability as a thermoplastic resin at high temperatures, it is widely used in the fields of footwear, plastic modification, asphalt modification, adhesives, etc. Yes.

  However, the block copolymer with a relatively small proportion of the vinyl aromatic hydrocarbon compound has good flexibility and resilience, but is inferior in adhesiveness with a polar resin, and cannot provide sufficient shock buffering properties. Has drawbacks.

  On the other hand, conventionally, as a material having flexibility, a vinyl aromatic hydrocarbon compound content is a random copolymer having a content of 3 to 50% by mass, the molecular weight distribution (Mw / Mn) is 10 or less, and A composition in which a hydrogenated diene copolymer obtained by hydrogenating a copolymer having a vinyl bond content of 10 to 90% in a diene part in the copolymer and a polypropylene resin is disclosed (for example, (See Patent Document 1). Further, a random copolymer having a vinyl aromatic hydrocarbon compound content of 5 to 60% by mass, and a copolymer having a vinyl bond content of the diene portion in the copolymer of 60% or more is hydrogenated. The composition which combined the hydrogenated diene type copolymer and polypropylene resin is disclosed (for example, refer patent document 2).

  Furthermore, a thermoplastic elastomer composition having less oil bleed and having excellent mechanical strength, transparency, and flexibility has also been disclosed (see, for example, Patent Document 3).

  Furthermore, an attempt has been made to obtain a flexible material in a block copolymer having a relatively high content of vinyl aromatic hydrocarbon compound, and a block mainly composed of styrene and a block mainly composed of butadiene / styrene. There has been disclosed a molding material based on a hydrogenated block copolymer comprising the copolymer contained (see, for example, Patent Document 4).

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

  However, the compositions disclosed in Patent Documents 1 and 2 have problems that the flexibility is not sufficient and the adhesion to the polar resin is insufficient.

  The thermoplastic elastomer composition disclosed in Patent Document 3 is excellent in flexibility, transparency, and high resilience, has few oil bleeds and excellent moldability, but has insufficient adhesion to polar resins. Has the problem of being.

  Furthermore, although the hydrogenated copolymer disclosed in Patent Document 4 is excellent in low resilience, it is poor in flexibility and also has insufficient shock buffering properties, and also for softening rubber for the purpose of imparting flexibility. When an agent is added, the flexibility is improved, but there is a problem that oil bleeding occurs.

  The present inventors have developed a composition comprising a hydrogenated block copolymer, a hydrogenated block copolymer, and a rubber softener that can be used as a material excellent in impact buffering properties that has both flexibility and low resilience. The product was developed (see WO06 / 088187 pamphlet). However, the present situation is that further improvement is required for adhesiveness with polar resins.

  Therefore, in the present invention, in view of the circumstances described above, it has practically sufficient mechanical strength, is excellent in flexibility, has high resilience, is excellent in adhesiveness with a polar resin, and has an appearance ( It is an object of the present invention to provide a modified hydrogenated block copolymer composition that is also suitable as a soft material that requires transparency and color development associated therewith.

As a result of intensive studies to solve the above problems, the present inventors have determined that a modified hydrogenated block copolymer composition containing a specific modified hydrogenated block copolymer and a rubber softener in a specific ratio. However, the present inventors have found that the problems of the prior art are solved and have completed the present invention.
Details are as follows.

[1]
(I-1) A polymer block A mainly composed of a vinyl aromatic hydrocarbon compound and a polymer block B mainly composed of a conjugated diene compound, wherein the content of the vinyl aromatic hydrocarbon compound is 10 to 40 An atom having at least one functional group selected from the group consisting of a glycidyl group, a glycidoxy group, an alkoxysilyl group, a urea bond, a 5-membered lactam, and a 6-membered lactam in a hydrogenated block copolymer of mass% Modified hydrogenated block copolymer to which a group is bonded: 100 parts by mass;
(II) Rubber softener: 50 to 200 parts by mass;
A modified hydrogenated block copolymer composition.

[2]
(I-1) A polymer block A mainly composed of a vinyl aromatic hydrocarbon compound and a polymer block B mainly composed of a conjugated diene compound, wherein the content of the vinyl aromatic hydrocarbon compound is 10 to 40 An atom having at least one functional group selected from the group consisting of a glycidyl group, a glycidoxy group, an alkoxysilyl group, a urea bond, a 5-membered lactam, and a 6-membered lactam in a hydrogenated block copolymer of mass% A modified hydrogenated block copolymer to which a group is bonded;
(I-2) A hydrogenated block copolymer composed of a conjugated diene compound and a vinyl aromatic compound, which satisfies the following (1) to (6), a glycidyl group, a glycidoxy group, A modified hydrogenated block copolymer to which an atomic group having at least one functional group selected from the group consisting of an alkoxysilyl group, a urea bond, a 5-membered lactam, and a 6-membered lactam is bonded. Modified hydrogenated block copolymer (I-3) mixed at a ratio of 90 to 90/10: 1
00 parts by mass,
(II) Rubber softener: 50 to 200 parts by mass;
A modified hydrogenated block copolymer composition.
(1) It has at least one polymer block of the following (a), (b), and (c).
(A) Vinyl aromatic compound polymer block (b) Hydrogenated copolymer block comprising conjugated diene compound and vinyl aromatic compound (c) Hydrogenated polymer of conjugated diene compound polymer having a vinyl bond content of 40% or more Block (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.
(4) The vinyl bond content of the conjugated diene compound monomer unit constituting the pre-hydrogenation polymer of the hydrogenated polymer block (b) is 10% or more and less than 20%.
(5) The hydrogenation rate of the double bond of the conjugated diene compound monomer unit constituting the block copolymer before hydrogenation of (I-2) 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). 30% by mass or more and 50% by mass or less, and the content of the hydrogenated polymer block (c) exceeds 35% by mass and is 50% by mass or less.
[3]
(I-1) modified hydrogenated block copolymer: 100 parts by mass;
(II) softener for rubber: 50 to 150 parts by mass;
The modified hydrogenated block copolymer composition as described in [1] above.

[4]
The modified hydrogenated block according to any one of [1] to [3] , wherein the hardness according to JIS K6253 is 5 to 35, and the rebound resilience measured at 23 ° C. is 50% or more according to BS903. Polymer composition.

[5]
A modified hydrogenated block copolymer composition obtained by crosslinking the modified hydrogenated block copolymer composition according to any one of [1] to [4] .

[6]
A molded article obtained by molding the modified hydrogenated block copolymer composition according to any one of [1] to [5] .

[7]
The molded product according to [6] , further including a urethane film on a surface of the molded product.

  According to the present invention, processability, flexibility, high resilience, surface feel is good, there is no softening bleed, excellent adhesion with a polar resin, and appearance such as transparency and color developability is good. A modified hydrogenated block copolymer composition that can be suitably applied to various uses is obtained.

  Hereinafter, modes for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described. However, the present invention is not limited to the modes shown below, and various modifications can be made within the scope of the gist. Can be implemented.

  Modified hydrogenated block containing 100 parts by mass of modified hydrogenated block copolymer (I-1) described later as a first embodiment and 50 to 200 parts by mass of a softening agent for rubber (II) described later. A copolymer composition is provided.

  As 2nd Embodiment, the modified hydrogenated block copolymer (I-1) mentioned later and the modified hydrogenated block copolymer (I-2) mentioned later are in ratio of 10 / 90-90 / 10. Provided is a modified hydrogenated block copolymer composition containing 100 parts by mass of a mixed modified hydrogenated block copolymer (I-3) and a softening agent for rubber (II) described later: 50 to 200 parts by mass. To do.

[Modified Hydrogenated Block Copolymer Composition of First Embodiment]
As described above, the modified hydrogenated block copolymer composition of the first embodiment is
(I-1) It has a polymer block A mainly composed of a vinyl aromatic hydrocarbon compound and a polymer block B mainly composed of a conjugated diene compound, and the content of the vinyl aromatic hydrocarbon compound is 5 to 50 Modified hydrogenated block copolymer in which an atomic group having a functional group is bonded to the hydrogenated block copolymer of 100% by mass: 100 parts by mass;
(II) Rubber softener: 50 to 200 parts by mass;
Is a modified hydrogenated block copolymer composition.

((I-1) Modified hydrogenated block copolymer)
(I-1) The modified hydrogenated block copolymer has a polymer block A mainly composed of a vinyl aromatic hydrocarbon compound and a polymer block B mainly composed of a conjugated diene compound.
The above “mainly composed of a vinyl aromatic hydrocarbon compound” means that the content of the vinyl aromatic hydrocarbon compound in the polymer block A is 50% by mass or more. “Mainly” means that the content of the conjugated diene in the polymer block B is 50% by mass or more.
The vinyl aromatic hydrocarbon compound content of the hydrogenated block copolymer before modification of this (I-1) modified hydrogenated block copolymer is the same as the machine of the modified hydrogenated block copolymer composition of this embodiment. From the viewpoint of strength, it should be 5% by mass or more, and from the viewpoint of hardness, it should be 50% by mass or less, preferably 10 to 40% by mass, and more preferably 15 to 35% by mass.

((I-1) Method for Producing Modified Hydrogenated Block Copolymer)
First, a method for producing a block copolymer before modification and before hydrogenation will be described. Examples of the method for producing this block copolymer include Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-17879, Japanese Patent Publication No. 46-32415, Japanese Patent Publication No. 49-36957, Japanese Patent Publication No. 48-2423. The methods described in Japanese Patent Publication No. 48, Japanese Patent Publication No. 48-4106, Japanese Patent Publication No. 51-49567, Japanese Patent Publication No. 59-166518, and the like can be applied.
The production method described above includes a “conjugated diene compound” described later and a “vinyl aromatic hydrocarbon compound” using “polymerization solvent” and “polymerization catalyst” described later, “polymerization conditions” described later. To obtain a block copolymer before the modification and before hydrogenation.
A modified block copolymer containing a functional group is obtained by subjecting the living end of the block copolymer obtained by these methods to an addition reaction according to a modification reaction described later using a modification agent described later.
The modified block copolymer has a structure represented by the following general formula, for example.

(AB) _n -Z, A- (BA) _n -Z, B- (AB) _n -Z, Z- (AB) _n ,
Z- (AB) _n -Z, ZA- (BA) _n -Z, ZB- (AB) _n -Z,
_{[(B-A) n]} m -Z, [(A-B) n] m -Z, [(B-A) n -B] m -Z,
[(A−B) _n −A] _m −Z

In the above general formula, A is a polymer block mainly composed of a vinyl aromatic hydrocarbon compound.
B is a polymer block mainly composed of a conjugated diene compound.
The boundary between the A block and the B block does not necessarily have to be clearly distinguished.
n is an integer of 1 or more, preferably an integer of 1 to 5.
m is an integer of 2 or more, preferably an integer of 2 to 11.
Z shows the residue of the modifier | denaturant which the atomic group which has a functional group mentioned later has couple | bonded.
When adding Z by the metallation reaction mentioned later, it has couple | bonded with the side chain of A block and / or B block.
When a plurality of A blocks and B blocks are present in the block copolymer, their structures may be the same or different.
Moreover, the structure of the polymer chain bonded to Z may be the same or different.

In the above, the polymer block A mainly composed of a vinyl aromatic hydrocarbon compound is preferably a vinyl aromatic hydrocarbon compound containing 50% by mass or more, more preferably 70% by mass or more of a vinyl aromatic hydrocarbon compound. A copolymer block of a conjugated diene compound or a vinyl aromatic hydrocarbon compound homopolymer block is shown.
In the above, the polymer block B mainly composed of a conjugated diene compound is preferably a conjugated diene compound containing more than 50% by mass, more preferably 60% by mass or more, and a vinyl aromatic hydrocarbon. A copolymer block with a compound or a conjugated diene compound homopolymer block is shown.

The vinyl aromatic hydrocarbon compound in the polymer block B mainly composed of the conjugated diene compound may be distributed uniformly or in a tapered shape.
In the copolymer block part, a part where the vinyl aromatic hydrocarbon compound is uniformly distributed and / or a part where the vinyl aromatic hydrocarbon compound is distributed in a tapered shape may coexist.
Further, a plurality of portions having different vinyl aromatic hydrocarbon compound contents may coexist in the copolymer block portion.
The block copolymer for forming the modified hydrogenated block copolymer composition of this embodiment may be an arbitrary mixture of block copolymers represented by the above general formula.

The microstructure (cis, trans, vinyl ratio) of the conjugated diene compound portion in the block copolymer for forming the modified hydrogenated block copolymer composition of the present embodiment can be determined by using a polar compound or the like described later. It can be changed arbitrarily. Specifically, when 1,3-butadiene is used as the conjugated diene compound, the 1,2-vinyl bond content is preferably 10 to 80%, more preferably 25 to 75%. When isoprene is used as the conjugated diene compound or when 1,3-butadiene and isoprene are used in combination, the total amount of 1,2-vinyl bond and 3,4-vinyl bond is preferably 5 to 70%. is there.
In this specification, the total amount of 1,2-vinyl bond and 3,4-vinyl bond (however, when 1,3-butadiene is used as the conjugated diene compound, 1,2-vinyl bond is used. Amount) is hereinafter referred to as the vinyl bond amount.

(Conjugated diene compounds)
The conjugated diene compound constituting the block copolymer for forming the modified hydrogenated block copolymer composition of the present embodiment is a diolefin having a pair of conjugated double bonds.
Examples include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, Particularly common are 1,3-butadiene and isoprene.
These may be used alone or in combination of two or more when producing one block copolymer.

When isoprene and 1,3-butadiene are used in combination as the conjugated diene constituting the block copolymer for forming the modified hydrogenated block copolymer composition of the present embodiment, isoprene and 1,3-butadiene. The mass ratio is preferably 95/5 to 5/95, more preferably 90/10 to 10/90, and still more preferably 85/15 to 15/85.
In particular, when isoprene and 1,3-butadiene are used in combination, a modified hydrogenated block copolymer composition having a good balance between appearance characteristics and mechanical characteristics can be obtained even during molding at high temperatures.

(Vinyl aromatic hydrocarbon compounds)
Examples of the vinyl aromatic hydrocarbon compound constituting the block copolymer for forming the modified hydrogenated block copolymer composition of the present embodiment include styrene, o-methylstyrene, p-methylstyrene, p -Tert-butyl styrene, 1,3-dimethyl styrene, α-methyl styrene, vinyl naphthalene, vinyl anthracene and the like can be mentioned, and styrene is particularly common.
These may be used alone or in combination of two or more when producing one block copolymer.

The content of the vinyl aromatic hydrocarbon compound in the hydrogenated block copolymer before modification of the modified hydrogenated block copolymer constituting the modified hydrogenated block copolymer composition of the present embodiment is determined by the UV method. , And can be measured by NMR method.
In addition, the content of the vinyl aromatic hydrocarbon compound present in the block A can be determined by the following analysis method.
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 block 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) using a block copolymer before hydrogenation or a block copolymer after hydrogenation as a specimen (Y. Tanaka, et al. , RUBBER 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 block copolymer before hydrogenation by the osmium tetroxide method and the copolymer after hydrogenation by the NMR method are used. The content (referred to as Ns) of the polymer block A measured in this manner 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.

(Polymerization solvent)
Examples of the solvent used for producing the block copolymer for forming the modified hydrogenated block copolymer composition of the present embodiment include fats such as butane, pentane, hexane, isopentane, heptane, octane, and isooctane. And hydrocarbon solvents such as alicyclic hydrocarbons such as aromatic hydrocarbons, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane and ethylcyclohexane, and aromatic hydrocarbons such as benzene, toluene, ethylbenzene and xylene. These may be used alone or in combination of two or more.

(Polymerization catalyst)
An organic lithium compound is used as a polymerization catalyst used for producing the block copolymer for forming the modified hydrogenated block copolymer composition of the present embodiment.
The organic lithium compound is a compound in which one or more lithium atoms are bonded in the molecule, such as ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, hexamethylene. Examples include dilithium, butadienyl dilithium, and isoprenyl dilithium. These may be used alone or in combination of two or more. Further, the organolithium compound may be added in one or more divided portions during the polymerization in the production of the block copolymer.

In the polymerization step of the block copolymer to form the modified hydrogenated block copolymer composition of the present embodiment, the polymerization rate is adjusted, the microstructure of the polymerized conjugated diene compound portion is changed, the conjugated diene compound and vinyl For the purpose of adjusting the reactivity ratio with the aromatic hydrocarbon compound, a polar compound or a randomizing agent may be used.
Examples of polar compounds and randomizing agents include ethers, amines, thioethers, phosphoramides, potassium or sodium salts of alkylbenzene sulfonic acids, potassium or sodium alkoxides, and the like.
Examples of ethers include dimethyl ether, diethyl ether, diphenyl ether, tetrahydrofuran, diethylene glycol dimethyl ether, and diethylene glycol dibutyl ether.
Examples of amines include tertiary amines, trimethylamine, triethylamine, tetramethylethylenediamine, and other cyclic tertiary amines.
Examples of phosphoramides include triphenylphosphine and hexamethylphosphoramide.

(Polymerization conditions)
In the block copolymer production process for forming the modified hydrogenated block copolymer composition of the present embodiment, the polymerization temperature is preferably −10 to 150 ° C., more preferably 30 to 120 ° C.
The time required for the polymerization varies depending on the conditions, but is preferably within 48 hours, particularly preferably 0.5 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 preferable that impurities such as water, oxygen, carbon dioxide gas, etc. that inactivate the catalyst and the living polymer are not mixed in the polymerization system.

As described above, a block copolymer obtained using an organolithium compound as a polymerization catalyst is mainly composed of a polymer block A mainly composed of at least one vinyl aromatic hydrocarbon compound and at least one conjugated diene compound. As described later, a functional group-containing modifier is added to the living end of this block copolymer to obtain a modified block copolymer. Thereafter, hydrogenation is performed to obtain a modified hydrogenated block copolymer (I-1).
The modification reaction may be carried out after hydrogenation of the polymer block copolymer.

(Denaturation reaction)
The block copolymer obtained as described above is subjected to a modification reaction as follows.
In the modified block copolymer, at least one atomic group having at least one functional group is bonded.
By the addition reaction with the living terminal of the block copolymer obtained as described above, a modified block copolymer in which an atomic group having at least one functional group is bonded to the block copolymer is generated. It can be obtained by addition reaction of a modifier having a functional group or a modifier having an atomic group protected by a known method.
As another method, the block copolymer is reacted with an organic alkali metal compound such as an organolithium compound (metalation reaction), and a polymer obtained by adding an organic alkali metal to the block copolymer is added to a predetermined modifier. Can be added.
In the case of the latter method, after obtaining the hydrogenated product of the block copolymer, a metallation reaction may be performed, and the above modifier may be reacted.

Depending on the type of modifier, at the stage of reaction of the modifier, generally hydroxyl groups, amino groups, etc. may be alkali metal salts, but in that case they have active hydrogen such as water, alcohol, inorganic acid, etc. By treating with a compound (active hydrogen-containing compound), a hydroxyl group, an amino group, or the like can be obtained.
In addition, when making a modifier react with the living terminal of a block copolymer, the block copolymer which is not modified | denatured partially may be mixed in the modified hydrogenated block copolymer of (I-1).
The proportion of the unmodified hydrogenated block copolymer mixed in the modified hydrogenated block copolymer (I-1) is preferably 70% by mass or less, preferably 60% by mass or less, and 50 More preferably, it is at most mass%.

(Modifier)
Examples of the modifying agent include the following.
For example, tetraglycidyl metaxylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl-p-phenylenediamine, tetraglycidyldiaminodiphenylmethane, diglycidylaniline, diglycidylorthotoluidine, 4,4'-diglycidyl Examples include polyepoxy compounds such as diphenylmethylamine, 4,4′-diglycidyldibenzylmethylamine, and diglycidylaminomethylcyclohexane.

  Also, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxy Silane, γ-glycidoxypropyl tributoxysilane, γ-glycidoxypropyltriphenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldi Ethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycine Sidoxypropi Dimethylmethoxysilane, γ-glycidoxypropyldiethylethoxysilane, γ-glycidoxypropyldimethylethoxysilane, γ-glycidoxypropyldimethylphenoxysilane, γ-glycidoxypropyldiethylmethoxysilane, γ-glycidoxypropyl Examples thereof include methyldiisopropeneoxysilane, bis (γ-glycidoxypropyl) dimethoxysilane, and bis (γ-glycidoxypropyl) diethoxysilane.

  Also, bis (γ-glycidoxypropyl) dipropoxysilane, bis (γ-glycidoxypropyl) dibutoxysilane, bis (γ-glycidoxypropyl) diphenoxysilane, bis (γ-glycidoxypropyl) Methylmethoxysilane, bis (γ-glycidoxypropyl) methylethoxysilane, bis (γ-glycidoxypropyl) methylpropoxysilane, bis (γ-glycidoxypropyl) methylbutoxysilane, bis (γ-glycidoxy) Propyl) methylphenoxysilane, tris (γ-glycidoxypropyl) methoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxymethyltrimethoxysilane, γ-methacryloxyethyl Triethoxysilane, bis (γ-me Tacryloxypropyl) dimethoxysilane, tris (γ-methacryloxypropyl) methoxysilane.

  Β- (3,4-epoxycyclohexyl) ethyl-trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-triethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-tripropoxysilane, Examples include β- (3,4-epoxycyclohexyl) ethyl-tributoxysilane and β- (3,4-epoxycyclohexyl) ethyl-triphenoxysilane.

  Β- (3,4-epoxycyclohexyl) propyl-trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-ethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-ethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldipropoxysilane , Β- (3,4-epoxycyclohexyl) ethyl-methyldibutoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiphenoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylmethoxysilane , Β- (3,4-epoxycyclohexyl) ) Ethyl-diethylethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylpropoxysilane, β- (3,4-epoxycyclohexyl) ethyl -Dimethylbutoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylphenoxysilane.

  Further, β- (3,4-epoxycyclohexyl) ethyl-diethylmethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiisopropeneoxysilane, N- (1,3-dimethylbutylidene) -3 -(Triethoxysilyl) -1-propanamine is mentioned.

  1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N, N′-dimethylpropyleneurea, 1,3-diethyl-2-imidazolidinone, 1,3 -Dipropyl-2-imidazolidinone, 1-methyl-3-ethyl-2-imidazolidinone, 1-methyl-3-propyl-2-imidazolidinone, 1-methyl-3-butyl-2-imidazolidinone 1-methyl-3- (2-methoxyethyl) -2-imidazolidinone, 1-methyl-3- (2-ethoxyethyl) -2-imidazolidinone, 1,3-di- (2-ethoxyethyl) ) -2-imidazolidinone, 1,3-dimethylethylenethiourea, N, N′-diethylpropyleneurea, N-methyl-N′-ethylpropyleneurea and the like.

  1-methyl-2-pyrrolidone, 1-cyclohexyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-propyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, 1-isopropyl-2-pyrrolidone, 1,5-dimethyl-2-pyrrolidone, 1-methoxymethyl-2-pyrrolidone, 1-methyl-2-piperidone, 1,4-dimethyl-2-piperidone, 1-ethyl-2-piperidone, 1-isopropyl-2 -Piperidone, 1-isopropyl-5,5-dimethyl-2-piperidone and the like.

By reacting the above modifier, a modified hydrogenated block copolymer (I-1) to which a residue of the modifier to which an atomic group having at least one functional group is bonded is bonded is obtained.
Since the modified hydrogenated block copolymer (I-1) has a nitrogen atom, an oxygen atom, a carbonyl group, etc., the modified hydrogenated block copolymer (I-1) interacts with each other by physical affinity such as hydrogen bonding between polar groups of the polar resin. The effect is effectively expressed, and the effect of improving the adhesiveness with the polar resin is exhibited.

  When the functional group-containing modifier is added to the living end of the block copolymer described above, the living end of the block copolymer may be either the polymer block A or the polymer block B. In the modified hydrogenated block copolymer composition, it is preferably bonded to the end of the polymer block A in order to have an excellent balance of mechanical strength and impact resistance.

The use amount of the functional group-containing modifier described above is preferably more than 0.5 equivalent and less than or equal to 10 equivalents, more preferably greater than 0.7 equivalents and less than or equal to 5 equivalents with respect to 1 equivalent of the living terminal of the block copolymer. More preferably, the equivalent is more than 4 equivalents.
In the present invention, the amount of the living end of the block copolymer can be calculated from the amount of the organolithium compound of the polymerization catalyst used for the polymerization.

(Hydrogenation reaction)
The modified hydrogenated block copolymer (I-1) can be obtained by hydrogenating the modified block copolymer obtained as described above.
(Hydrogenation catalyst)
The hydrogenation catalyst is not particularly limited and is conventionally known (1) A supported heterogeneous hydrogenation in which a metal such as Ni, Pt, Pd, or Ru is supported on carbon, silica, alumina, diatomaceous earth, or the like. A catalyst, (2) a 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 organoaluminum, (3) Ti, Ru, A homogeneous hydrogenation catalyst such as a so-called organometallic complex such as an organometallic compound such as Rh or Zr is used.
Specifically, JP-B-42-8704, JP-B-43-6636, JP-B-63-4841, JP-B-1-37970, JP-B-1-53851, JP-B-2-9041 Can be used.

Preferred hydrogenation catalysts include mixtures with titanocene compounds and / or reducing organometallic compounds.
As the titanocene compound, compounds described in JP-A-8-109219 can be used. Specific examples include at least one or more ligands having a (substituted) cyclopentadienyl skeleton, indenyl skeleton or fluorenyl skeleton such as biscyclopentadienyl titanium dichloride and monopentamethylcyclopentadienyl titanium trichloride. Compounds.
Examples of the reducing organometallic compound include organic alkali metal compounds such as organolithium, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds.

(Hydrogenation reaction conditions)
The hydrogenation reaction is preferably carried out in a temperature range of 0 to 200 ° C, more preferably 30 to 150 ° C.
The pressure of hydrogen used for the hydrogenation reaction is preferably 0.1 to 15 MPa, more preferably 0.2 to 10 MPa, and still more preferably 0.3 to 5 MPa.
The hydrogenation reaction time is preferably 3 minutes to 10 hours, more preferably 10 minutes to 5 hours.
The hydrogenation reaction can be applied as a batch process, a continuous process, or a combination thereof.

The total hydrogenation rate of the unsaturated double bond based on the conjugated diene compound constituting the modified hydrogenated block copolymer (I-1) can be arbitrarily selected according to the purpose and is not particularly limited.
70% or more of the unsaturated double bond based on the conjugated diene compound in the block copolymer before hydrogenation before the modification of the modified hydrogenated block copolymer (I-1), preferably 80% or more, More preferably, 90% or more may be hydrogenated, or only a part may be hydrogenated.
When only a part is hydrogenated, it is recommended that the hydrogenation rate be 10% or more and less than 70%, or 15% or more and less than 65%, or 20% or more and less than 60% as desired.
When heat stability is highly required, it is preferably 70% or more. When high heat stability is not required, only a part of the material may be hydrogenated as described above. .

Furthermore, in the modified hydrogenated block copolymer, the hydrogenation rate of the vinyl bond based on the conjugated diene compound before hydrogenation is preferably 85% or more, more preferably 90% or more, and 95% or more. More preferably. Thereby, the composition excellent in thermal stability is obtained.
Here, the hydrogenation rate of vinyl bonds refers to the ratio of hydrogenated vinyl bonds among vinyl bonds based on the conjugated diene compound before hydrogenation incorporated in the block copolymer.
The amount of vinyl bonds based on the conjugated diene compound in the modified hydrogenated block copolymer can be known using a nuclear magnetic resonance apparatus (NMR).
The hydrogenation rate can also be known using the same apparatus.
The hydrogenation rate of the vinyl aromatic double bond based on the vinyl aromatic hydrocarbon compound in the modified 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 can be measured by a nuclear magnetic resonance apparatus (NMR).

[(I-1) Weight Average Molecular Weight of Modified Hydrogenated Block Copolymer]
The weight average molecular weight of the modified hydrogenated block copolymer (I-1) is preferably 30,000 or more from the viewpoint of mechanical strength of the composition, and preferably 1,000,000 or less from the viewpoint of workability, more preferably 40,000. ˜500,000, more preferably 5 to 300,000.
The weight average molecular weight of the modified hydrogenated block copolymer was measured by gel permeation chromatography (GPC), and a calibration curve obtained from measurement of commercially available standard polystyrene (created using the peak molecular weight of standard polystyrene) Is the weight average molecular weight determined using

The solution of the modified hydrogenated block copolymer (I-1) obtained as described above can be separated from the solution by removing the catalyst residue as necessary.
Solvent separation methods include, for example, a method in which a polar solvent that is a poor solvent for a polymer such as acetone or alcohol is added to a solution after polymerization or hydrogenation, and the polymer is precipitated and recovered. Examples thereof include a method in which the mixture is poured into hot water with stirring and the solvent is removed by steam stripping, or a method in which the solvent is distilled off by directly heating the polymer solution.
In addition, stabilizers such as various phenol stabilizers, phosphorus stabilizers, sulfur stabilizers and amine stabilizers may be added to the modified hydrogenated block copolymer (I-1).

[Modified Hydrogenated Block Copolymer Composition of Second Embodiment]
The modified hydrogenated block copolymer composition of the second embodiment comprises the above-described (I-1) modified hydrogenated block copolymer and (I-2) modified hydrogenated block copolymer described later. The mixture is mixed at a ratio of 10/90 to 90/10 (the mixture is referred to as (I-3)), and the mixture (I-3): 100 parts by mass is further added with (II) a rubber softener described later. 50 to 200 parts by mass are contained.

The (I-2) modified hydrogenated block copolymer is a hydrogenated block copolymer comprising a conjugated diene compound and a vinyl aromatic compound, and the hydrogenated block copolymer satisfying the following (1) to (6): An atomic group having a functional group is bonded to the polymer.
(1) It has at least one polymer block of the following (a), (b), and (c).
(A) Vinyl aromatic compound polymer block (b) Hydrogenated copolymer block comprising conjugated diene compound and vinyl aromatic compound (c) Hydrogenated polymer of conjugated diene compound polymer having a vinyl bond content of 40% or more Block (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.
(4) The vinyl bond content of the conjugated diene compound monomer unit constituting the pre-hydrogenation polymer of the hydrogenated polymer block (b) is 10% or more and less than 20%.
(5) The hydrogenation rate of the double bond of the conjugated diene compound monomer unit constituting the block copolymer before hydrogenation of (I-2) 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). 30% by mass or more and 50% by mass or less, and the content of the hydrogenated polymer block (c) exceeds 35% by mass and is 50% by mass or less.

  The (I-2) modified hydrogenated block copolymer can be produced in the same manner as the above-described modified hydrogenated block copolymer (I-1), but is disclosed in International Publication No. 06/088187. The block copolymer having the structure as described above is a copolymer which has been modified and hydrogenated by the production method disclosed in the modified hydrogenated block copolymer of (I-1).

((II) Rubber softener)
In the first embodiment, the above-described modified hydrogenated block copolymer (I-1) is used, and in the second embodiment, the above-described modified water (I-1) and (I-2) are used. By using a modified hydrogenated block copolymer in which a block copolymer is mixed at a predetermined ratio and obtaining a composition in combination with (II) a rubber softener, effective softening is achieved, and further better Processability can be imparted.
Examples of the rubber softener (II) include mineral oil rubber softeners and liquid or low molecular weight synthetic softeners, and naphthenic and / or paraffinic process oils or extender oils are particularly 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, Those having 30 to 45% carbon are called naphthenes, and those having more than 30% aromatics are called aromatics.

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

The compounding amount of the rubber softener (II) is the above-mentioned (I-1) modified hydrogenated block copolymer or a mixture of the modified hydrogenated block copolymer of (I-1) and (I-2). The amount is 50 to 200 parts by mass, preferably 70 to 150 parts by mass with respect to 100 parts by mass.
The amount of the rubber softener (II) is 200 parts by mass with respect to 100 parts by mass of the modified hydrogenated block copolymer ((I-1) alone or a mixture of (I-1) and (I-2)). If it exceeds 1, the rubber softener tends to bleed out and the surface feel deteriorates.
On the other hand, when the rubber softener is less than 50 parts by mass, the hardness of the modified hydrogenated block polymer composition of the present embodiment becomes too high, and it becomes difficult to obtain practically sufficient flexibility, which is not preferable.

[Additives]
An arbitrary additive can be blended with the modified hydrogenated block copolymer composition of the present embodiment, if necessary.
The 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, reinforcing agents such as organic fibers, glass fibers, carbon fibers, and metal whiskers.
These may be used alone or in any combination.

In the modified hydrogenated block copolymer composition of the present embodiment, an optional filler and a flame retardant may 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 may be used alone or in combination of two or more.

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 aid 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 that has been surface-treated with a surface treatment agent such as a silane coupling agent in advance may be used.

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

[Bridge]
The modified hydrogenated block copolymer composition of the present embodiment can be subjected to a crosslinking treatment as necessary.
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, phenols, isocyanates, thiurams, and morpholine disulfides.
These can be used in combination with a crosslinking aid such as stearic acid, oleic acid, zinc stearate, and zinc oxide, a co-crosslinking agent, and a vulcanization accelerator.

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.

[Method for Producing Modified Hydrogenated Block Copolymer Composition]
The method for producing the modified hydrogenated block copolymer composition of the present embodiment is not particularly limited, and known methods can be applied.
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.
The shape of the resulting modified hydrogenated block copolymer composition is not particularly limited, and examples thereof include pellets, sheets, strands, and chips.

[Molded product of modified hydrogenated block copolymer composition]
A molded article can be obtained by molding the modified hydrogenated block copolymer composition described above. After the above composition is melt-kneaded, it may be formed directly.
As the molding method, 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 applied.

The modified hydrogenated block copolymer composition of the present embodiment may be a foam molded article.
Examples of methods applicable for obtaining foamed molded products include chemical methods, physical methods, and the like. Chemical foaming agents such as inorganic foaming agents and organic foaming agents, and foaming such as physical foaming agents, respectively. Bubbles can be distributed inside the material by adding an agent or the like.
By using the modified hydrogenated block copolymer composition as a foam material, effects such as weight reduction, flexibility improvement, and design improvement can be obtained.

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

  Examples of the organic foaming agent include azodicarbonamide, azobisformamide, azobisisobutyronitrile, barium azodicarboxylate, N, N′-dinitrosopentamethylenetetramine, N, N′-dinitroso-N, N Examples include '-dimethyl terephthalamide, benzenesulfonyl hydrazide, p-toluenesulfonyl hydrazide, p, p'-oxybisbenzenesulfonyl hydrazide, p-toluenesulfonyl semicarbazide and the like.

  Examples of 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, and trichlorotrifluoroethane. Fluorinated hydrocarbons such as chlorodifluoroethane and hydrofluorocarbon.

  The molded article of the modified hydrogenated block copolymer composition may be formed by subjecting the modified hydrogenated block copolymer composition to a crosslinking treatment.

  The molded product of the modified hydrogenated block copolymer composition of the present embodiment is subjected to predetermined printing, painting, coating for the purpose of improving the appearance, weather resistance, scratch resistance, etc. on the surface as necessary. , Decoration such as wrinkles 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 formed 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 modified hydrogenated block copolymer composition of the present embodiment can be mixed with various additives as necessary to have various modes and can be used according to the application.

  With respect to specific aspects of the modified hydrogenated block copolymer composition of this embodiment, (i) a reinforcing filler formulation, (ii) a crosslinked product, (iii) a foam, (iv) a multilayer film and a multilayer sheet (V) building materials, (vi) vibration damping / soundproof materials, (vii) wire covering materials, (viii) high frequency fusible compositions, (ix) slush molding materials, (x) adhesives And (xi) asphalt composition, (xii) medical device material, (xiii) automobile material and the like.

(Use of molded products)
The molded product can be used as a sheet, a film, a tube, a nonwoven fabric, a fibrous molded product, synthetic leather, or the like.

Examples of the present invention and comparative examples will be specifically described below.
The physical property measurement method and evaluation method applied to the examples and comparative examples are shown below.

[(1) Properties of hydrogenated block copolymer]
(1-1) Content of vinyl aromatic hydrocarbon compound (styrene) in hydrogenated block copolymer Using a block copolymer before hydrogenation, an ultraviolet spectrophotometer (manufactured by Shimadzu Corporation, UV-2450) is used. And measured.

(1-2) Content of Vinyl Aromatic Hydrocarbon Compound in Hydrogenated Block Copolymer Using the block copolymer before hydrogenation, M.M. Kolthoff, et al. , J .; Polym. Sci. 1, 429 (1946).
For the decomposition of the block copolymer, an osmic acid 0.1 g / 125 ml tertiary butanol solution was used.

(1-3) Vinyl Bond Amount of Hydrogenated Block Copolymer A block 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 Measured by GPC [Equipment: Tosoh Co., Ltd., HLC-8120GPC].
Tetrahydrofuran was used as the solvent, and the measurement was performed at a temperature of 35 ° C.
The weight average molecular weight and number average molecular weight were determined using a calibration curve prepared using a known commercially available standard polystyrene.
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 compound monomer unit of hydrogenated block copolymer
The hydrogenated block 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 modification rate was measured using the property that the modified hydrogenated block copolymer was adsorbed on a silica gel column but not adsorbed on a polystyrene gel column.
For a sample solution containing a measurement 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 modified 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 was less than 10 kg / cm ² , it was judged that the strength was insufficient from a practical viewpoint.

(2-4) Transparency A press sheet having a thickness of 2 mm was prepared, five sheets were stacked and placed on a newspaper, and the degree to which the printed characters could be read visually was determined and evaluated 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: Rebound resilience The rebound resilience was measured at 23 ° C. according to BS903 using a Dunlop rebound resilience tester.
When it was 50% or more, it was judged to be practically good.

(2-6) Surface feel A press sheet having a thickness of 2 mm was prepared and evaluated by the following method.
(Adhesive feeling): The surface of the sheet was touched with a finger to confirm the presence or absence of stickiness.
(Oil bleed): Paper was sandwiched between sheets, and after 24 hours, the presence or absence of oil transfer to the paper was confirmed. As the evaluation paper, color monochrome paper C2 A4 version (Fuji Xerox Co., Ltd.) was used.
When there was either stickiness or oil bleed, it was judged that the practical characteristics were poor.

(2-8) Adhesiveness Adhesiveness was evaluated from the measurement of adhesive strength by a T-type peel test.
The greater the adhesive strength, the better the adhesiveness.
The adhesion conditions and peel test conditions are shown below.
[Adhesion conditions]
The modified hydrogenated block copolymer composition was press-molded at 200 ° C. into a 2 mm thick sheet.
Thereafter, the surface of the sheet was surface-treated with a 3% ethyl acetate solution of triallyl isocyanurate containing hypochlorous acid, and further immersed in a butyl acetate solution of moisture-curable polyurethane, and the surface was urethane-coated sample sheet. Was made.
The urethane-coated sample sheet and a 2 mm thick sheet made of urethane elastomer were bonded with a two-component curable urethane adhesive.
Then, the sheet | seat was cut | disconnected in 2 cm width strip shape, and the peeling test mentioned later was measured.
[Peel test]
The peeling speed was 200 mm / min.
The peel strength was measured in units of kg / 2 cm.
It was judged that the higher the peel strength, the better.
When the adhesion was not sufficient, peeling occurred on the adhesive surface between the urethane coating layer and the composition.
When it was excellent in adhesiveness, the inside of the sheet | seat which consists of a composition fractured | ruptured, and it was confirmed that peeling strength was strong.

[Preparation of Modified Hydrogenated Block Copolymer Composition]
(Preparation of hydrogenation catalyst)
The hydrogenation catalyst used in the hydrogenation reaction of the block copolymer to obtain the hydrogenated block copolymer constituting the modified hydrogenated block copolymer composition prepared in the examples and comparative examples described later, 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 carried out at room temperature for about 3 days.

(Preparation of Modified Hydrogenated Block Copolymer (I-1))
<Living polymer of block copolymer (I-1) -1: Pa-1>
An autoclave equipped with a stirrer and a jacket was washed, dried and purged with nitrogen, and a cyclohexane solution (concentration 20% by mass) containing 10 parts by mass of styrene purified in advance was added.
Next, n-butyllithium and tetramethylethylenediamine were added and polymerized at 70 ° C. for 1 hour.
Then, a cyclohexane solution (concentration 20% by mass) containing 80 parts by mass of pre-purified butadiene was added and polymerized at 70 ° C. for 1 hour, and a cyclohexane solution containing 10 parts by mass of styrene was further added and polymerized at 70 ° C. for 1 hour. A living polymer of a block copolymer was obtained. The properties of the obtained block copolymer are shown in Table 1 below.

<Living polymer of block copolymer (I-1) -2 to (I-1) -4: Pa-2 to Pa-4>
The block copolymer living polymer having the characteristics shown in Table 1 was obtained in the same manner as the above-described block copolymer living polymer (I-1) -1: Pa-1.
In these, the charge ratio of styrene and butadiene was adjusted, the content of styrene was changed, and further the amount of tetramethylethylenediamine was changed to prepare the vinyl bond amount.

Next, a modified block copolymer and a hydrogenated product thereof were prepared using the block copolymer living polymer obtained as described above, a modifier, and a hydrogenation catalyst.
The block copolymer living polymer (I-1) -1: Pa-1 to (I-1) -4: Pa-4 was added with a predetermined amount of modifier shown in Table 2 below, and 70 A modified block copolymer was obtained by reacting at 20 ° C. for 20 minutes.
Next, 100 ppm of a hydrogenation catalyst as Ti is added to the solution of the above modified block copolymer, and a hydrogenation reaction is performed at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. for 1 hour to obtain a solution of the modified hydrogenated block copolymer. Got.
Next, 10 times mole of methanol was added to this solution with respect to n-butyllithium used for the polymerization, and then carbonated water was added to adjust the pH to 8 or less.
The properties of the modified block copolymer and hydrogenated products (Pa-1: HPa-1) to (Pa-4: HPa-5) thus obtained are shown in Table 2 below.

In addition, the specific material name of the modifier shown in Table 2 is shown below.
M1: 1,3-dimethyl-2-imidazolidinone M2: tetraglycidyl-1,3-bisaminomethylcyclohexane M3: γ-glycidoxypropyltrimethoxysilane

(Preparation of modified hydrogenated block copolymer (I-2))
(Living polymer of block copolymer (I-2) -1 to (I-2) -2)
Batch polymerization was carried out using a tank reactor equipped with a stirrer and a jacket having an internal volume of 10 L.
First, a cyclohexane solution (concentration 20% by mass) containing 10 parts by mass of styrene was added.
Next, 0.05 parts by mass of n-butyllithium with respect to 100 parts by mass of all monomers and 0.85 mol of TMEDA (tetramethylethylenediamine) are added to 1 mol of n-butyllithium, and 1 at 70 ° C. Polymerized for hours.
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.

To the living polymer (I-2) -1 of the block copolymer, 1,3-dimethyl-2-imidazolidinone as an modifier was added in an equimolar amount with n-butyllithium used in the polymerization, and 70 The mixture was reacted at 20 ° C. for 20 minutes to obtain a modified block copolymer.
On the other hand, a polymer to which no modifier was added was designated as a block copolymer living polymer (I-2) -2.
The living polymer (I-2) -1 of the modified block copolymer and the living polymer (I-2) -2 of the unmodified block copolymer thus obtained have a styrene content of 46 mass. %, Polystyrene block content 18% by weight, polybutadiene block part vinyl bond content 48% by weight, molecular weight 121,000, molecular weight distribution 1.1.

Next, the living polymer (I-2) -1 of the modified block copolymer thus obtained and the living polymer (I-2) -2 of the unmodified block copolymer were added to the water described above. As a catalyst, 100 ppm of living polymers (I-2) -1 and (I-2) -2 were added as titanium with respect to 100 parts by mass, respectively, and a hydrogenation reaction was performed at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. went.
Thereafter, methanol was added, and then 0.3 parts by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by mass of the hydrogenated polymer. did.
The hydrogenated block copolymer obtained by hydrogenating the living polymer (I-2) -1 of the modified block copolymer is referred to as HPb-1, and the living polymer (I-2)-of the unmodified block copolymer. A hydrogenated block copolymer obtained by hydrogenating 2 is referred to as HPb-2.
The hydrogenation rate of the obtained hydrogenated block copolymer was 71%.
Further, when DSC of the obtained hydrogenated copolymer was measured, no crystallization peak was present.

[Examples 1-9], [Comparative Examples 1-5]
Next, the hydrogenated block copolymer and modified hydrogenated block copolymer (HPa-1 to HPa-5) shown in Table 2 and the hydrogenated block copolymer and modified shown in Table 3 were prepared as described above. Hydrogenated block copolymers (HPb-1, HPb-2) are made into pellets, and according to the compositions shown in Tables 4 and 5 below, a rubber softener (oil) is added and kneaded with a twin screw extruder (PCM30). Then, a modified hydrogenated block copolymer composition was obtained by pelletization.
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 produce a sheet having a thickness of 2 mm, and used as a physical property measurement piece.
The rubber softener used was paraffin oil (PW-90: manufactured by Idemitsu Kosan Co., Ltd.).

  The physical property values and evaluation results of the test pieces of the modified hydrogenated block copolymer compositions of Examples 1 to 9 and Comparative Examples 1 to 5 are shown in Tables 4 and 5 below.

  As is clear from the results of Tables 4 and 5, Examples 1 to 9, which are the hydrogenated block copolymer compositions of the present embodiment, have practically good workability, flexibility and high resilience. It was excellent in elasticity, had practically sufficient mechanical strength, and had excellent adhesion to polar resins. Moreover, since transparency was also favorable, it turned out that it is suitable as a soft material by which a favorable external appearance is requested | required.

Further, in Comparative Example 1, the rubber softener was excessive, the mechanical strength was reduced, and oil bleed and the like were also generated.
In Comparative Example 2, on the contrary, the rubber softener was insufficient, the hardness was high, and it was unsuitable for practical use.
In Comparative Example 3, the hydrogenated block copolymer (HPa-3) was not modified and the adhesiveness was poor. Furthermore, also in Comparative Example 4, the hydrogenated block copolymer (HPa-3) was not modified, and the adhesiveness was poor.
In Comparative Example 5, the hydrogenated block copolymer was unmodified (HPb-2), and the adhesiveness was poor.

  The modified hydrogenated block copolymer composition of the present invention and the molded product thereof have industrial applicability as impact buffer materials, medical device materials, household appliances, industrial parts, sports equipment, toys and the like.

Claims (7)

(I-1) A polymer block A mainly composed of a vinyl aromatic hydrocarbon compound and a polymer block B mainly composed of a conjugated diene compound, wherein the content of the vinyl aromatic hydrocarbon compound is 10 to 40 An atom having at least one functional group selected from the group consisting of a glycidyl group, a glycidoxy group, an alkoxysilyl group, a urea bond, a 5-membered lactam, and a 6-membered lactam in a hydrogenated block copolymer of mass% Modified hydrogenated block copolymer to which groups are bonded: 1
00 parts by mass,
(II) Rubber softener: 50 to 200 parts by mass;
A modified hydrogenated block copolymer composition. (I-1) A polymer block A mainly composed of a vinyl aromatic hydrocarbon compound and a polymer block B mainly composed of a conjugated diene compound, wherein the content of the vinyl aromatic hydrocarbon compound is 10 to 40 An atom having at least one functional group selected from the group consisting of a glycidyl group, a glycidoxy group, an alkoxysilyl group, a urea bond, a 5-membered lactam, and a 6-membered lactam in a hydrogenated block copolymer of mass% A modified hydrogenated block copolymer to which a group is bonded;
(I-2) A hydrogenated block copolymer composed of a conjugated diene compound and a vinyl aromatic compound, which satisfies the following (1) to (6), a glycidyl group, a glycidoxy group, A modified hydrogenated block copolymer to which an atomic group having at least one functional group selected from the group consisting of an alkoxysilyl group, a urea bond, a 5-membered lactam, and a 6-membered lactam is bonded. Modified hydrogenated block copolymer (I-3) mixed at a ratio of 90 to 90/10: 1
00 parts by mass,
(II) Rubber softener: 50 to 200 parts by mass;
A modified hydrogenated block copolymer composition.
(1) It has at least one polymer block of the following (a), (b), and (c).
(A) Vinyl aromatic compound polymer block (b) Hydrogenated copolymer block comprising conjugated diene compound and vinyl aromatic compound (c) Hydrogenated polymer of conjugated diene compound polymer having a vinyl bond content of 40% or more Block (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.
(4) The vinyl bond content of the conjugated diene compound monomer unit constituting the pre-hydrogenation polymer of the hydrogenated polymer block (b) is 10% or more and less than 20%.
(5) The hydrogenation rate of the double bond of the conjugated diene compound monomer unit constituting the block copolymer before hydrogenation of (I-2) 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). 30% by mass or more and 50% by mass or less, and the content of the hydrogenated polymer block (c) exceeds 35% by mass and is 50% by mass or less. (I-1) modified hydrogenated block copolymer: 100 parts by mass;
(II) softener for rubber: 50 to 150 parts by mass;
The modified hydrogenated block copolymer composition according to claim 1. The hardness according to JIS K6253 is 5 to 35,
According to BS903, the rebound resilience measured at 23 ° C. is 50% or more.
The modified hydrogenated block copolymer composition according to any one of claims 1 to 3. A modified hydrogenated block copolymer composition obtained by crosslinking the modified hydrogenated block copolymer composition according to any one of claims 1 to 4. A molded article obtained by molding the modified hydrogenated block copolymer composition according to any one of claims 1 to 5.   The molded product according to claim 6, further comprising a urethane film on a surface of the molded product.