JP2002201333A - Block copolymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a modified block copolymer composition having excellent mechanical strength, compression set, impact resistance and processability. SOLUTION: This block copolymer composition is characterized in that at least one atomic group having at least one functional group selected from hydroxy group, epoxy group, amino group, silanol group and an alkoxysilane is bound to a polymer block A and/or a polymer block B in the block copolymer composition comprising (1) 100 pts. mass of a block copolymer or its hydrogenated substance composed of at least the one polymer block A consisting essentially of a vinyl aromatic hydrocarbon and at least the one polymer block B consisting essentially of a conjugated diene and having 5-95 wt.% vinyl aromatic hydrocarbon content and (2) 0.5-50 pts. mass of a silica inorganic filler or/and a metal oxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to heat resistance, transparency,
Abrasion resistance, a thermoplastic polymer composition excellent in processability, more specifically, a functional group-containing block copolymer comprising a vinyl aromatic hydrocarbon and a conjugated diene or a hydrogenated product thereof and a silica-based inorganic filler or And / or a thermoplastic block copolymer composition comprising a metal oxide. The present invention also relates to a thermoplastic polymer composition having excellent mechanical strength, compression set, impact resistance, and processability. The present invention relates to a thermoplastic block copolymer composition comprising a polymer or a hydrogenated product thereof, a silica-based inorganic filler or / and a metal oxide, and an olefin-based polymer.

[0002]

2. Description of the Related Art Hitherto, in order to obtain high-performance and high-functional polymer materials, studies have been made to obtain compositions having excellent properties by polymer alloys combining different kinds of organic polymers. A thermoplastic elastomer composition that is a soft material and does not require a vulcanization step, a moldability, a thermoplastic resin composition with excellent recyclability,
It is used in various fields such as automobile parts, home electric parts, electric wire coating, medical parts, footwear, sundries and the like. At present, various types of polymers such as polyolefins, polyurethanes, polyesters, and polystyrenes have been developed and marketed as thermoplastic elastomers and thermoplastic resins. Among them, vinyl aromatic hydrocarbon-conjugated diene block copolymers such as styrene-butadiene block copolymer and styrene-isoprene block copolymer and hydrogenated products thereof (hereinafter referred to as hydrogenated block copolymers) contain styrene. When the amount is small, the composition is rich in flexibility, shows good rubber elasticity at room temperature, and the composition obtained therefrom has excellent moldability. In addition, when the styrene content is relatively high, a transparent thermoplastic resin having excellent impact resistance can be obtained, so that it is used for food packaging containers, home electric parts, industrial parts, household goods, toys and the like. However, there are limits to the functions that can be exhibited only by the organic polymer material depending on the application, and attempts have been made to combine an organic polymer material and an inorganic material.

[0003] For example, JP-A-59-131613 discloses an elastomer composition comprising a hydrogenated block copolymer, a hydrocarbon oil, an olefin polymer, and an inorganic filler. An elastomeric composition that has been partially cross-linked using and has improved compression set is
JP-A-10-58098 discloses a resin composition having excellent conductivity by blending a polyphenylene ether resin, a hydrogenated block copolymer, and a conductive inorganic filler. The publication discloses a thermoplastic resin composition which is excellent in moisture absorption resistance and vibration damping properties, in which a polycarbonate resin, a styrene-butadiene block copolymer and a ceramic hollow body are blended. However, even in such a thermoplastic block copolymer, a composition with an inorganic filler has a low affinity for each other because one is a hydrophobic organic substance and the other is a hydrophilic inorganic substance. Poor kneading properties and insufficient effect of expected performance improvement.

[0004] As a method for improving the mutual affinity between a thermoplastic block copolymer and a different material, it is known to add a functional group to the thermoplastic block copolymer. For example, JP-B-62-54138 and JP-B-62-54140 disclose an affinity for an inorganic filler by adding maleic anhydride to a block copolymer of a vinyl aromatic hydrocarbon and a conjugated diene compound. Are disclosed. In addition, Japanese Patent Publication No. 4-39495,
Japanese Patent Publication No. 4-28034 and Japanese Patent Publication No. 4-38777 disclose a thermoplastic resin and a tackifying resin in which a functional group is added to a terminal of a block copolymer of a vinyl aromatic hydrocarbon and a conjugated diene compound. And compositions having improved affinity with asphalt.

[0005]

Under these circumstances, the composition of a vinyl aromatic hydrocarbon-conjugated diene block copolymer or a hydrogenated product thereof and an inorganic filler effectively exerts mutual functions. There has been a further need for a method of providing a more sophisticated material.

[0006]

Means for Solving the Problems The present inventors have conducted various studies to solve the above-mentioned problems, and as a result, have found that a modified block copolymer having a specific structure provided with a specific functional group and a specific amount of The present inventors have found that a thermoplastic polymer composition having excellent mechanical strength, compression set, impact resistance, and processability can be obtained by using a composition containing a silica-based inorganic filler and / or a metal oxide. The invention has been completed. That is, the present invention is as follows. 1. (1) Consisting of at least one polymer block A mainly composed of vinyl aromatic hydrocarbons and at least one polymer block B mainly composed of conjugated dienes, and having a vinyl aromatic hydrocarbon content of 5 to 95 wt. % Of the block copolymer or a hydrogenated product thereof and (2) a silica-based inorganic filler or / and 0.5 to 50 parts by mass of a metal oxide. A block in which at least one atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane is bonded to the united block A and / or the polymer block B. Copolymer composition.

[0007] 2. 2. The block copolymer composition according to the above item 1, wherein the block copolymer composition contains 10 to 500 parts by mass of (3) an olefin polymer based on 100 parts by mass of the block copolymer or a hydrogenated product thereof. . 3. (1) The hydrogenated product of the block copolymer comprises at least one polymer block A mainly composed of a vinyl aromatic hydrocarbon and at least one polymer block B mainly composed of a conjugated diene. Vinyl aromatic hydrocarbon content is 5 to 95 wt%, 70% of total vinyl aromatic hydrocarbon content
The above is a vinyl aromatic hydrocarbon homopolymer block having a number average molecular weight of 20,000 or more, and the polymer block A and / or the polymer block B contains a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane. At least one atomic group having at least one selected functional group is bonded, and the number ratio of the structural units (A) to (E) based on the conjugated diene is represented by the following formulas (I) to (II).
3. The block copolymer composition as described in 1 or 2 above, which is a hydrogenated product of a block copolymer satisfying I).

[0008]

Embedded image

4. 4. The polymer block A and / or the polymer block B, wherein at least one atomic group having at least one functional group selected from the following is bonded to the polymer block A and / or the polymer block B. Block copolymer composition.

[0010]

Embedded image (In the above formula, R ⁹ and R ^{12 to} R ¹⁴ represent hydrogen or carbon 1
A hydrocarbon group having 1 to 24 carbon atoms having a functional group selected from a hydroxyl group, an epoxy group, a silanol group and an alkoxysilane. R ¹⁰ has 1 to 3 carbon atoms
0 hydrocarbon chain or a hydrocarbon chain having 1 to 30 carbon atoms having a functional group selected from a hydroxyl group, an epoxy group, a silanol group and an alkoxysilane. Note that R ⁹ and R ^{12 to} R
¹⁴ hydrocarbon group, and the hydrocarbon chain of R ^10, hydroxyl, epoxy group, a silanol group, in bonding mode other than alkoxysilane, oxygen, nitrogen, an element such as silicon may be bonded. R ¹¹ is hydrogen or an alkyl group having 1 to 8 carbon atoms. )

5. (2) Silica-based inorganic filler or /
And at least one silica-based inorganic filler whose metal oxide is selected from inorganic fibrous substances such as silica, wollastonite, montmorillonite, zeolite, alumina, titanium oxide, magnesium oxide, zinc oxide, slug wool, and glass fiber. 5. The block copolymer composition according to any one of the above items 1 to 4, wherein the composition is a metal oxide.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The modified block copolymer used in the present invention comprises, for example, at least one polymer block A mainly composed of a vinyl aromatic hydrocarbon and at least one polymer block A mainly composed of a conjugated diene.
The block copolymer is a block copolymer obtained by the addition reaction of a later-described modifier to the living terminal of a block copolymer composed of individual polymer blocks B, or a hydrogenated product thereof. The block copolymer obtained by these methods has, for example, a structure represented by the following general formula.

(AB) _n -X, (BA) _n -X, A
-(BA) _n -X, B- (AB) _n -X, X-
(AB) _n -X, XA- (BA) _n -X, X-
B- (AB) _n -X, [(BA) _n ] _m -X,
[(AB) _n ] _m -X, [(BA) _n -B] _m-
X, [(AB) _n -A] _m -X (in the above formula, A is a polymer block mainly composed of vinyl aromatic hydrocarbon, and B is a polymer block mainly composed of conjugated diene. N is an integer of 1 or more, generally an integer of 1 to 5, and m is an integer of 2 or more, generally 2
It is an integer of 10 to 10. X is a modifying agent residue to which an atomic group having a functional group described below is bonded. When X is added by a metallation reaction described later, the A block and / or
Or, it is bonded to the side chain of the B block. )

In the above description, the polymer block A mainly composed of a vinyl aromatic hydrocarbon is preferably 50% by weight or more of vinyl aromatic hydrocarbon, more preferably 70% by weight or more.
a copolymer block of a vinyl aromatic hydrocarbon and a conjugated diene containing at least wt%, and / or a homopolymer block of a vinyl aromatic hydrocarbon. Is 50wt%
And more preferably 60% by weight or more of a conjugated diene and vinyl aromatic hydrocarbon copolymer block or / and a conjugated diene homopolymer block.
The vinyl aromatic hydrocarbons in the copolymer block may be distributed uniformly or tapered. The copolymer block may have a plurality of portions where vinyl aromatic hydrocarbons are uniformly distributed and / or a plurality of portions where tapered shapes are distributed.
The modified block copolymer used in the present invention may be any mixture of the modified block copolymer represented by the above general formula.

As a method for producing the block copolymer, for example, JP-B-36-19286 and JP-B-43-17
No. 979, JP-B-46-32415, JP-B-49-36957, JP-B-48-2423, JP-B-48-4106, and JP-B-56-289.
No. 25, Japanese Patent Publication No. 51-49567,
Examples thereof include methods described in JP-A-9-166518 and JP-A-60-186577. Examples of the vinyl aromatic hydrocarbon used in the present invention include styrene, o-
Methylstyrene, p-methylstyrene, p-tert-
One or more of butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, vinylanthracene and the like can be used, and styrene is generally mentioned. Examples of the conjugated diene include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene. One or more of them can be used, and generally 1,3
-Butadiene, isoprene.

In the present invention, the solvent used for producing the block copolymer includes, for example, butane, pentane,
Aliphatic hydrocarbons such as hexane, isopentane, heptane, octane and isooctane; cycloaliphatic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane; and aromatics such as benzene, toluene, ethylbenzene, and xylene Group hydrocarbons and the like can be used. These may be used alone or in combination of two or more. In the present invention, the organic lithium compound used as a polymerization initiator in the production of the block copolymer is a compound in which one or more lithium atoms are bonded in a molecule, for example, ethyl lithium, n-propyl lithium, isopropyl lithium , N
-Butyl lithium, sec-butyl lithium, tert
-Butyllithium, hexamethylenedilithium, butadienyldilithium, isoprenyldilithium and the like can be used. These may be used alone or in combination of two or more. The organolithium compound may be dividedly added one or more times during the polymerization in the production of the block copolymer.

In the present invention, for the purpose of controlling the polymerization rate during the production of the block copolymer, controlling the microstructure of the polymerized conjugated diene portion, and controlling the reactivity ratio between the vinyl aromatic hydrocarbon and the conjugated diene, etc. Compounds and randomizers can be used. Examples of the polar compound and the randomizing agent include ethers, amines, thioethers, phosphine, phosphoramide, potassium or sodium salt of alkylbenzenesulfonic acid, and alkoxide of potassium or sodium. As specific examples, ethers include dimethyl ether, diethyl ether, diphenyl ether, tetrahydrofuran, diethylene glycol dimethyl ether, and diethylene glycol dibutyl ether. Examples of the amines include tertiary amines, trimethylamine, triethylamine, tetramethylethylenediamine, and other cyclic tertiary amines. Examples of the phosphine and phosphoramide include triphenylphosphine, hexamethylphosphoramide and the like.

In the present invention, the polymerization temperature for producing the block copolymer is preferably from -10 to 150 ° C, more preferably from 30 to 120 ° C. The polymerization time 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 a nitrogen gas. The polymerization pressure is not particularly limited as long as it is a pressure within a range sufficient to maintain the monomer and the solvent in a liquid phase within the above-mentioned polymerization temperature range. Furthermore, it is preferable to take care that impurities such as water, oxygen, and carbon dioxide that inactivate the catalyst and the living polymer are not mixed in the polymerization system.

The (1) block copolymer used in the present invention comprises a polymer block A and / or a polymer block B,
A block copolymer having at least one atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane, or a hydrogenated product thereof. A method for obtaining a block copolymer to which an atomic group having a functional group is bonded is a known method in which a living group of the block copolymer is modified with an atomic group having a functional group, or a known functional group. And a method of reacting a denaturant to which the protected atomic group is bonded. As another method, there is a method in which an organic alkali metal is reacted with a block copolymer (metallation reaction), and the above-mentioned modifier is reacted with a polymer obtained by adding an organic alkali metal to the block copolymer. In the latter case, the hydrogenation of the block copolymer may be followed by a metallation reaction to react the above atomic groups. In addition, depending on the type of the modifier, the hydroxyl group or the amino group may become an organic metal salt at the stage of reacting the modifier, in which case, treatment with a compound having active hydrogen such as water or alcohol is required. Can convert to a hydroxyl group or an amino group. In the present invention, the unmodified block copolymer may be partially mixed with the modifying terminal at the living end of the block copolymer. The ratio of the unmodified block copolymer mixed in the modified block copolymer is preferably 60% by weight or less, more preferably 50% by weight or less.

In the present invention, an atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane includes an atomic group selected from the following general formula.

[0021]

Embedded image (In the above formula, R ⁹ and R ^{12 to} R ¹⁴ represent hydrogen or carbon 1
A hydrocarbon group having 1 to 24 carbon atoms having a functional group selected from a hydroxyl group, an epoxy group, a silanol group and an alkoxysilane. R ¹⁰ has 1 to 3 carbon atoms
0 hydrocarbon chain or a hydrocarbon chain having 1 to 30 carbon atoms having a functional group selected from a hydroxyl group, an epoxy group, a silanol group and an alkoxysilane. Note that R ⁹ and R ^{12 to} R
¹⁴ hydrocarbon group, and the hydrocarbon chain of R ^10, hydroxyl, epoxy group, a silanol group, in bonding mode other than alkoxysilane, oxygen, nitrogen, an element such as silicon may be bonded. R ¹¹ is hydrogen or an alkyl group having 1 to 8 carbon atoms. )

In the present invention, it is used to obtain a block copolymer in which at least one atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane is bonded. As the denaturing agent, for example, tetraglycidyl metaxylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl-p-phenylenediamine, tetraglycidyldiaminodiphenylmethane, diglycidylaniline, diglycidylorthotoluidine, γ-glycan Sidoxyethyltrimethoxysilane, γ
-Glycidoxypropyltrimethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ -Glycidoxypropyltriphenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylmethyldiethoxysilane , Γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycidoxypropyl Diethylethoxysilane, γ-glycidoxypropyldimethylethoxysilane, γ-glycidoxypropyldimethylphenoxysilane, γ-glycidoxypropyldiethylmethoxysilane, γ-glycidoxypropylmethyldiisopropeneoxysilane, bis (γ -Glycidoxypropyl) dimethoxysilane, bis (γ-glycidoxypropyl) diethoxysilane, 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-glycidoxypropyl) methylphenoxysilane, tris (γ-glycidoxypropyl) methoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ- Methacryloxymethyltrimethoxysilane, γ-methacryloxyethyltriethoxysilane, bis (γ-methacryloxypropyl) dimethoxysilane, tris (γ-methacryloxypropyl) methoxysilane, 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, 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, β- (3,4-epoxycyclohexyl) ethyl-
Diethylmethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiisopropeneoxysilane, 1,3-dimethyl-2-imidazolidinone, 1,3
-Diethyl-2-imidazolidinone, N, N'-dimethylpropyleneurea, N-methylpyrrolidone and the like.

By reacting the above-mentioned modifier, a hydroxyl group is added to the polymer block A and / or the polymer block B.
A block copolymer or a hydrogenated product thereof, wherein at least one residue of a modifier to which an atomic group having at least one functional group selected from an epoxy group, an amino group, a silanol group, and an alkoxysilane is bonded is bonded. Is obtained. The position at which the residue of the modifying agent is bonded to the modified block copolymer is not particularly limited. However, it is preferable that the modified block copolymer is bonded to the polymer block A in order to obtain a composition having excellent properties at high temperatures.

In the present invention, the hydrogenated product of the block copolymer can be obtained by hydrogenating the above-obtained block copolymer. The hydrogenation catalyst used for hydrogenation is not particularly limited, and is conventionally known (1) Ni,
Supported heterogeneous catalysts in which metals such as Pt, Pd, and Ru are supported on carbon, silica, alumina, diatomaceous earth, and the like;
(2) a so-called Ziegler-based hydrogenation catalyst using an organic acid salt such as Ni, Co, Fe, Cr or the like, or a transition metal salt such as acetylacetone salt and a reducing agent such as organic aluminum.
(3) A homogeneous hydrogenation catalyst such as an organic metal complex such as an organic metal compound such as Ti, Ru, Rh, and Zr is used. As a specific hydrogenation catalyst, for example, Japanese Patent Publication No. Sho 42
JP-8704, JP-B-43-6636, JP-B-63-4841, JP-B1-37970, JP-B1-53851, JP-B2-9041.
Can be used. Preferred hydrogenation catalysts include a mixture with a titanocene compound and / or a reducing organic metal compound.

As the titanocene compound, JP-A-8-1
Compounds described in JP 09219 can be used,
Specific examples include at least one ligand having a (substituted) cyclopentadienyl skeleton, an indenyl skeleton, or a fluorenyl skeleton, such as biscyclopentadienyl titanium dichloride and monopentamethylcyclopentadienyl titanium trichloride. Compounds. Examples of the reducing organic metal compound include an organic alkali metal compound such as organic lithium, an organic magnesium compound, an organic aluminum compound, an organic boron compound, and an organic zinc compound. The hydrogenation reaction is generally carried out at a temperature in the range of 0 to 200C, preferably 30 to 150C. The pressure of hydrogen used for the hydrogenation reaction is 0.
The pressure is 1 to 15 MPa, preferably 0.2 to 10 MPa, more preferably 0.3 to 5 MPa. The hydrogenation reaction time is 3 minutes to 10 hours, preferably 10 minutes to 5 hours.
The hydrogenation reaction may use any of a batch process, a continuous process, or a combination thereof.

The (1) block copolymer or a hydrogenated product thereof used in the present invention has a vinyl aromatic hydrocarbon content of 5 to 95.
wt%, preferably 8-80 wt%, more preferably 1
0 to 70 wt%. If it is less than 5 wt%, compression set and tensile strength are inferior, and if it exceeds 95 wt%, impact resistance is undesirably reduced. When the content of the vinyl aromatic hydrocarbon is preferably 60 wt% or less, more preferably 55 wt% or less, the block copolymer or the hydrogenated product thereof used in the present invention has properties as a thermoplastic elastomer. The content of the vinyl aromatic hydrocarbon is preferably 6
When it exceeds 0 wt%, more preferably when it is 65 wt% or more, it exhibits properties as a thermoplastic resin. The weight average molecular weight of (1) the block copolymer or its hydrogenated product (hereinafter sometimes referred to as component (1)) used in the present invention is 30,000 or more from the viewpoint of the tensile strength of the composition, and the workability is high. 10 from the point
It is preferably at most 100,000, more preferably from 60,000 to 800,000, further preferably from 70,000 to 600,000.

The weight-average molecular weight was measured by gel permeation chromatography (GPC), and the molecular weight of the peak in the chromatogram was determined from a calibration curve obtained from the measurement of a commercially available standard polystyrene (using the peak molecular weight of the standard polystyrene). Can be determined using The molecular weight when there are a plurality of peaks in a chromatogram refers to the average molecular weight determined from the molecular weight of each peak and the composition ratio of each peak (determined from the area ratio of each peak in the chromatogram). Further, (1) used in the present invention
In the block copolymer or its hydrogenated product, 70% or more of the total vinyl aromatic hydrocarbon content in the block copolymer,
Preferably 80% or more, more preferably 90% or more,
It is a vinyl aromatic hydrocarbon homopolymer block having a number average molecular weight of 20,000 or more.

If less than 70% of the total vinyl aromatic hydrocarbon content in the block copolymer is a vinyl aromatic hydrocarbon homopolymer block having a number average molecular weight of 20,000 or more, the resulting composition is subjected to compression It is not preferable because the distortion is inferior. In the (1) block copolymer or a hydrogenated product thereof used in the present invention, for example, a structural unit based on a conjugated diene or a structural unit obtained by hydrogenating the same is represented by the following formulas (A) to (E). And the ratio of the number of structural units of (A) to (E) is represented by the following formulas (I) to (III).

[0029]

Embedded image

In the above formula (I), if the value of the central formula is less than 0.1, the flexibility and impact resistance are undesirably reduced. On the other hand, when it exceeds 0.85, the productivity of the block copolymer decreases, which is not preferable. Formula (II) above
When the value of the central formula is less than 0.1, thermal stability is undesirably reduced. In the above formula (III), when the value of the central formula exceeds 0.15, thermal stability is undesirably reduced. In addition, the preferable range of the value of the central formula of the above formula (I) is 0.3 to 0.75, more preferably 0.1 to 0.7.
The preferred range of the value of the central formula of the above formula (II) is 0.3 to 1, more preferably 0.5 to 1.
The preferable range of the value of the central formula of the above formula (III) is 0 to 0.07, more preferably 0 to 0.03.

In the present invention, the content of the vinyl aromatic hydrocarbon in the block copolymer can be determined using an ultraviolet spectrophotometer or the like. Further, the vinyl bond content and the hydrogenation rate based on the conjugated diene compound are determined by a nuclear magnetic resonance apparatus (NM
R) can be determined. The molecular weight of the vinyl aromatic hydrocarbon homopolymer block can be determined by a method of oxidative decomposition with di-tert-butyl hydroperoxide using osmium tetroxide as a catalyst (IM KO).
LTHOFF, et-al. , J. et al. Polym. Sc
i. 1,429 (1946)), GPC of a vinyl aromatic hydrocarbon homopolymer block component obtained by decomposing a modified block copolymer before hydrogenation (however, a component having a degree of polymerization of 30 or less is removed). It can be obtained by performing measurement. The content can be determined using an ultraviolet spectrophotometer or the like.

The solution of the block copolymer or its hydrogenated product obtained as described above is subjected to removal of the catalyst residue if necessary, and separation of the block copolymer or its hydrogenated product from the solution. Can be. As a method for separating the solvent, for example, a polar solvent which is a poor solvent for the polymer such as acetone or alcohol is added to the polymer solution, and the polymer is precipitated and collected, and the polymer solution is stirred in boiling water. Throw in,
A method of removing and recovering the solvent by steam stripping, a method of directly heating the polymer solution to distill off the solvent, and the like can be given. In addition, stabilizers such as various phenolic stabilizers, phosphorus-based stabilizers, sulfur-based stabilizers, and amine-based stabilizers can be added to the block copolymer or its hydrogenated product used in the present invention.

In the present invention, (2) silica-based inorganic filler refers to solid particles containing SiO ₂ or Si ₃ Al as a main component of the structural unit, for example, silica, clay, talc, mica , Wollastonite, montmorillonite, zeolite, inorganic fibrous substances such as glass fiber and the like can be used. In addition, a silica-based inorganic filler having a hydrophobic surface or a mixture of a silica-based inorganic filler and a non-silica-based inorganic filler can also be used. As silica, dry method white carbon, wet method white carbon,
Synthetic silicate-based white carbon, colloidal silica, and the like can be used. On the other hand a metal oxide, the chemical formula M _X O _y (M is a metal atom, x, y are each 1
(Integer of 6) as a main component of the structural unit, for example, alumina, titanium oxide, magnesium oxide, zinc oxide, or the like can be used. Also, a mixture of a metal oxide and an inorganic filler other than the metal oxide can be used.

In the present invention, silica and glass fiber are preferred, and silica is particularly preferred. In the composition of the present invention, silica is dispersed in the composition, and in order to sufficiently exhibit the effect of adding silica, the average dispersed particle diameter is 0.05%.
To 1 μm, more preferably 0.05 to 0.5
μm. In the present invention, the blending amount of the (2) silica-based inorganic filler and / or metal oxide (hereinafter, sometimes referred to as component (2)) is determined by the amount of the block copolymer of component (1) or its hydrogenation. It is 0.5 to 50 parts by mass, more preferably 3 to 40 parts by mass, per 100 parts by mass of the product. Ingredient (2)
Is less than 0.5 parts by mass, the effect of adding the silica-based inorganic filler and / or the metal oxide is not exhibited. This is not preferable because of poor properties and mechanical strength.

In the present invention, the (3) olefin polymer (hereinafter, sometimes referred to as component (3)) is a polymer mainly composed of α-olefin such as ethylene and propylene. Ethylene-
A propylene copolymer and the like can be mentioned. This olefin polymer other than olefins such as ethylene and propylene,
A copolymer obtained by copolymerizing a small amount of a vinyl monomer can also be used. For example, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid derivative copolymer may be mentioned. Further, hydrogenated products of polymers of conjugated diene monomers such as butadiene and isoprene are also included. These resins can be used as a mixture of two or more kinds. Considering the processability and mechanical properties of the resulting composition, polypropylene or a mixture of polypropylene and an ethylene-propylene copolymer is preferred.

In the present invention, the blending amount of the (3) olefin-based polymer may be a block copolymer or a hydrogenated product thereof (1).
10 to 500 parts by mass, preferably 20 to 100 parts by mass
３００300 parts by mass. If the amount is less than 10 parts by mass, the compression set and the tensile strength of the composition become insufficient, while if it exceeds 150 parts by mass, the composition becomes poor in elasticity, which is not preferable. In the block copolymer composition of the present invention, (1) the block copolymer or a hydrogenated product thereof
Since an atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane is bonded, the silica-based inorganic filler or /
Has high affinity for metal oxides and disperses silica-based inorganic fillers and / or metal oxides more finely, and at the same time, effectively interacts with them by chemical bonding such as hydrogen bonding. It is possible to obtain a modified block copolymer composition which has been developed and is excellent in mechanical strength, compression set, impact resistance and processability which are the objects of the present invention.

In the present invention, a rubber softener can be blended in order to improve processability. Mineral oils or liquid or low molecular weight synthetic softeners are suitable as rubber softeners. In particular, in general, rubber softening, volume increase,
A mineral oil-based rubber softener called process oil or extender oil used for improving processability is a mixture of an aromatic ring, a naphthenic ring, and a paraffin chain. What is occupied is called paraffinic, and the naphthene ring carbon number is 30-4.
Those having 5% are called naphthenes and those having more than 30% of aromatic carbons are called aromatic. The rubber softener used in the present invention is preferably a naphthene-based and / or paraffin-based softener, and an aromatic-based softener is not preferred in terms of dispersibility and solubility in the composition with the hydrogenated block copolymer. As the synthetic softener, polybutene, low molecular weight polybutadiene and the like can be used, but the above-mentioned softener for mineral oil-based rubber gives better results.

The compounding amount of the rubber softener in the present invention is as follows:
From the viewpoint of suppressing bleed-out, the amount is preferably 300 parts by mass or less based on 100 parts by mass of the block copolymer (1). The block copolymer composition of the present invention includes a block copolymer or a hydrogenated product thereof different from the block copolymer or a hydrogenated product thereof used in the present invention, such as an unmodified block copolymer, a thermoplastic resin, It may be used as a composition with a rubbery polymer or the like.

As the thermoplastic resin, a block copolymer resin of a conjugated diene compound and a vinyl aromatic compound different from the block copolymer defined in the present invention, a vinyl aromatic compound polymer resin such as polystyrene, a vinyl aromatic resin Compounds and other vinyl monomers, such as ethylene, propylene,
Butylene, vinyl chloride, vinylidene chloride, vinyl acetate,
Copolymer resins with acrylic acid esters such as acrylic acid and acrylic methyl, methacrylic acid esters such as methacrylic acid and methyl methacrylate, acrylonitrile, methacrylonitrile, etc., rubber-modified styrene resins (HIP
S), acrylonitrile-butadiene-styrene copolymer resin (ABS), methacrylate-butadiene-
Copolymerization of styrene copolymer resin (MBS), polyvinyl chloride, polyvinylidene chloride, vinyl chloride and / or vinylidene chloride containing at least 50% by weight of vinylidene chloride and other monomers copolymerizable therewith. A polyvinyl acetate-based resin which is a coalesced product, a polyvinyl acetate-based resin which is a copolymer of vinyl acetate having a vinyl acetate content of 50 wt% or more and another monomer copolymerizable therewith, and a hydrolyzate thereof; Polymers of acrylic acid and its esters and amides, polymers of methacrylic acid and its esters and amides, 50% by weight of these acrylic acid monomers
A polyacrylate resin which is a copolymer with other copolymerizable monomers contained above, acrylonitrile and / or
Or, a methacrylonitrile polymer, a nitrile resin which is a copolymer with another copolymerizable monomer containing 50% by weight or more of these acrylonitrile-based monomers, and structural units of the polymer are bonded by repeating amide group bonds. Linear polymers such as ring-opening polymers and copolymers such as ε-aminocaprolactam and ω-aminolaurolactam, condensation polymers of ε-aminoundecanoic acid, hexamethylenediamine and adipic acid and sebacic acid. Polycondensates with basic acids, specifically nylon-46, nylon-
6, Nylon-66, Nylon-610, Nylon-1
1, polyamide-12 resins such as nylon-12 and nylon-6-nylon-12 copolymers, and linear polymers in which structural units of the polymer are linked by repeating ester bonds, for example, adipic acid, sebacic acid, terephthalic acid ,
Isophthalic acid, P, P'-dicarboxydiphenyl,
Dibasic acids such as 2,6-naphthalene dicarboxylic acid or derivatives thereof, and ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol, P-xylene glycol , Polycondensates with glycols (or diols) such as bisphenol A, polyester-based resins such as ring-opening polymers such as pivalolactone, β-propiolactone, and ε-caprolactone; poly (1,4-butylene adipate); (1,6-hexane adipate), polyester diols such as polycaprolactone, polyether diols such as polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, ethylene glycol, 1,4-butanediol,
A glycol component selected from glycols such as 1,6-hexanediol and an aromatic, alicyclic or aliphatic diisocyanate such as tolylene diisocyanate;
4,4′-diphenylmethane diisocyanate, a thermoplastic polyurethane polymer obtained by a polyaddition reaction with a diisocyanate component such as hexamethylene diisocyanate, a linear polymer in which constituent units of the polymer are bonded by repeating carbonic acid ester bonds, For example 4,
Polymers obtained by the reaction of phosgene with dihydroxy compounds such as 4'-dihydroxydiphenylalkane and 4,4'-dihydroxydiphenylsulfide, or polymers obtained by transesterification of the dihydroxy compounds with diphenyl carbonate, specifically Are polycarbonate polymers such as poly-4,4'-dioxydiphenyl-2,2'-propane carbonate, thermoplastic polysulfones such as polyether sulfone and polyallyl sulfone, specifically poly (ether sulfone);
Poly (4,4'-bisphenol ether sulfone),
Polysulfone resins such as poly (thioethersulfone), polymers of formaldehyde or trioxane, polyoxymethylene resins such as copolymers of formaldehyde or trioxane with other aldehydes, cyclic ethers, epoxides, isocyanates, vinyl compounds, etc., poly Polyphenylene ether resins such as (2,6-dimethyl-1,4-phenylene) ether, polyphenylene sulfide resins such as polyphenylene sulfide and poly 4,4′-diphenylene sulfide, bisphenol A
Polyarylate resin, polyetherketone polymer or copolymer, specifically a polyketone resin such as polyetheretherketone, and hydrogen of a chain hydrocarbon polymer compound. A polymer having a structure in which part or all of is substituted by fluorine, specifically, polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkylvinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychloro Fluoro resins such as trifluoroethylene, tetrafluoroethylene-ethylene copolymer, chlorotrifluoroethylene-ethylene copolymer, polyvinylidene fluoride, polyvinyl fluoride, paraoxybenzoic acid, terephthalic acid, isophthalic acid, 4,4 '-Dihydroxy A polyoxybenzoyl-based polymer such as a polymer or copolymer produced by solution polycondensation or melt polycondensation using sidiphenyl or a derivative thereof, a polymer having an imide bond in the main chain, for example, polyimide, polyaminobis Polyimide resins such as maleimide (polybismaleimide), bismaleimide / triazine resin, polyamideimide, polyetherimide,
Examples thereof include polybutadiene-based resins such as 1,2-polybutadiene and trans polybutadiene. The number average molecular weight of these thermoplastic resins is preferably 1,000 or more, more preferably 5,000 to 5,000,000, and further preferably 10,000 to 1,000,000.
One million. Further, two or more of these thermoplastic resins may be used in combination.

Examples of the rubbery polymer include butadiene rubber and its hydrogenated product, styrene-butadiene rubber different from the block copolymer defined in the present invention and its hydrogenated product, isoprene rubber, acrylonitrile-butadiene rubber and its hydrogenated product. Additives, chloroprene rubber, ethylene-
Propylene rubber, ethylene-propylene-diene rubber,
Ethylene-butene-diene rubber, butyl rubber, ethylene-butene rubber, ethene-hexene rubber, ethylene-octene rubber, acrylic rubber, fluorine rubber, silicone rubber, chlorinated polyethylene rubber, epichlorohydrin rubber, α, β-unsaturated nitrile-acrylic acid ester-conjugated Examples thereof include diene copolymer rubber, urethane rubber, polysulfide rubber, styrene butadiene block copolymer and hydrogenated product thereof, styrene-isoprene block copolymer, and natural rubber. These rubbery polymers may be modified rubbers having a functional group.

In the composition of the present invention, the following polystyrene resins and polyphenylene ether resins are preferred as the resins to be blended among the above-mentioned thermoplastic resins. As the polystyrene resin, those obtained by a known radical polymerization method or ionic polymerization method can be suitably used. The number average molecular weight is preferably 5000 to 500,000,
More preferably, it is 10,000 to 300,000, and the molecular weight distribution (the ratio of the weight average molecular weight Mw to the number average molecular weight Mn (Mw / M
n)) is preferably 5 or less. The polystyrene resin is blended for the purpose of improving the processability of the obtained composition, and the blending amount is 1000 parts by mass or less based on 100 parts by mass of the block copolymer (a) from the viewpoint of the impact strength of the composition. , And more preferably 900 parts by mass or less.

The polyphenylene ether resin has the following general formula:

Embedded image (Where R ^{19 to} R ²² each represent a substituent selected from hydrogen, halogen, and hydrocarbon, and may be the same or different from each other). 3 in a 0.5 g / dl chloroform solution
Those having a reduced viscosity of 0.05 to 0.70 measured at 0 ° C. are preferred, and more preferably 0.10 to 0.6.
0, more preferably in the range of 0.15 to 0.60. Especially when obtaining a good mechanical strength, 0.30 to 0.60 is recommended. As the polyphenylene ether resin, a known resin can be used. Specific examples include poly (2,6-dimethyl-1,4-phenylene ether) and poly (2-methyl-
6-ethyl-1,4-phenylene ether), poly (2,6-diphenyl-1,4-phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2,6-phenyl-1,4-phenylene ether) 6-dichloro-1,4-
Phenylene ether), and 2,6-dimethylphenol and other phenols (for example, 2,3,6
-Trimethylphenol or 2-methyl-6-butylphenol). Among them, poly (2,6-dimethyl-1,4-phenylene ether),
A copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol is preferred, and poly (2,6-dimethyl-1,4-phenylene ether) is more preferred.

When poly (2,6-dimethyl-1,4-phenylene ether) is used, its reduced viscosity is preferably in the range described above. In the present invention, the polyphenylene ether resin is blended in order to improve the compression set of the composition obtained, the amount of the composition, hardness of the composition, impact resistance, from the balance with compression set,
The weight ratio of the block copolymer of component (1) or its hydrogenated product / polyphenylene ether resin is 90/10 to 10/9.
It is preferably within the range of 0.

Further, any additives can be blended according to various purposes within a range that does not significantly impair the effects of the present invention. The type of the additive is not particularly limited as long as it is generally used for blending a thermoplastic resin or a rubber-like polymer. For example, calcium carbonate, magnesium carbonate,
Magnesium hydroxide, calcium sulfate, barium sulfate,
Inorganic fillers, such as carbon black, pigments such as iron oxide,
Lubricants such as stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, ethylene bisstearamide, mold release agents, paraffinic process oil, naphthenic process oil, aromatic process oil, paraffin, organic poly Softeners and plasticizers such as siloxane and mineral oil, hindered phenolic antioxidants, antioxidants such as phosphorus heat stabilizers, hindered amine light stabilizers, benzotriazole ultraviolet absorbers, flame retardants, antistatic agents , Organic fiber, glass fiber,
Examples thereof include reinforcing agents such as carbon fibers and metal whiskers, coloring agents, and other additives or mixtures thereof described in "Rubber / Plastic Compounding Chemicals" (Rubber Digest).

The method for producing the block copolymer composition of the present invention is not particularly limited, and a known method can be used. For example, it can be manufactured using a melt kneader such as a single screw extruder, a twin screw extruder, a Banbury mixer, a heating roll, a Brabender, various kneaders, and the like. At this time, the order of addition of each component is not limited. For example, all components may be kneaded at once, or after kneading arbitrary components, the remaining components may be added at once or sequentially and kneaded. A method of dispersing the component (2) in a solution after the polymerization of the component (1), a solution after the hydrogenation reaction, or a solution in which the component (1) is dissolved in a solvent, mixing, and then removing the solvent by heating. Is used. In the present invention, a melt mixing method using an extruder is preferable from the viewpoint of productivity, but a mixing method in a solvent is particularly recommended to obtain a composition having good dispersibility.

In the block copolymer composition of the present invention, as described above, a hydrogen bond between a specific functional group bonded to the block copolymer and the silica-based inorganic filler or / and metal oxide. A complex state in which these are integrated is expressed by a chemical bond such as Such a complex state is expressed, for example, when the component (1) and the component (2) are mixed in a solution, or when the component (2) is added to the solution of the component (1) and mixed. In this case, it can be confirmed that even when the mixed solution is allowed to stand for a certain period of time, the ratio of the component (2) separating from the mixed solution and settling is small, and the ratio of the finely dispersed and floating component (2) is large. Under such circumstances, when the average particle size of the component (2) is small (for example, when the secondary particle size is 1 to 50 mμ), the presence of the component (2) settled at the bottom of the container is substantially scarcely observed. Absent. On the other hand, when the component (1) does not have the functional group defined in the present invention, substantially the most of the component (2) settles at the bottom of the container when the mixed solution with the component (2) is allowed to stand for a certain period of time. .

The block copolymer composition of the present invention can be molded by a commonly used thermoplastic resin molding machine, and can be formed into sheets, films, injection molded articles of various shapes, hollow molded articles, pressure molded articles. It can be used as various molded products such as vacuum molded products, extrusion molded products and the like. These molded products can be used as food packaging materials, medical equipment materials, home electric appliances and parts thereof, materials for automobile parts, industrial goods, daily necessities, toys, footwear materials, and the like.

[0048]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the invention thereto. In the following examples, (1) the properties of the block copolymer or its hydrogenated product and the physical properties of the block copolymer composition were measured as follows. 1. Characteristics of block copolymer or hydrogenated product thereof (1) Styrene content Using a UV spectrophotometer (Hitachi UV200), 262
It calculated from the absorption intensity of nm.

(2) 1,2 Bonding Amount, Hydrogenation Rate, and 1,2-Vinyl Unit Remaining Nuclear Porcelain Resonator (DPX-400 manufactured by BRUCKER)
It measured using. Incidentally, the amount of 1,2 bonds corresponds to [the value of the central formula of the formula (I) in the specification [claims] of claim 3] × 100, and the hydrogenation rate is expressed in [the description [ Claims] The value of the central formula of formula (II) in claim 3] × 100, and the residual amount of 1,2-vinyl unit is:
[Description [Claims] Formula (II) in claim 3
Value of the central formula of I)] × 100.

(3) Weight average molecular weight GPC [The equipment is LC10 manufactured by Shimadzu Corporation, and the column is Shimpac GPC805 + GPC804 + G manufactured by Shimadzu Corporation.
PC804 + GPC803], tetrahydrofuran was used as a solvent, and the measurement was performed at a temperature of 35 ° C. The weight average molecular weight was determined by using a calibration curve (prepared using the peak molecular weight of standard polystyrene) obtained by measuring the molecular weight of the peak of the chromatogram from the measurement of commercially available standard polystyrene. The molecular weight when there are a plurality of peaks in a chromatogram refers to the average molecular weight determined from the molecular weight of each peak and the composition ratio of each peak (determined from the area ratio of each peak in the chromatogram). Tables 1 and 3
In it, it is simply abbreviated as molecular weight.

(4) Number average molecular weight of styrene homopolymer block A method of oxidatively decomposing the block copolymer with di-tert-butyl hydroperoxide using osmium tetroxide as a catalyst (IM KOLTHOFF, et-a)
l. , J. et al. Polym. Sci. 1,429 (194
According to 6)), a styrene homopolymer block component was obtained from the block copolymer before hydrogenation (however, components having a degree of polymerization of 30 or less were removed), and the component was determined by GPC measurement. (5) Styrene homopolymer block content (block ratio) The styrene homopolymer block obtained by the above oxidative decomposition was analyzed by an ultraviolet spectrophotometer, and calculated by the following equation. Block ratio (%) = (wt% of styrene homopolymer block in hydrogenated block copolymer) / (total styrene weight% in hydrogenated block copolymer) × 100

2. Measurement of Physical Properties of Block Copolymer Composition (1) Transparency (Haze) A compression molded sheet having a thickness of 2 mm was prepared from the block copolymer composition, and this was used as a test piece and subjected to ASTM D1003.
It measured according to. (2) Heat resistance The temperature change of the dynamic storage elastic modulus (E ') of the block copolymer composition was measured using a DMA spectrometer (983 DMA manufactured by DuPont Instruments) under the following conditions. The heat resistance was evaluated at the inflection temperature of the high temperature part. Test specimen thickness: 2 mm, span length: 16 mm, measurement temperature 0 ° C to 200 ° C, heating rate 2 ° C / min. , Measurement frequency mode: resonance frequency (3) Abrasion resistance
-301), the change in weight before and after abrasion 1000 times was observed.

(4) Processability The block copolymer composition is prepared by using a biaxial open roll for 20 minutes.
The mixture was melted and kneaded at a temperature of 0 ° C., and the workability was determined based on the state of winding around a roll. ：: Good state of winding around the roll. Δ: There is no winding around the roll, but the sheet is formed. X: It does not form a sheet, and kneading is substantially difficult. (5) JIS-A hardness Measured according to JIS-K6301.

(6) Compression set (%) Measured by the method described in JIS-K-6301 (70 ° C. × 22 hours). (7) Tensile breaking strength (MPa) Based on JIS-K-6251. Tensile speed is 500m
m / min. (8) Flexural strength (MPa) Measured according to ASTM-D790. (9) Notched Izod impact strength (J / m) Measured according to JIS-K-7110.

The hydrogenation catalyst used for the hydrogenation reaction was prepared by the following method. 1) Hydrogenation catalyst I Into a nitrogen-purged reaction vessel, 1 liter of dried and purified cyclohexane was charged, and 100 mmol of bis (η ⁵ -cyclopentadienyl) titanium dichloride was added. While sufficiently stirring, 200 mmol of trimethylaluminum was added. The n-hexane solution was added and reacted at room temperature for about 3 days. 2) Hydrogenation catalyst II A nitrogen-substituted reaction vessel was charged with 2 liters of dried and purified cyclohexane, and 40 mmol of bis (η ⁵ -cyclopentadienyl) titanium di- (p-tolyl) and 1,000 having a molecular weight of about 1,000 were added. After adding 150 g of 2-polybutadiene (the amount of 1,2 bonds is about 85%), a cyclohexane solution containing 60 mmol of n-butyllithium was added and reacted at room temperature for 5 minutes, and 40 mmol of n-butanol was immediately added with stirring. And stored at room temperature.

In the following examples, the following components were used as each component. (1) Block copolymer Tables 1 and 3 show the properties of the block copolymer. (2) Inorganic filler Silica A: precipitated silica (Siper manufactured by Degussa)
nat500LS: secondary particle size 3.5 μm) Silica B: Dry high-dispersibility silica (HDK N20 manufactured by Asahi Kasei Wacker Silicone) Silica C: Wet silica (Ultra manufactured by Degussa)
(sil VN3: secondary particle diameter 16 μm)

(3) Olefin polymer Polypropylene (PM801A manufactured by Montell SDK) Other components Softener for rubber: Diana Process Oil P manufactured by Idemitsu Kosan Co., Ltd.
W-380 polystyrene resin: polystyrene 685 manufactured by A & M Styrene Co., Ltd. polyphenylene ether resin: poly (2,6-dimethyl-1,4-phenylene ether) (reduced viscosity 0.54)

[0058]

Example 1 Autoclave with stirrer and jacket
Styrene 1
Cyclohexane solution containing 0 parts by mass (concentration: 20 wt%)
Was introduced. Next, n-butyllithium and tetramethylethylenediamine were added, polymerization was performed at 70 ° C. for 1 hour, and a cyclohexane solution (concentration: 20 wt%) containing 80 parts by mass of butadiene purified in advance was added, and polymerization was performed at 70 ° C. for 1 hour. A cyclohexane solution containing 10 parts by mass of styrene was added, and polymerized at 70 ° C. for 1 hour. Thereafter, tetraglycidyl-1,3-bisaminomethylcyclohexane (hereinafter, referred to as modifier M1) as a modifier was reacted equimolarly with n-butyllithium used for the polymerization. The obtained block copolymer has a styrene content of 20.
wt%, the amount of 1,2 bonds in the polybutadiene portion was 50%.

To the block copolymer obtained above, 100 ppm of hydrogenation catalyst I was added as Ti per polymer, and a hydrogenation reaction was performed at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. for 1 hour. Thereafter, methanol was added, and octadecyl-3- (3,5-di-tert-butyl-4- as a stabilizer was then added.
0.3 parts by weight of (hydroxyphenyl) propionate was added to 100 parts by weight of the block copolymer. Table 1 shows the properties of the obtained block copolymer (Polymer 1). The ratio of the unmodified block copolymer mixed in the polymer 1 was 20% by weight.

Next, silica A (Ship manufactured by Degussa) was added to the cyclohexane solution of the polymer 1 obtained above.
ernat500LS) was added and mixed in an amount of 5 parts by mass per 100 parts by mass of the polymer 1. A part of this mixed solution was sampled and left at room temperature for 24 hours. Silica A was finely dispersed uniformly, and almost no silica A separated and settled from the mixed solution. In this way, it was confirmed that the polymer 1 and the silica A formed a complex state in which they were intimately integrated. Next, the above polymer 1
Cyclohexane was removed from the mixed solution of silica and silica A by heating to obtain a block copolymer composition. Table 2 shows the physical properties of the obtained composition.

[0061]

Comparative Example 1 Silica A was added to a solution of a block copolymer (polymer 2) obtained in the same manner as in Example 1 except that no modifier was used, and mixed as in Example 1. When a part of this solution was sampled and allowed to stand for 24 hours, silica A was precipitated, and the composite state as in Example 1 was not exhibited. Next, cyclohexane was removed by heating from the solution obtained by mixing the polymer 2 and the silica A to obtain a block copolymer composition. Table 2 shows the physical properties of the obtained composition.

Comparative Examples 2 and 3 A block copolymer composition containing silica A in an amount less than the range specified in the present invention (Comparative Example 2) and a block containing silica A in an amount larger than the range Example 1 was prepared using a copolymer composition (Comparative Example 3).
It was produced in the same manner as described above. Table 2 shows the physical properties of the obtained composition.

[0062]

Example 2 Autoclave with stirrer and jacket
Styrene 1
Cyclohexane solution containing 0 parts by mass (concentration: 20 wt%)
Was introduced. Next, n-butyllithium and tetramethylethylenediamine were added, polymerization was performed at 70 ° C. for 1 hour, and a cyclohexane solution (concentration: 20 wt%) containing 60 parts by mass of butadiene purified in advance was added, and polymerization was performed at 70 ° C. for 1 hour. A cyclohexane solution containing 10 parts by weight of styrene was added, and polymerization was performed at 70 ° C. for 1 hour. Thereafter, a cyclohexane solution containing 20 parts by mass of butadiene was further added, and the mixture was polymerized at 70 ° C. for 1 hour. Then, tetra-glycidyl meta-xylene diamine (hereinafter, referred to as a modifier M2) was used as a modifier, and n-butyl lithium used for the polymerization was used. The reaction was carried out in equimolar amounts. The obtained block copolymer had a styrene content of 20% by weight and a 1,2 bond amount in the polybutadiene portion of 50%.

To the block copolymer obtained above, hydrogenation catalyst II was added at 100 ppm as Ti per polymer, and a hydrogenation reaction was performed at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. for 1 hour. Thereafter, methanol was added, and octadecyl-3- (3,5-di-tert-butyl-4- as a stabilizer was then added.
0.3 parts by mass of (hydroxyphenyl) propionate was added to 100 parts by mass of the block copolymer. Table 1 shows the properties of the obtained block copolymer (Polymer 3). The ratio of the unmodified block copolymer mixed in the polymer 3 was 20% by weight.

Next, 100 parts by mass of the polymer A was added to the cyclohexane solution of the polymer 3 obtained above.
And 5 parts by mass of the mixture. A part of the solution was sampled and left at room temperature for 24 hours. Silica A was finely dispersed uniformly, and almost no silica A separated and precipitated from the solution. In this way, it was confirmed that the polymer 3 and the silica A formed a complex state in which they were intimately integrated. Next, cyclohexane was removed from the mixed solution of the polymer 3 and silica A by heating to obtain a block copolymer composition. Table 2 shows the physical properties of the obtained composition. When the wear resistance of this composition was examined, the wear amount was 14 mg.

[0065]

Comparative Example 4 Silica A was added to a solution of a block copolymer (polymer 4) obtained in the same manner as in Example 2 except that no modifier was used, and mixed as in Example 2. When a part of this solution was sampled and allowed to stand for 24 hours, silica A was precipitated, and the composite state as in Example 2 was not expressed. Next, cyclohexane was removed by heating from the above solution obtained by mixing the polymer 4 and the silica A to obtain a block copolymer composition. Table 2 shows the physical properties of the obtained composition. In addition, when the wear resistance of this composition was examined, the wear amount was 25 mg.

[0066]

Embodiment 3 Autoclave with stirrer and jacket
Styrene 2 which has been washed, dried and purged with nitrogen
Cyclohexane solution containing 0 parts by mass (concentration: 20 wt%)
Was introduced. Next, n-butyllithium and tetramethylethylenediamine were added, and polymerization was carried out at 70 ° C. for 1 hour. A cyclohexane solution containing parts by mass was added, and polymerization was performed at 70 ° C. for 1 hour. Then, the modifier M
1 is 1/1 based on the n-butyl lithium used for the polymerization.
A 4-fold molar reaction was performed. The obtained block copolymer had a styrene content of 40% by weight and a 1,2 bond amount in the polybutadiene portion of 17%.

After methanol was added to the block copolymer obtained above to deactivate it, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl was used as a stabilizer. ) -4-Methylphenyl acrylate was added in an amount of 0.3 part by mass based on 100 parts by mass of the block copolymer. Table 1 shows the properties of the block copolymer (Polymer 5) obtained by removing cyclohexane from the cyclohexane solution of the block copolymer by the steam stripping method. The ratio of the unmodified block copolymer mixed in the polymer 5 was 30% by weight. Next, 100 parts by mass of the polymer 5 obtained above was mixed with silica B
(Asahi Kasei Wacker Silicon HDK N-20)
0 parts by mass and L / D34 of 30 mmφ co-rotating twin-screw extruder were mixed to obtain a block copolymer composition. The extrusion temperature in the extruder was 210 ° C., and the rotation speed was 200 rpm. Haze of the obtained composition was 55%.

[0068]

Comparative Example 5 A block copolymer obtained by the same method as in Example 3 except that silicon tetrachloride was used in place of the modifier M1 in a molar amount of 1/4 times the n-butyllithium used in the polymerization. A block copolymer composition was obtained in the same manner as in Example 3 using the coalesced polymer (polymer 6). H of the resulting composition
The aze was 80%, which was inferior to the composition of Example 3 in transparency.

[0069]

Embodiment 4 Autoclave with stirrer and jacket
Styrene 3
Cyclohexane solution containing 5 parts by mass (concentration: 20 wt%)
Was introduced. Next, n-butyllithium and tetramethylethylenediamine were added, and polymerized at 70 ° C. for 1 hour.
A cyclohexane solution containing 20 parts by mass (concentration: 20 wt%) was added, and polymerization was carried out at 70 ° C. for 1 hour. A cyclohexane solution containing 35 parts by mass of styrene was added, and polymerization was carried out at 70 ° C. for 1 hour. Thereafter, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine (hereinafter referred to as a modifier M3) as a modifier was added to n-butyllithium used for the polymerization. To make an equimolar reaction. The obtained block copolymer had a styrene content of 80 wt.
%, And the amount of 1,2 bonds in the polybutadiene portion was 35%.

To the block copolymer obtained above, hydrogenation catalyst I was added at 100 ppm as Ti per polymer, and a hydrogenation reaction was performed at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. for 1 hour. Thereafter, methanol was added, and octadecyl-3- (3,5-di-tert-butyl-4- as a stabilizer was then added.
0.3 parts by mass of (hydroxyphenyl) propionate was added to 100 parts by mass of the block copolymer. Table 1 shows the properties of the obtained block copolymer (polymer 7). The ratio of the unmodified block copolymer mixed in the polymer 7 was 40% by weight. Next, 5 parts by mass of silica B (HDK N20 manufactured by Asahi Kasei Wacker Silicon Co., Ltd.) was added to the cyclohexane solution of the polymer 7 obtained above and mixed with 100 parts by mass of the polymer 7. A part of this solution was sampled and left at room temperature for 24 hours. Silica B was finely dispersed uniformly, and almost no silica B separated and precipitated from the solution. In this way, it was confirmed that the polymer 7 and the silica B formed a complex state in which they were intimately integrated.

[0071]

Embodiment 5 Autoclave with stirrer and jacket
Styrene 1
Cyclohexane solution containing 5 parts by mass (concentration: 20 wt%)
Was introduced. Next, n-butyllithium and tetramethylethylenediamine were added, polymerization was performed at 70 ° C. for 1 hour, and a cyclohexane solution (concentration: 20 wt%) containing 70 parts by mass of butadiene purified in advance was added, and polymerization was performed at 70 ° C. for 1 hour. A cyclohexane solution containing 15 parts by mass of styrene was added, and polymerization was performed at 70 ° C. for 1 hour. Thereafter, γ-glycidoxypropyltrimethoxysilane (hereinafter, referred to as modifier M4) as a modifier was reacted in an equimolar amount to n-butyllithium used for the polymerization. The obtained block copolymer had a styrene content of 30% by weight and a 1,2 bond amount in the polybutadiene portion of 40%.

To the block copolymer obtained above, hydrogenation catalyst II was added in an amount of 100 ppm as Ti per polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. for 1 hour. Thereafter, methanol was added, and octadecyl-3- (3,5-di-tert-butyl-4- as a stabilizer was then added.
0.3 parts by mass of (hydroxyphenyl) propionate was added to 100 parts by mass of the block copolymer. Table 1 shows the properties of the block copolymer (polymer 8) obtained by removing cyclohexane from the cyclohexane solution of the block copolymer by a steam stripping method. The ratio of the unmodified block copolymer mixed in the polymer 8 was 25 wt%. Next, silica C (De) was added to the cyclohexane solution of polymer 8 obtained above.
Gussa Ultrasil VN3) was added and mixed at 10 parts by mass per 100 parts by mass of polymer 8.
A part of this solution was sampled and left at room temperature for 24 hours. Silica C was finely dispersed uniformly, and almost no silica C separated and precipitated from the solution. In this way, it was confirmed that the polymer 8 and the silica C formed a complex state in which they were intimately integrated.

[0073]

Example 6 In Example 3, isoprene was used in place of butadiene, and the styrene content was 15% by weight in the same manner as in Example 3;
A block copolymer (Polymer 9) having a total amount of bonding of 30 wt% was obtained. Next, silica A (Si produced by Degussa) was added to the cyclohexane solution of the polymer 9 obtained above.
pernat500LS) was added and mixed with 20 parts by mass per 100 parts by mass of polymer 9. A part of the solution was sampled and left at room temperature for 24 hours. Silica A was finely dispersed uniformly, and almost no silica A separated and precipitated from the solution. In this way, it was confirmed that the polymer 9 and the silica A formed a complex state in which they were intimately integrated.

[0074]

Example 7 In Example 1, 1,3-
A block copolymer (Polymer 10) was obtained in the same manner as in Example 1 except that dimethyl-2-imidazolidinone (M5) was used. Next, silica A (Sipernat 500 LS manufactured by Degussa) was added to the cyclohexane solution of the polymer 10 obtained above.
5 parts by weight per part by weight was added and mixed. A part of this solution was sampled and left at room temperature for 24 hours.
Was uniformly finely dispersed, and there was almost no silica A separated and settled from the solution. In this manner, it was confirmed that the polymer 10 and the silica A formed a composite state in which they were intimately integrated.

[0075]

[Table 1]

[0076]

[Table 2]

[0077]

Examples 8 and 9 A cyclohexane solution containing 14.7 parts by weight of styrene (concentration: 20) was washed, dried, and purged with nitrogen to wash an autoclave equipped with a stirrer and a jacket.
wt%). Next, n-butyllithium and tetramethylethylenediamine were added, polymerization was performed at 70 ° C. for 1 hour, and a cyclohexane solution (concentration: 20% by weight) containing 72 parts by mass of butadiene purified in advance was added, and polymerization was performed at 70 ° C. for 1 hour. A cyclohexane solution containing 13.3 parts by mass of styrene was added, and polymerization was performed at 70 ° C. for 1 hour. Thereafter, the modifier M5 was reacted equimolarly to n-butyllithium used for the polymerization. The obtained block copolymer had a styrene content of 28% by weight and a 1,2 bond amount in the polybutadiene portion of 38%.

To the block copolymer obtained above, 100 ppm of Ti per hydrogenation catalyst per polymer was added, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. for 1 hour. Thereafter, methanol was added, and octadecyl-3- (3,5-di-tert-butyl-4- as a stabilizer was then added.
0.3 parts by mass of (hydroxyphenyl) propionate was added to 100 parts by mass of the block copolymer. Thereafter, cyclohexane was removed by heating from the obtained block copolymer cyclohexane solution to obtain a block copolymer (polymer 11). Table 3 shows the analysis results of the polymer 11. The ratio of the unmodified block copolymer mixed in the polymer 11 was 20% by weight.

100 parts by mass of polymer 11 and a softening oil for rubber (Diana Process Oil PW-38 manufactured by Idemitsu Kosan Co., Ltd.)
0) was previously melt-kneaded with a 30 mmφ twin screw extruder at 230 ° C. with the composition shown in Table 4, and then the amount of silica A or C shown in Table 4 as Component (2) was used as the component (3). 0.88 parts by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer was further added to the amount of polypropylene resin shown in No. 4 and a 25 mmφ twin screw extruder. Melt kneading at 230 ° C,
A block copolymer composition was obtained. Table 4 shows the physical properties of the obtained composition.

[0080]

Comparative Example 6 A block copolymer composition was obtained in the same manner as in Examples 8 and 9 except that silica was not blended. Table 4 shows the physical properties of the obtained composition.

Comparative Example 7 A block copolymer composition was obtained in the same manner as in Examples 8 and 9 except that 80 parts by mass of silica B was blended. Table 4 shows the physical properties of the obtained composition.

Comparative Example 8 A block copolymer (polymer 12) obtained in the same manner as in Example 8 except that no modifier was used was used.
A block copolymer composition was obtained in the same manner as in Example 8. Table 4 shows the physical properties of the obtained composition.

Comparative Example 9 A block copolymer (polymer 13) obtained in the same manner as in Example 8 except that silicon tetrachloride was used instead of the modifier M5 was used. A polymer composition was obtained. Table 4 shows the physical properties of the obtained composition.

[0081]

Example 10 A cyclohexane solution containing 20.5 parts by mass of styrene previously purified by washing, drying, and purging with a stirrer and a jacketed autoclave was replaced with nitrogen (concentration: 20 watts).
t%). Next, n-butyllithium and tetramethylethylenediamine were added, and polymerization was carried out at 70 ° C. for 1 hour.
After polymerization for 1 hour, a cyclohexane solution containing 18.5 parts by mass of styrene was added, and polymerization was performed at 70 ° C. for 1 hour. Thereafter, the modifier M1 was reacted equimolarly with n-butyllithium used for the polymerization. The obtained block copolymer had a styrene content of 39% by weight and a 1,2 bond amount in the polybutadiene portion of 37%.

The block copolymer obtained above was added with 100 ppm of hydrogenation catalyst II as Ti per polymer, and a hydrogenation reaction was performed at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. for 1 hour. Thereafter, methanol was added, and octadecyl-3- (3,5-di-tert-butyl-4- as a stabilizer was then added.
0.3 parts by mass of (hydroxyphenyl) propionate was added to 100 parts by mass of the block copolymer. Thereafter, cyclohexane was removed from the obtained block copolymer cyclohexane solution by heating to obtain a block copolymer (polymer 14). Table 3 shows the analysis results of the polymer 14. The ratio of the unmodified block copolymer mixed in the polymer 14 was 25% by weight. 100 parts by mass of polymer 14 and 100 parts by mass of a softening oil for rubber (Diana Process Oil PW-380 manufactured by Idemitsu Kosan Co., Ltd.)
After melt-kneading at 230 ° C. with a mmφ twin-screw extruder, 15 parts by mass of silica A as component (2), 34 parts by mass of polypropylene resin as component (3), and octadecyl-3- (3,5 0.88 parts by mass of -di-t-butyl-4-hydroxyphenyl) propionate was added, and the mixture was melt-kneaded at 230 ° C with a 25 mmφ twin-screw extruder.
A block copolymer composition was obtained. Table 4 shows the physical properties of the obtained composition.

[0083]

EXAMPLE 11 A cyclohexane solution containing 17.8 parts by mass of styrene (purity: 20 w
t%). Next, n-butyllithium and tetramethylethylenediamine were added, and polymerization was carried out at 70 ° C. for 1 hour.
Polymerization was carried out for 1 hour, and a cyclohexane solution containing 16.2 parts by mass of styrene was further added, and polymerization was carried out at 70 ° C. for 1 hour. Thereafter, the modifier M4 was reacted equimolarly with n-butyllithium used for the polymerization. The obtained block copolymer had a styrene content of 34% by weight and a 1,2 bond amount in the polybutadiene portion of 42%.

To the block copolymer obtained above, 100 ppm of Ti per hydrogenation catalyst II was added per polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. for 1 hour. Thereafter, methanol was added, and octadecyl-3- (3,5-di-tert-butyl-4- as a stabilizer was then added.
0.3 parts by mass of (hydroxyphenyl) propionate was added to 100 parts by mass of the block copolymer. Thereafter, cyclohexane was removed from the obtained block copolymer cyclohexane solution by heating to obtain a block copolymer (polymer 15). Table 3 shows the analysis result of the polymer 15. The ratio of the unmodified block copolymer mixed in the polymer 15 was 25% by weight. 100 parts by mass of polymer 15 and 100 parts by mass of a softening oil for rubber (Diana Process Oil PW-380 manufactured by Idemitsu Kosan Co., Ltd.)
After melt-kneading at 230 ° C. with a mmφ twin-screw extruder, 15 parts by mass of silica A as component (2), 34 parts by mass of polypropylene resin as component (3), and octadecyl-3- (3,5 0.88 parts by mass of -di-t-butyl-4-hydroxyphenyl) propionate was added, and the mixture was melt-kneaded at 230 ° C with a 25 mmφ twin-screw extruder.
A block copolymer composition was obtained. Table 4 shows the physical properties of the obtained composition.

[0085]

[Table 3]

[0086]

[Table 4]

[0087]

Examples 12 and 13 100 parts by weight of polymer 11
100 parts by mass or 136 parts by mass of a softening oil for rubber (Diana Process Oil PW-380 manufactured by Idemitsu Kosan Co., Ltd.)
After melt-kneading at 230 ° C. in a mmφ twin screw extruder, the amount of silica B shown in Table 5 as component (2) and component (3)
3 parts by mass of a polystyrene resin, 7 parts by mass of a polyphenylene ether resin, and octadecyl-3-
(3,5-di-t-butyl-4-hydroxyphenyl)
0.88 parts by mass of propionate was added, and the mixture was melt-kneaded at 270 ° C. with a 25 mmφ twin-screw extruder to obtain a block copolymer composition. Table 5 shows the physical properties of the obtained composition.

Comparative Example 10 Example 12 was repeated except that polymer 12 was used.
A block copolymer composition was obtained in the same manner as in the above. Table 5 shows the physical properties of the obtained composition.

[0088]

Comparative Example 11 A cyclohexane solution containing 20 parts by mass of styrene (concentration 20 wt.
%). Then n-butyllithium was added,
After polymerization for 1 hour at 70 ° C, pre-purified butadiene 3
Cyclohexane solution containing 0 parts by mass (concentration: 20 wt%)
Was added, and the mixture was polymerized at 70 ° C. for 1 hour. Further, a cyclohexane solution containing 50 parts by mass of styrene was added, and the mixture was polymerized at 70 ° C. for 1 hour. The obtained block copolymer had a styrene content of 70% by weight and a 1,2 bond amount of the polybutadiene portion of 11%.
%Met. Octadecyl-3- as a stabilizer
(3,5-di-t-butyl-4-hydroxyphenyl)
0.3 parts by mass of propionate was added to 100 parts by mass of the block copolymer. Thereafter, cyclohexane was removed by heating from the resulting block copolymer cyclohexane solution to obtain a block copolymer (polymer 18). Table 3 shows the analysis results of the polymer 18. A block copolymer composition was obtained using Polymer 18 in the same manner as in Example 12. Table 5 shows the physical properties of the obtained composition.

[0089]

[Table 5]

[0090]

EXAMPLE 14 A cyclohexane solution containing 35.1 parts by mass of styrene (purity: 20 w
t%). Next, n-butyllithium and tetramethylethylenediamine were added, and the mixture was polymerized at 70 ° C. for 1 hour.
The mixture was polymerized at 70 ° C. for 1 hour, and a cyclohexane solution containing 31.9 parts by mass of styrene was added. Thereafter, the modifier M5 was reacted equimolarly with n-butyllithium used for the polymerization. The obtained block copolymer had a styrene content of 67% by weight and a 1,2 bond amount in the polybutadiene portion of 18%.

To the block copolymer obtained above, hydrogenation catalyst II was added at 100 ppm as Ti per polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. for 1 hour. Thereafter, methanol was added, and octadecyl-3- (3,5-di-tert-butyl-4- as a stabilizer was then added.
0.3 parts by mass of (hydroxyphenyl) propionate was added to 100 parts by mass of the block copolymer. Thereafter, cyclohexane was removed by heating from the obtained block copolymer cyclohexane solution to obtain a block copolymer (polymer 16). Table 3 shows the analysis results of the polymer 16. The ratio of the unmodified block copolymer mixed in the polymer 16 was 30% by weight. 100 parts by mass of polymer 16, 15 parts by mass of silica A as component (2), 271 parts by mass of polypropylene resin and 834 parts by mass of polystyrene resin as component (3), and octadecyl-3- (3,3) as a stabilizer 5-di-t-butyl-4
-Hydroxyphenyl) propionate was added in an amount of 0.88 parts by mass and melt-kneaded at 230 ° C with a 25 mmφ twin-screw extruder to obtain a block copolymer composition. Table 6 shows the physical properties of the obtained composition.

[0092]

Embodiment 15 The hydrogenation time was shortened and the hydrogenation rate was reduced to 60%.
A block copolymer (Polymer-17) was obtained in the same manner as for Polymer 16, except that Table 3 shows the analysis results of the polymer 17. The ratio of the unmodified block copolymer mixed in the polymer 17 was 30% by weight. Using Polymer 17, a block copolymer composition was obtained in the same manner as in Example 14. Table 6 shows the physical properties of the obtained composition.

Comparative Example 12 A block copolymer composition was obtained in the same manner as in Example 15 except that silica was not used. Table 6 shows the physical properties of the obtained composition.

[0093]

Comparative Example 13 A block copolymer composition was obtained in the same manner as in Example 15 except that Polymer 18 was used and silica A was not used. Table 6 shows the physical properties of the obtained composition.

[Table 6] From the results of Examples 1 to 15 and Comparative Examples 1 to 13, it is understood that the block copolymer composition of the present invention is excellent in mechanical strength, compression set, impact resistance, and workability.

[0094]

The modified block copolymer composition of the present invention is excellent in heat resistance, transparency, abrasion resistance and workability. Further, the hydrogenated block copolymer composition of the present invention is excellent in mechanical strength, compression set, impact resistance and workability. Taking advantage of these features, it can be processed into molded articles of various shapes by injection molding, extrusion molding, etc., and can be used for automobile parts, home electric parts, electric wire coatings, medical parts, footwear, sundries and the like.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Shigeki Takayama 1-3-1, Yoko, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture Asahi Kasei Corporation (72) Inventor Toshinori Shiraki 1-3-1, Yoko, Kawasaki-ku, Kawasaki-shi, Kanagawa No. Asahi Kasei Corporation F-term (reference) 4J002 BB00X BB03X BB06X BB07X BB08X BB12X BB15X BL01X BL02X BP01W DE076 DE106 DE136 DE146 DJ006 DJ016 DJ036 DJ046 DJ056 DL006 DM006 FA046 HA16 FD010 HA16HAB4H HB26 HB32 HB39 HB45 HB48 HC06 HC26 HC32 HC39 HC45 HC49 HC50 HE02

Claims (5)

[Claims] (1) It comprises at least one polymer block A mainly composed of a vinyl aromatic hydrocarbon and at least one polymer block B mainly composed of a conjugated diene, and contains a vinyl aromatic hydrocarbon. 100 parts by mass of a block copolymer having an amount of 5 to 95 wt% or a hydrogenated product thereof,
(2) Silica-based inorganic filler and / or metal oxide 0.5
In the block copolymer composition comprising from 50 to 50 parts by mass, the polymer block A and / or the polymer block B are used.
A block copolymer composition characterized in that at least one atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane is bonded thereto. 2. The method according to claim 1, wherein the olefin polymer is contained in an amount of 10 to 500 parts by mass based on 100 parts by mass of the block copolymer or a hydrogenated product thereof. Block copolymer composition. 3. The hydrogenated product of the block copolymer (1) comprises at least one polymer block A mainly composed of a vinyl aromatic hydrocarbon and at least one polymer mainly composed of a conjugated diene. The block B is a vinyl aromatic hydrocarbon homopolymer block having a vinyl aromatic hydrocarbon content of 5 to 95 wt% and 70% or more of the total vinyl aromatic hydrocarbon content having a number average molecular weight of 20,000 or more, And a hydroxyl group in the polymer block A and / or the polymer block B;
At least one atomic group having at least one functional group selected from an epoxy group, an amino group, a silanol group, and an alkoxysilane is bonded, and the number of structural units of structural units (A) to (E) based on a conjugated diene The block copolymer composition according to claim 1 or 2, wherein the block copolymer is a hydrogenated product of a block copolymer satisfying the following formulas (I) to (III). Embedded image 4. The polymer block A and / or the polymer block B has at least one functional group selected from the following.
The block copolymer composition according to any one of claims 1 to 3, wherein at least one atomic group having the same is bonded. Embedded image (In the above formula, R ⁹ and R ^{12 to} R ¹⁴ represent hydrogen or carbon 1
A hydrocarbon group having 1 to 24 carbon atoms having a functional group selected from a hydroxyl group, an epoxy group, a silanol group and an alkoxysilane. R ¹⁰ has 1 to 3 carbon atoms
0 hydrocarbon chain or a hydrocarbon chain having 1 to 30 carbon atoms having a functional group selected from a hydroxyl group, an epoxy group, a silanol group and an alkoxysilane. Note that R ⁹ and R ^{12 to} R
¹⁴ hydrocarbon group, and the hydrocarbon chain of R ^10, hydroxyl, epoxy group, a silanol group, in bonding mode other than alkoxysilane, oxygen, nitrogen, an element such as silicon may be bonded. R ¹¹ is hydrogen or an alkyl group having 1 to 8 carbon atoms. ) 5. The (2) silica-based inorganic filler and / or metal oxide includes silica, wollastonite, montmorillonite, zeolite, alumina, titanium oxide, magnesium oxide, zinc oxide, slug wool, glass fiber, and the like. The block copolymer composition according to any one of claims 1 to 4, wherein the block copolymer composition is at least one kind of silica-based inorganic filler and / or metal oxide selected from inorganic fibrous substances.