JP2012036299A - Modified hydrogenated block copolymer composition and molding using the same - Google Patents

Abstract

The modified hydrogenated block co-polymer has excellent processability, flexibility, mechanical strength, high resilience, good appearance (color development, transparency), no softener bleed and excellent surface feel. A coalescence composition is provided.
(I-1) A polymer block A mainly composed of a vinyl aromatic hydrocarbon and a polymer block B mainly composed of a conjugated diene, wherein an atomic group having a functional group is bonded. And a hydrogenated hydrogenated modified block copolymer having a vinyl aromatic hydrocarbon content of 5 to 50% by mass: 100 parts by mass;
(II) Rubber softener: 50 to 200 parts by mass;
(III) Secondary modifier: 0.05-5 parts by mass;
A modified hydrogenated block copolymer composition.
[Selection figure] None

Description

  The present invention relates to a modified hydrogenated block copolymer composition and a molded body using the same.

  A block copolymer consisting of a conjugated diene and a vinyl aromatic hydrocarbon has the same content as a vulcanized natural rubber or synthetic rubber even if it is not vulcanized when the content of vinyl aromatic hydrocarbon is relatively small. Since it has elasticity at room temperature and has processability similar to that of a thermoplastic resin at high temperatures, it is widely used in the fields of footwear, plastic modification, asphalt modification, adhesives and the like.

  However, the block copolymer having a relatively low vinyl aromatic hydrocarbon content has good flexibility, resilience, and processability, but has poor impact buffering properties due to poor adhesion to polar resins. have.

Conventionally, as a material having flexibility, a random copolymer having a vinyl aromatic hydrocarbon content of 3 to 50% by mass, a molecular weight distribution (Mw / Mn) of 10 or less, and a copolymer A composition of a hydrogenated diene copolymer obtained by hydrogenating a copolymer having a vinyl bond content of 10 to 90% in the diene portion and a polypropylene resin has been proposed (for example, see Patent Document 1). .
Also, a random copolymer having a vinyl aromatic hydrocarbon 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 was hydrogenated. A composition of a hydrogenated diene copolymer and a polypropylene resin has been proposed (see, for example, Patent Document 2).

  Further, a proposal has been made for a thermoplastic elastomer composition that has less oil bleed and has excellent mechanical strength, transparency, and flexibility (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 hydrocarbons, including a block mainly composed of styrene and a block mainly composed of butadiene / styrene. There has also been proposed a molding material based on a hydrogenated block copolymer made of such a copolymer (see, for example, Patent Document 4).

  Furthermore, the present invention relates to a hydrogenated block copolymer that can be used as a material excellent in impact buffering properties that has both flexibility and low resilience, and a composition comprising the hydrogenated block copolymer and a rubber softener. Disclosure is also made (see, for example, Patent Document 5).

Japanese Patent Laid-Open No. 2-158463 JP-A-6-287365 Japanese Patent Laid-Open No. 2005-281489 International Publication No. 98/012240 Pamphlet International Publication No. 06/088187 Pamphlet

  However, the compositions disclosed in Patent Documents 1 and 2 are insufficient in practical use for adhesion to polar resins.

  Further, the thermoplastic elastomer composition disclosed in Patent Document 3 has good flexibility and transparency, has sufficient mechanical strength in practical use, has few oil bleeds, and is excellent in moldability. Adhesiveness with resin is practically insufficient.

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

  Furthermore, the composition disclosed in Patent Document 5 has a problem that adhesiveness with a polar resin is insufficient.

  Therefore, in the present invention, modified water having excellent processability, flexibility, mechanical strength, high resilience, good appearance (color development, transparency), no softener bleed, and excellent surface feel. It is an object to provide a block copolymer composition.

As a result of intensive studies to solve the above-mentioned problems, the present inventors contain a specific modified hydrogenated block copolymer, a rubber softener, and a secondary modifier in a predetermined ratio. The present inventors have found that the composition effectively solves the above problems and have completed the present invention.
The present invention is as follows.

[1]
(I-1) A polymer block A mainly composed of vinyl aromatic hydrocarbons and a polymer block B mainly composed of conjugated dienes, wherein functional groups are bonded, and hydrogenated A modified hydrogenated block copolymer that has been treated, and a modified hydrogenated block copolymer having a vinyl aromatic hydrocarbon content of 5 to 50% by mass: 100 parts by mass;
(II) Rubber softener: 50 to 200 parts by mass;
(III) Secondary modifier: 0.05-5 parts by mass;
A modified hydrogenated block copolymer composition.

[2]
(I-1) A polymer block A mainly composed of vinyl aromatic hydrocarbons and a polymer block B mainly composed of conjugated dienes, wherein functional groups are bonded, and hydrogenated A modified hydrogenated block copolymer that has been treated, wherein the vinyl aromatic hydrocarbon content is 5 to 50% by mass; and
(I-2) A modified water-added block copolymer comprising a conjugated diene and a vinyl aromatic compound, having an atomic group having a functional group bonded thereto, and subjected to a hydrogenation treatment. ) To (6) modified hydrogenated block copolymer,
The
Modified hydrogenated block copolymer mixture mixed at a ratio of 10/90 to 90/10: 100 parts by mass;
(II) Rubber softener: 50 to 200 parts by mass;
(III) Secondary modifier: 0.05-5 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 having conjugated diene and vinyl aromatic compound (c) Hydrogenated polymer block of conjugated diene polymer having a vinyl bond content of 40% or more ( 2) The content of the vinyl aromatic compound in the modified hydrogenated block copolymer (I-2) 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 monomer unit constituting the copolymer before hydrogenation of the hydrogenated copolymer block of (b) is 10% or more and less than 20%.
(5) The hydrogenation rate of the double bond of the conjugated diene monomer unit constituting the copolymer before hydrogenation of the hydrogenated copolymer block of (b) is 50% or more.
(6) The content of the (a) vinyl aromatic compound polymer block in the modified hydrogenated block copolymer (I-2) is 5% by mass or more and 30% by mass or less, and (b) the hydrogenated copolymer. The content of the polymer block is 30% by mass or more and 50% by mass or less, and the content of the (c) hydrogenated polymer block is more than 35% by mass and 50% by mass or less.

[3]
The modified hydrogenated block copolymer composition according to [1] or [2] above, having a hardness according to JIS K6253 of 5 to 35 and a rebound resilience measured by BS903 at 23 ° C. of 50% or more.

[4]
A modified hydrogenated block copolymer composition obtained by crosslinking the modified hydrogenated block copolymer composition according to any one of [1] to [3].

[5]
The molded object which shape | molded the modified hydrogenated block copolymer composition as described in any one of said [1] thru | or [4].

  The molded product according to [5], further including a urethane film formed on the surface by coating.

  According to the present invention, modified hydrogenation having excellent processability, flexibility, mechanical strength, high resilience, good appearance (transparency and color development), no softener bleed, and excellent surface feel. A block copolymer composition is obtained.

  Hereinafter, a 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.

[Modified hydrogenated block copolymer composition]
The modified hydrogenated block copolymer composition of this embodiment has the following first and second embodiments. [Modified Hydrogenated Block Copolymer Composition in First Embodiment]
(I-1) A polymer block A mainly composed of vinyl aromatic hydrocarbons and a polymer block B mainly composed of conjugated dienes, wherein functional groups are bonded, and hydrogenated A modified hydrogenated block copolymer that has been treated, and a modified hydrogenated block copolymer having a vinyl aromatic hydrocarbon content of 5 to 50% by mass: 100 parts by mass;
(II) Rubber softener: 50 to 200 parts by mass;
(III) Secondary modifier: 0.05-5 parts by mass;
A modified hydrogenated block copolymer composition.

[Modified Hydrogenated Block Copolymer Composition in Second Embodiment]
(I-1) A polymer block A mainly composed of vinyl aromatic hydrocarbons and a polymer block B mainly composed of conjugated dienes, wherein functional groups are bonded, and hydrogenated A modified hydrogenated block copolymer that has been treated, wherein the vinyl aromatic hydrocarbon content is 5 to 50% by mass; and
(I-2) A modified water-added block copolymer comprising a conjugated diene and a vinyl aromatic compound, having an atomic group having a functional group bonded thereto, and subjected to a hydrogenation treatment. ) To (6) modified hydrogenated block copolymer,
The
Modified hydrogenated block copolymer mixture mixed at a ratio of 10/90 to 90/10: 100 parts by mass;
(II) Rubber softener: 50 to 200 parts by mass;
(III) Secondary modifier: 0.05-5 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 having conjugated diene and vinyl aromatic compound (c) Hydrogenated polymer block of conjugated diene polymer having a vinyl bond content of 40% or more (2) The content of the vinyl aromatic compound in the modified hydrogenated block copolymer (I-2) 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 monomer unit constituting the copolymer before hydrogenation of the hydrogenated copolymer block of (b) is 10% or more and less than 20%.
(5) The hydrogenation rate of the double bond of the conjugated diene monomer unit constituting the copolymer before hydrogenation of the hydrogenated copolymer block of (b) is 50% or more.
(6) The content of the (a) vinyl aromatic compound polymer block in the modified hydrogenated block copolymer (I-2) is 5% by mass or more and 30% by mass or less, and (b) the hydrogenated copolymer. The content of the polymer block is 30% by mass or more and 50% by mass or less, and the content of the (c) hydrogenated polymer block is more than 35% by mass and 50% by mass or less.

<(I-1) Modified Hydrogenated Block Copolymer>
(I-1) The modified hydrogenated block copolymer has a polymer block A mainly composed of vinyl aromatic hydrocarbons and a polymer block B mainly composed of conjugated dienes, and has an atomic group. Is a modified hydrogenated block copolymer that has been subjected to hydrogenation treatment and has a vinyl aromatic hydrocarbon content of 5 to 50% by mass.
By setting the vinyl aromatic hydrocarbon content in the (I-1) modified hydrogenated block copolymer to 5% by mass or more, the modified hydrogenated block copolymer composition of the present embodiment has excellent mechanical strength. Moreover, it is preferable from a viewpoint of suppressing hardness and ensuring a softness | flexibility by setting it as 50 mass% or less.
The vinyl aromatic hydrocarbon content is preferably 10 to 40% by mass, and more preferably 15 to 35% by mass.
In addition, vinyl aromatic hydrocarbon content can be measured by the ultraviolet absorption method described in the Example mentioned later.

(I-1) The block copolymer of the modified hydrogenated block copolymer before hydrogenation and before modification is, for example, Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-171979, Japanese Patent Publication No. 46. -32415, JP-B-49-36957, JP-B-48-2423, JP-B-48-4106, JP-B-51-49567, JP-A-59-166518, etc. It can be produced by a method.
A modified block copolymer containing a functional group is obtained by addition-reacting a modifying agent described later to the living terminal of the block copolymer produced by these methods.
Further, the modified block copolymer is hydrogenated to obtain (I-1) a modified hydrogenated block copolymer.

The modified block copolymer has a structure represented by the following general formula.
(A-B) _n -Z, A- (B-A) _n -Z, B- (A-B) _n -Z, Z- (A-B) _n , Z- (A-B) _n -Z , ZA- (BA) _n -Z, Z-B- (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 formula, A is a polymer block mainly composed of vinyl aromatic hydrocarbons, and B is a polymer mainly composed of conjugated dienes.
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 modified 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.

The polymer block A mainly composed of vinyl aromatic hydrocarbons contains 50% by mass or more, preferably 70% by mass or more of vinyl aromatic hydrocarbons, and is a co-polymer of vinyl aromatic hydrocarbon and conjugated diene. Polymer block and / or vinyl aromatic hydrocarbon homopolymer block.
The polymer block B mainly comprising a conjugated diene contains a copolymer block of a conjugated diene and a vinyl aromatic hydrocarbon, containing a conjugated diene in an amount exceeding 50% by mass, preferably 60% by mass or more, and / or Or it is a conjugated diene homopolymer block.

The vinyl aromatic hydrocarbon in the copolymer block constituting the modified block copolymer may be distributed uniformly or in a tapered shape.
In the copolymer block portion, a plurality of portions where the vinyl aromatic hydrocarbons are uniformly distributed and / or a portion where the portions are distributed in a tapered shape may coexist. Further, a plurality of portions having different vinyl aromatic hydrocarbon contents may coexist in the copolymer block portion.
The modified block copolymer may be a modified block copolymer represented by the above general formula, which may be used alone or in any mixture.

  The microstructure (the ratio of cis, trans, vinyl) of the conjugated diene moiety in the block copolymer composed of the polymer block A and the polymer block B can be arbitrarily adjusted by using a polar compound or the like described later. For example, when 1,3-butadiene is used as the conjugated diene, the amount of 1,2-vinyl bonds is preferably 10 to 80%, more preferably 25 to 75%. When isoprene is used as the conjugated diene Alternatively, when 1,3-butadiene and isoprene are used in combination, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds is preferably 5 to 70%.

  In this specification, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds (when 1,3-butadiene is used as the conjugated diene, the amount of 1,2-vinyl bonds) is expressed as vinyl. This is referred to as the amount of binding.

The conjugated diene constituting the block copolymer is a diolefin having a pair of conjugated double bonds, such as 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3- Examples include dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like. Particularly common examples include 1,3-butadiene and isoprene. These may use only 1 type in manufacture of one block copolymer, and may use 2 or more types together.
Examples of the vinyl aromatic hydrocarbon constituting the block copolymer include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinyl. Naphthalene, vinyl anthracene and the like can be mentioned, and styrene is particularly preferable.
These may use only 1 type in manufacture of one block copolymer, and may use 2 or more types together.

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

The vinyl aromatic hydrocarbon compound content in the modified hydrogenated block copolymer constituting the modified hydrogenated block copolymer composition of the present embodiment can be measured by a UV method or an 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 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)
Therefore, when calculating | requiring content of the polymer block A in the block copolymer after hydrogenation by NMR method, the polymer block A which prescribes | regulates the value of (Os) calculated | required by the said Formula (F) by this embodiment. Content.

<Method for Producing Modified Hydrogenated Block Copolymer (I-1)>
The modified hydrogenated block copolymer (I-1) is prepared by using a predetermined solvent, a polymerization catalyst, the above vinyl aromatic hydrocarbon and a conjugated diene, and a polymer block A mainly composed of vinyl aromatic hydrocarbon and a conjugated diene. Can be produced by preparing a block copolymer comprising a polymer block B mainly composed of the following, followed by a modification treatment using a modifier, followed by a hydrogenation reaction using a hydrogenation catalyst.

(solvent)
Examples of the solvent used for the production of the block copolymer include aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, octane, isooctane; cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, etc. And hydrocarbon solvents such as aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and xylene.
These may use only 1 type and may mix and use 2 or more types.

(Polymerization catalyst)
In the production of the block copolymer, an organolithium compound is used as a polymerization catalyst.
An organolithium compound is a compound in which one or more lithium atoms are bonded in the molecule, for example, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, hexa Examples include methylene dilithium, butadienyl dilithium, and isoprenyl dilithium.
These may use only 1 type and may use 2 or more types together.
Further, the organolithium compound may be added in one or more divided portions during the polymerization in the production of the block copolymer.

(Polar compound, randomizing agent)
In the block copolymer production process, polar compounds and randomization can be performed by adjusting the polymerization rate, changing the microstructure of the polymerized conjugated diene moiety, adjusting the reactivity ratio of conjugated diene and vinyl aromatic hydrocarbon, etc. An agent may be used.
Examples of polar compounds and randomizing agents include ethers, amines, thioethers, phosphines, 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.
As amines, tertiary amine, trimethylamine, triethylamine, tetramethylethylenediamine, and other cyclic tertiary amines can be used.
Examples of phosphine and phosphoramide include triphenylphosphine and hexamethylphosphoramide.

(Polymerization temperature, polymerization time)
In the step of preparing the block copolymer, 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.

(Polymerization atmosphere, polymerization pressure)
The atmosphere of the block copolymer polymerization system is preferably an inert gas atmosphere such as nitrogen gas.
The polymerization pressure is not particularly limited as long as a pressure range sufficient to maintain the monomer and solvent in the liquid phase within the above-described polymerization temperature range is selected.
In the polymerization system, it is preferable that impurities that inactivate the catalyst and the living polymer, for example, water, oxygen, carbon dioxide gas, and the like are not mixed.

(Denaturation reaction)
Living of a block copolymer obtained by using an organic lithium compound as a polymerization catalyst and comprising a polymer block A mainly composed of at least one vinyl aromatic hydrocarbon and a polymer block B mainly composed of at least one conjugated diene A modified block copolymer to which an atomic group having a functional group is bonded is obtained by addition reaction of a functional group-containing modifier at the terminal.

A modified block copolymer to which an atomic group having a functional group is bonded is obtained by adding a modifying agent to which an atomic group having a functional group is bonded, or the functional group by an addition reaction with the living end of the block copolymer. It can be obtained by addition reaction of a modifying agent to which an atomic group protected by a known method is bonded.
As another method, a block copolymer is reacted with an organic alkali metal compound such as an organic lithium compound (metalation reaction), and a modifier is added to the polymer obtained by adding an organic alkali metal to the block copolymer. The method of making it react is mentioned.
In the latter method, the block copolymer may be hydrogenated to obtain a hydrogenated product, followed by a metallation reaction, and then a modifier may be reacted.
Depending on the type of the modifying agent, the hydroxyl group or amino group may be an alkali metal salt at the stage of reacting the modifying agent. In that case, a compound having active hydrogen such as water, alcohol, inorganic acid ( By treatment with an 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 material. The proportion of the unmodified product is preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less.

(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.

  Furthermore, 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- And methacryloxypropyl) dimethoxysilane and tris (γ-methacryloxypropyl) methoxysilane.

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

  Furthermore, 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-methyldipropoxy Silane, β- (3,4-epoxycyclohexyl) ethyl-methyldibutoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiphenoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylmethoxy Silane, β- (3,4-epoxycyclo Xyl) ethyl-diethylethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylpropoxysilane, β- (3,4-epoxycyclohexyl) Examples thereof include ethyl-dimethylbutoxysilane and β- (3,4-epoxycyclohexyl) ethyl-dimethylphenoxysilane.

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

  Furthermore, 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.

  Furthermore, 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- Examples include 2-piperidone and 1-isopropyl-5,5-dimethyl-2-piperidone.

By reacting the above modifier, a modified block copolymer to which a modifier residue having an atomic group having a functional group is bonded is obtained.
By performing the modification, the functional group bonded to the atomic group has reactivity with the secondary modifier described later, and at the same time has a nitrogen atom, an oxygen atom, or a carbonyl group in the modified block copolymer. Therefore, interaction due to physical affinity such as hydrogen bonding between these and the polar group of the polar resin is effectively expressed, and the effect of improving the adhesiveness can be exhibited.
When the functional group-containing modifier is added to the living end of the block copolymer, the living end of the block copolymer may be either the polymer block A or the polymer block B, but the mechanical strength, impact resistance, etc. In order to obtain a composition having an excellent balance, it is preferably bonded to the end of the polymer block A.
The amount of the modifier used is more than 0.5 equivalents and 10 equivalents or less, preferably more than 0.7 equivalents and 5 equivalents or less, more preferably more than 1 equivalent, with respect to 1 equivalent of the living terminal of the polymer. It is below the equivalent.
The amount of the living terminal of the polymer can be calculated from the amount of the organic lithium compound used for the polymerization.

(Hydrogenation reaction)
The (I-1) modified hydrogenated block copolymer can be obtained by hydrogenating the modified block copolymer obtained as described above.
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 performed by a batch process, a continuous process, or a combination thereof.

(Hydrogenation catalyst)
The hydrogenation catalyst is not particularly limited, and is a conventionally known (1) supported heterogeneous hydrogenation catalyst in which a metal such as Ni, Pt, Pd, or Ru is supported on carbon, silica, alumina, diatomaceous earth, or the like. (2) So-called Ziegler type hydrogenation catalysts using organic acid salts such as Ni, Co, Fe, Cr or transition metal salts such as acetylacetone salts and reducing agents such as organic aluminum, (3) Ti, Ru, Rh Homogeneous hydrogenation catalysts such as so-called organometallic complexes such as organometallic compounds such as Zr are 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 The hydrogenation catalyst described in the publication No. is mentioned.

In particular, a mixture with a titanocene compound and / or a reducing organometallic compound is preferred.
As the titanocene compound, compounds described in JP-A-8-109219 can be used. Specifically, it has at least one ligand 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 rate)
The total hydrogenation rate of the unsaturated double bond based on the conjugated diene compound of the modified hydrogenated block copolymer (I-1) can be arbitrarily selected according to the purpose and is not particularly limited.
70% or more, preferably 80% or more, more preferably 90% or more of the unsaturated double bonds based on the conjugated diene compound in the block copolymer may be hydrogenated, or only a part is hydrogenated. It may be.
When only a part is hydrogenated, the hydrogenation rate is preferably 10% or more and less than 70%, 15% or more and less than 65%, and preferably 20% or more and less than 60%.
Further, the hydrogenation rate of the vinyl bond based on the conjugated diene before hydrogenation is preferably 85% or more, more preferably 90% or more, and even more preferably 95% or more. It is suitable for obtaining a product.
Here, the hydrogenation rate of vinyl bonds refers to the proportion of vinyl bonds that have been hydrogenated out of vinyl bonds based on conjugated dienes that have been incorporated into the block copolymer prior to hydrogenation.
The hydrogenation rate of the aromatic double bond based on the vinyl aromatic hydrocarbon in the modified block copolymer is not particularly limited, but is preferably 50% or less, more preferably 30% or less, and still more preferably 20 % Or less.
The amount and hydrogenation rate of vinyl bonds based on the conjugated diene compound and the hydrogenation rate of aromatic double bonds based on the vinyl aromatic hydrocarbon can be measured by a nuclear magnetic resonance apparatus (NMR).

(Recovery of modified hydrogenated block copolymer (I-1))
From the solution of the modified hydrogenated block copolymer (I-1) produced by the above-described production method, the catalyst residue is removed as necessary, and the solvent is separated, whereby the modified hydrogenated block copolymer (I -1) is obtained.
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 hydrogenation to precipitate and recover the polymer, and the polymer solution is heated under stirring. And a method of removing the solvent by steam stripping and recovering the solvent, a method of directly heating the polymer solution to distill off the solvent, and the like.
In addition, stabilizers, such as various phenol type stabilizers, phosphorus type stabilizers, sulfur type stabilizers, and amine type stabilizers, can be added to the modified hydrogenated block copolymer.

(Weight average molecular weight of the modified hydrogenated block copolymer (I-1))
The weight average molecular weight of the modified hydrogenated block copolymer is preferably 30,000 or more from the viewpoint of mechanical strength of the polymer composition of this embodiment, and preferably 1,000,000 or less from the viewpoint of workability. It is 10,000 to 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

<(I-2) Modified hydrogenated block copolymer>
(I-2) The modified hydrogenated block copolymer can be produced by the same method as the modified hydrogenated block copolymer (I-1). Specifically, International Publication No. 06/088187. The block copolymer having the structure disclosed in (1) is a copolymer modified and hydrogenated by the production method disclosed in the modified hydrogenated block copolymer (I-1).

<Modified hydrogenated block copolymer composition>
The modified hydrogenated block copolymer composition in the first embodiment includes (I-1) modified hydrogenated block copolymer: 100 parts by mass, and (II) a rubber softener described later: 50 to 200 parts by mass. Part and (III) secondary modifier described later: 0.05 to 5 parts by mass of a modified hydrogenated block copolymer composition.
The modified hydrogenated block copolymer composition according to the second embodiment comprises (I-1) the modified hydrogenated block copolymer and (I-2) the modified hydrogenated block copolymer. Modified hydrogenated block copolymer mixture mixed at a ratio of 90 to 90/10: 100 parts by mass, (II) rubber softener described later: 50-200 parts by mass, and (III) secondary modifier described later : A modified hydrogenated block copolymer composition containing 0.05 to 5 parts by mass.
Oil mixing can be prevented and hardness can be reduced by the mixing ratio of (I-1) modified hydrogenated block copolymer and (I-2) modified hydrogenated block copolymer being 10/90 to 10/90. , The balance between flexibility and resilience absorption is good.

((II) Rubber softener)
In the modified hydrogenated block copolymer composition of this embodiment, the rubber composition can be softened by combining the modified hydrogenated block copolymer with a rubber softening agent at a predetermined ratio, and good workability is imparted. it can.
Examples of the rubber softening material include mineral oil and liquid or low molecular weight synthetic softening agents.
In particular, naphthenic and / or paraffinic process oils or extender oils are preferred.

  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.

  In addition, synthetic softeners such as polybutene, low molecular weight polybutadiene, and liquid paraffin may be used, but the mineral oil rubber softener described above is more preferable.

The blending amount of (II) rubber softener in the modified hydrogenated block copolymer composition of the present embodiment is 50 to 200 parts by mass, preferably 70 to 100 parts by mass with respect to 100 parts by mass of the modified hydrogenated block copolymer. 150 parts by mass.
(II) When the amount of the rubber softener exceeds 200 parts by mass, the rubber softener tends to bleed out, and the surface feel is deteriorated.
Further, if the amount of the softening agent for rubber (II) is less than 50 parts by mass, the hardness of the hydrogenated block polymer composition increases, which is not preferable.

((III) Secondary modifier)
In the modified hydrogenated block copolymer composition of the present embodiment, the functional group of the modified hydrogenated block copolymer is obtained by combining the modified hydrogenated block copolymer with a (III) secondary modifier at a specific ratio. The secondary denaturing agent reacts with the nitrogen atom, oxygen atom, or carbonyl group contained in the secondary denaturing agent, and the interaction with physical affinity such as hydrogen bonding is effectively expressed to the polar resin. Thus, the effect of increasing the adhesion of the modified hydrogenated block copolymer composition to the polar resin is obtained.
The secondary modifier is a secondary modifier having a functional group reactive with the functional groups (I-1) and (I-2) described above. A secondary modifier having a functional group selected from a carboxyl group, an acid anhydride group, an isocyanate group, an epoxy group, a silanol group, and an alkoxysilane group is preferable.
(III) The secondary modifier is a cross-linking agent having at least two functional groups selected from the group consisting of the above functional groups. However, when the functional group is an acid anhydride group, it may be a crosslinking agent having one acid anhydride group.

Specific examples of (III) secondary modifiers are listed below.
For example, secondary modifiers having a carboxyl group include aliphatic acids such as maleic acid, oxalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, carbaryl acid, cyclohexanedicarboxylic acid, and cyclopentanedicarboxylic acid. Examples thereof include aromatic carboxylic acids such as carboxylic acid, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, trimesic acid, trimellitic acid, and pyromellitic acid.
Examples of the secondary modifier having an acid anhydride group include maleic anhydride, itaconic anhydride, pyromellitic anhydride, cis-4-cyclohexane-1,2-dicarboxylic anhydride, 1,2,4,5. -Benzenetetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride and the like.
Examples of the secondary modifier having an isocyanate group include tolylene diisocyanate, diphenylmethane diisocyanate, polyfunctional aromatic isocyanate and the like.
Examples of the secondary modifier having an epoxy group include tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl-m-xylenediamine, diglycidylaniline, ethylene glycol diglycidyl, propylene glycol diglycidyl, and terephthalic acid. And diglycidyl ester acrylate.
Examples of the secondary modifier having a silanol group include a hydrolyzate of an alkoxysilane compound. Examples of the secondary modifier having an alkoxysilane group include bis- (3-triethoxysilylpropyl) -tetrasulfane, bis- (3-triethoxysilylpropyl) -disulfane, and ethoxysiloxane oligomer.

Preferable (III) secondary modifier is, for example, a carboxylic acid having two or more carboxyl groups or an acid anhydride thereof, or an acid anhydride group, an isocyanate group, an epoxy group, a silanol group, or an alkoxysilane group. It has a secondary modifier.
For example, maleic anhydride, pyromellitic anhydride, 1,2,4,5-benzenetetracarboxylic dianhydride, toluylene diisocyanate, tetraglycidyl-1,3-bisaminomethylcyclohexane, bis- (3- And triethoxysilylpropyl) -tetrasulfane.

The blending amount of the (III) secondary modifier in the modified hydrogenated block copolymer composition of the present embodiment is 0.05 to 5 parts by mass with respect to 100 parts by mass of the modified hydrogenated block copolymer. Preferably it is 0.1-1.0 mass part.
(III) When the blending amount of the secondary modifier exceeds 5 parts by mass with respect to 100 parts by mass of the modified hydrogenated block copolymer, the amount of unreacted (III) secondary modifier increases and bleed out occurs. It tends to deteriorate the surface feel of the modified hydrogenated block copolymer composition.
Further, when the blending amount of the (III) secondary modifier is less than 0.05 parts by mass with respect to 100 parts by mass of the modified hydrogenated block copolymer, it reacts with the functional group of the modified hydrogenated block copolymer. This is not preferable because the amount of the secondary modifier that can exhibit the effect of enhancing the adhesion of the modified hydrogenated block copolymer composition to the polar resin is reduced.

(Additive)
An arbitrary additive can be blended in the modified hydrogenated block copolymer composition of the present embodiment as necessary.
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, reinforcing agents such as organic fibers, glass fibers, carbon fibers, and metal whiskers.
These may be used alone or in combination of two or more.

  If necessary, the modified 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.), a mixture thereof, and the like. May be.

(Filler, flame retardant)
In the modified hydrogenated block copolymer composition of the present embodiment, an optional filler and flame retardant can be blended as necessary.
The filler and the flame retardant are not particularly limited as long as they are those 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 various shapes such as scales, spheres, granules, powders, and irregular shapes can be used.
A filler may be used individually by 1 type and may use 2 or more types together.

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 above-mentioned flame retardants include so-called flame retardant aids that exhibit a low flame retardant effect but have a synergistic effect when used in combination with other flame retardants.

As the filler and flame retardant, those that have been previously surface treated with a surface treating agent such as a silane coupling agent can be used.
A filler and a flame retardant may be used independently and may use 2 or more types together.

(Crosslinking agent, crosslinking treatment)
The modified hydrogenated block copolymer composition of the present embodiment may be subjected to a crosslinking treatment as necessary.
As a method for the crosslinking treatment, 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 applied.
As the crosslinking process, a static method, a dynamic vulcanization method, or the like can be applied.

  Examples of the crosslinking agent include organic peroxides, sulfur, phenols, isocyanates, thiurams, morpholine disulfides, and the like. 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 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 applied.
In particular, a melt mixing method using an extruder is preferable from the viewpoints of productivity and good kneading properties.
The shape of the modified hydrogenated block copolymer composition is not particularly limited, but may be any of pellets, sheets, strands, chips, and the like.
Moreover, you may manufacture the target molded article directly after melt-kneading.

The modified hydrogenated block copolymer composition of the present embodiment may be obtained in the form of a foam molded article, and can be made into a foam molded article by a chemical method, a physical method, or the like. Bubbles can be distributed inside the material by adding a chemical foaming agent such as an inorganic foaming agent or an organic foaming agent or a foaming agent such as a physical foaming agent.
By making the modified hydrogenated block copolymer composition into a foamed molded product, 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.

  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.

[Molded body of modified hydrogenated block copolymer composition]
The modified hydrogenated block copolymer composition of the present embodiment is a material for producing various molded articles.
Examples of the molding method include extrusion molding, injection molding, hollow molding, pressure molding, vacuum molding, foam molding, multilayer extrusion molding, multilayer injection molding, high frequency fusion molding, slush molding, and calendar molding.
The molded body using the modified hydrogenated block copolymer composition may be subjected to a decoration treatment such as printing, painting, coating, or embossing on the surface as necessary. Thereby, effects such as improved appearance, improved weather resistance, and improved scratch resistance can be obtained.

As the coating agent used for the coating treatment, a two-component curing type, a moisture curing type, and a solvent volatilization curing type urethane coating agent are preferable, whereby a urethane film can be provided on the surface of the molded body.
When the surface to be coated is pretreated for the purpose of improving printability, paintability, coating properties, etc., the surface treatment method is not particularly limited, and physical methods, chemical methods, etc. may be used. Examples thereof include corona discharge treatment, ozone treatment, plasma treatment, flame treatment, and acid / alkali treatment.
In particular, corona discharge treatment is preferable from the viewpoints of ease of implementation, cost, and continuous treatment.

[Use of Modified Hydrogenated Block Copolymer Composition and Molded Body]
The modified hydrogenated block copolymer composition of this embodiment can be used for various applications.
For example, reinforcing filler blends, cross-linked products, foams, multilayer films and sheets, building materials, vibration control / sound insulation materials, wire coating materials, high frequency fusible compositions, slush molding materials, adhesive properties It can be suitably used as a composition, asphalt composition, medical device material, automobile material and the like.
Moreover, as a use of a molded object, a sheet | seat, a film, a tube, a nonwoven fabric, a fibrous molded product, synthetic leather, etc. are mentioned.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention more concretely, this invention is not limited to the following Example.

First, methods for measuring properties and physical properties of polymers in the following Examples and Comparative Examples are shown below.
[(1) Properties of block copolymer or modified hydrogenated block copolymer]
(1-1) Vinyl aromatic hydrocarbon content (styrene content) (mass%)
It measured using the ultraviolet spectrophotometer (Shimadzu Corporation UV-2450) using the block copolymer before hydrogenation.

(1-2) Styrene block ratio A block copolymer before hydrogenation was used. M.M. Kolthoff, et al. J. et al. Polym. Sci. 1, 429 (1946).
For the decomposition of the copolymer, an osmic acid 0.1 g / 125 mL tertiary butanol solution was used.

(1-3) Amount of vinyl bond Using a block copolymer before hydrogenation, measured using an infrared spectrophotometer (manufactured by JASCO Corporation, FT / IR-230), and the amount of vinyl bond was determined by the Hampton method. Calculated.

(1-4) Weight average molecular weight and molecular weight distribution A modified hydrogenated block copolymer was used and measured by GPC [manufactured by Tosoh Corporation, HLC-8120GPC].
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 compound monomer unit
Using a modified hydrogenated block copolymer after modification and hydrogenation, measurement was performed with a nuclear magnetic resonance apparatus (device name: DPX-400; manufactured by BRUKER, Germany).

(1-6) Modification rate The modified hydrogenated block copolymer is adsorbed on a silica gel column, but not adsorbed on a polystyrene gel column. Measurements were made using this adsorption selectivity.
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 not sufficient practically.

(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: 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.
Stickiness: The surface of the sheet was touched with a finger, and the presence or absence of stickiness was confirmed.
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 was either stickiness or oil bleed, it was judged as not practically good.

(2-7) 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 shown below.
<Adhesion conditions>
The modified hydrogenated block copolymer composition was pressed into a 2 mm thick sheet at 200 ° C., and then the sheet surface was treated with a 3% ethyl acetate solution of triallyl isocyanurate containing hypochlorous acid, followed by moisture curing. A sample sheet having a urethane coating on the surface was prepared by dipping in a butyl acetate solution of a polyurethane of a type, 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 the measurement was performed by the following peel test.
<Peel test>
Peeling speed: 200 mm / min, peel strength was measured in units of kg / 2 cm.
The higher the peel strength, the more desirable the evaluation.
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 modified hydrogenated block copolymer composition is removed. Breaking occurs and peel strength is improved.

(Preparation of modified hydrogenated block copolymer composition)
First, a hydrogenation catalyst was prepared according to the following.
(Preparation of hydrogenation catalyst)
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 to obtain a hydrogenation catalyst.

<Preparation of Modified Hydrogenated Block Copolymer (I-1) -1, (I-1) -2, Unmodified Hydrogenated Block Copolymer (I-1) -3>
First, a block copolymer (indicated as Pa-1 in Table 1 below) was prepared using a conjugated diene and an aromatic vinyl compound.
The autoclave equipped with a stirrer and a jacket was washed, dried and purged with nitrogen, and a cyclohexane solution (concentration 20% by mass) containing 15 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.
Next, a cyclohexane solution (concentration 20% by mass) containing 70 parts by mass of butadiene purified in advance is added and polymerized at 70 ° C. for 1 hour, and further a cyclohexane solution containing 15 parts by mass of styrene is added and polymerized at 70 ° C. for 1 hour. Thus, a living polymer of a block copolymer was obtained.
Similarly, a polymer (Pa-2) was produced.
A block copolymer living polymer having the characteristics shown in Table 1 below was obtained in the same manner as for the polymer (Pa-1).

  A modified hydrogenated block copolymer and a hydrogenated block copolymer were produced using the block copolymers (Pa-1, Pa-2) produced as described above.

As shown in the following Table 2, modified hydrogenated block copolymers HPa-1 ((I-1) -1) and HPa-2 ((I-1) -2) were prepared using Pa-1. An unmodified hydrogenated block copolymer HPa-3 ((I-1) -3) was prepared using Pa-2.
A predetermined amount of the modifier shown in Table 2 below was added to the living solution of the block copolymer and reacted at 70 ° C. for 20 minutes to obtain a modified block copolymer.
As the modifying agent (M1), 1,3-dimethyl-2-imidazolidinone was used.
Subsequently, 100 ppm of a hydrogenation catalyst as Ti was added to the above solution of the modified block copolymer, and a hydrogenation reaction was performed at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. for 1 hour.
Subsequently, methanol was added 10-fold mol with respect to n-butyllithium used for the polymerization of the block copolymer, and then carbonated water was added to adjust pH to 8 or less. HPa-1, HPa- 2 was obtained.
On the other hand, the unmodified hydrogenated block copolymer HPa-3 did not undergo the modification reaction.

<Preparation of Modified Hydrogenated Block Copolymer (I-2) -1 and Unmodified Hydrogenated Block Copolymer (I-2) -2>
First, a block copolymer was prepared using a conjugated diene and an aromatic vinyl compound.
Batch polymerization was carried out using a stirring device having an internal volume of 10 L and a jacketed tank reactor.
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 (tetramethylethylenediamine) are added with respect to 1 mol of n-butyllithium, and then at 70 ° C. for 1 hour. Polymerized.
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. Thereby, a block copolymer was obtained.

Using the block copolymer, a modified polymer and an unmodified polymer were obtained.
For the modified block copolymer, 1,3-dimethyl-2-imidazolidinone as a modifier is added to the above block copolymer in an equimolar amount with n-butyllithium used in the polymerization, and the mixture is added at 70 ° C. for 20 minutes. Reaction was carried out to obtain a modified block copolymer.
These modified block copolymer and unmodified block copolymer have a styrene content of 46% by mass, a polystyrene block content of 18% by mass, a vinyl bond content of polybutadiene block of 48% by mass, a molecular weight of 121,000, and a molecular weight. The distribution was 1.1.

Next, using each of the modified block copolymer and the unmodified block copolymer obtained as described above, a hydrogenation catalyst was added at 100 ppm as titanium with respect to 100 parts by mass of the polymer, and the hydrogen pressure was 0.7 MPa. The hydrogenation reaction was performed at a temperature of 65 ° C.
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 polymer. .
The hydrogenation rate was 71%. Further, when DSC of the obtained hydrogenated copolymer was measured, no crystallization peak was present.
By performing a hydrogenation treatment using the modified block copolymer, a modified hydrogenated block copolymer (I-2) -1 (referred to as HPb-1 in Table 3 below) was obtained.
Further, by performing a hydrogenation treatment using an unmodified block copolymer, (unmodified) hydrogenated block copolymer (I-2) -2 (in the following Table 3, represented as HPb-2). )

[Examples 1 to 9] [Comparative Examples 1 to 6]
The modified hydrogenated block copolymer and the unmodified hydrogenated block copolymer produced as described above are formed into pellets, and then, according to the composition shown in Tables 4 and 5 below, rubber softener (oil), secondary The modifier was added, kneaded with a twin screw extruder (PCM30), and pelletized to obtain a modified hydrogenated block copolymer composition and an unmodified hydrogenated block copolymer composition.
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 a physical property measurement piece was obtained.
Paraffin oil (PW-90: manufactured by Idemitsu Kosan Co., Ltd.) was used as the rubber softener.
Maleic anhydride was used as the secondary modifier.
The compositions, physical property values, and evaluations of the compositions of Examples 1 to 9 and Comparative Examples 1 to 6 are shown in Tables 4 and 5 below.

  As shown in Table 4 and Table 5, the modified hydrogenated block copolymer compositions of Examples 1 to 9 are all excellent in processability, flexibility, mechanical strength, and high resilience, and have an appearance (coloring property, It was found that (transparency) was good, and there was no bleed of the softening agent and the surface feel was excellent.

  The modified hydrogenated block copolymer composition of the present invention has industrial applicability as various molded articles such as medical device materials, household appliances, industrial parts, sports equipment, and toys.

Claims (6)

(I-1) A polymer block A mainly composed of vinyl aromatic hydrocarbons and a polymer block B mainly composed of conjugated dienes, wherein functional groups are bonded, and hydrogenated A modified hydrogenated block copolymer that has been treated, and a modified hydrogenated block copolymer having a vinyl aromatic hydrocarbon content of 5 to 50% by mass: 100 parts by mass;
(II) Rubber softener: 50 to 200 parts by mass;
(III) Secondary modifier: 0.05-5 parts by mass;
A modified hydrogenated block copolymer composition. (I-1) A polymer block A mainly composed of vinyl aromatic hydrocarbons and a polymer block B mainly composed of conjugated dienes, wherein functional groups are bonded, and hydrogenated A modified hydrogenated block copolymer that has been treated, wherein the vinyl aromatic hydrocarbon content is 5 to 50% by mass; and
(I-2) A modified water-added block copolymer comprising a conjugated diene and a vinyl aromatic compound, having an atomic group having a functional group bonded thereto, and subjected to a hydrogenation treatment. ) To (6) modified hydrogenated block copolymer,
The
Modified hydrogenated block copolymer mixture mixed at a ratio of 10/90 to 90/10: 100 parts by mass;
(II) Rubber softener: 50 to 200 parts by mass;
(III) Secondary modifier: 0.05-5 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 having conjugated diene and vinyl aromatic compound (c) Hydrogenated polymer block of conjugated diene polymer having a vinyl bond content of 40% or more ( 2) The content of the vinyl aromatic compound in the modified hydrogenated block copolymer (I-2) 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 monomer unit constituting the copolymer before hydrogenation of the hydrogenated copolymer block of (b) is 10% or more and less than 20%.
(5) The hydrogenation rate of the double bond of the conjugated diene monomer unit constituting the copolymer before hydrogenation of the hydrogenated copolymer block of (b) is 50% or more.
(6) The content of the (a) vinyl aromatic compound polymer block in the modified hydrogenated block copolymer (I-2) is 5% by mass or more and 30% by mass or less, and (b) the hydrogenated copolymer. The content of the polymer block is 30% by mass or more and 50% by mass or less, and the content of the (c) hydrogenated polymer block is more than 35% by mass and 50% by mass or less.   The modified hydrogenated block copolymer composition according to claim 1 or 2, which has a hardness according to JIS K6253 of 5 to 35 and a rebound resilience measured by BS903 at 23 ° C of 50% or more.   A modified hydrogenated block copolymer composition obtained by crosslinking the modified hydrogenated block copolymer composition according to any one of claims 1 to 3.   The molded object which shape | molded the modified | denatured hydrogenated block copolymer composition as described in any one of Claims 1 thru | or 4.   The molded product according to claim 5, further comprising a urethane film formed on the surface by coating.