JP3282364B2 - Hydrogenated block copolymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention has excellent properties such as heat resistance, weather resistance, and fluidity, and further has impact resistance, heat resistance, rigidity, workability, as a modifier for other thermoplastic resins. The present invention relates to a pelletizable hydrogenated block copolymer which is excellent in the effect of modifying the appearance of a molded product and the like, and which, when blended with another rubbery polymer, provides a thermoplastic elastomer composition having excellent mechanical properties.

[0002]

2. Description of the Related Art A diene copolymer having a double bond in a polymer is inferior in heat stability, weather resistance and ozone resistance.
As a means for improving this, a method of hydrogenating an unsaturated double bond (hereinafter also referred to as “hydrogenation”) is known. Examples of the hydrogenation method include JP-B-45-39275, JP-B-45-3555, and JP-A-56-62.
805 and JP-A-59-133203. Hydrogenated polymer obtained by these methods,
Since it exhibits the expected heat resistance, weather resistance and ozone resistance, it is often used for modifying resins. Also,
As a polymer having excellent heat stability and weather resistance, an ethylene-α-olefin copolymer and the like are known. However, when these polymers are blended with a thermoplastic resin, it is insufficient to obtain a composition having a good balance of impact resistance, heat resistance, rigidity, processability, and molded appearance.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and when formed into a pellet product, pelletization is easy, the blocking resistance of the pellet is improved, and the heat resistance is improved. Excellent in various properties such as weather resistance and fluidity, and as a modifier of other thermoplastic resins, it can improve properties such as impact resistance, heat resistance, rigidity, workability, molded appearance, etc. An object of the present invention is to provide a hydrogenated block copolymer from which a thermoplastic elastomer composition having excellent mechanical properties can be obtained when blended with the above rubbery polymer.

[0004]

According to the present invention, there is provided (a) a polymer containing polymer blocks A and B in the molecule (where A is a polybutadiene block having a 1,2-vinyl bond content of less than 25% by weight; Contains 50% by weight or more of a conjugated diene compound and has a vinyl bond content of 25% or less.
Indicates a conjugated diene polymer block which is not less than 10% by weight),
And a star-shaped block copolymer having a block structure represented by (AB) nX (where n is an integer of 3 or more and X represents a residue of a coupling agent). The content is 5 to 60% by weight, the content of the polymer block B is 95 to 40% by weight (A + B = 100% by weight), and 80% or more of the double bond residue of the conjugated diene portion is hydrogenated. Star-type hydrogenated block copolymer and (b) polymer blocks A and B in the molecule [provided that A and B
Is the same as the above (a)], and is a linear block copolymer having a block structure represented by AB, wherein the content of the polymer block A is 5 to 60% by weight, B
Is 95 to 40% by weight (however, A + B = 100
% Of the double bond residue of the conjugated diene moiety.
% Or more of a hydrogenated linear hydrogenated block copolymer, and the weight ratio of (a) / (b) is 95/5 to 80/2.
A hydrogenated block copolymer characterized by having a total weight average molecular weight of 0, (a) component and (b) component of 50,000 to 700,000.

The hydrogenated block copolymer of the present invention comprises (a)
Both the component and component (b) contain polymer blocks A and B in the molecule. Among them, the block A is a polybutadiene block segment having a 1,2-vinyl bond content before hydrogenation of less than 25% by weight, preferably 20% by weight or less, more preferably 18% by weight or less. Block A
Is hydrogenated ordinary low density polyethylene (LDPE)
Is a crystalline block segment having a structure similar to the above. Block A has a 1,2-vinyl bond content of 25% by weight.
Above, the obtained hydrogenated block copolymer is soft,
In the case of pellets, the pellets are liable to adhere to each other, which hinders operations such as blending and handling when producing a composition with a thermoplastic resin. Further, the impact resistance of the composition obtained by blending with the thermoplastic resin is lowered, and the mechanical properties of the composition obtained by blending with the rubbery polymer are inferior.

The block B contains 50% by weight or more of a conjugated diene compound before hydrogenation, and has a vinyl bond content of the conjugated diene compound.
Conjugated diene polymer block segment having a total of 25% by weight or more. Block B is a conjugated diene polymer or a copolymer of another monomer and a conjugated diene compound, and is similar to a rubbery ethylene-butene copolymer or another monomer-ethylene-butene copolymer by hydrogenation. Is a block segment indicating the structure of.

The conjugated diene compound used for the block B includes 1,3-butadiene, isoprene,
2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3
-One or more of hexadiene, 4,5-diethyl-1,3-octadiene, chloroprene and the like can be mentioned. In order to obtain a hydrogenated block copolymer which is industrially usable and has excellent physical properties. , 1,3-butadiene, isoprene and 1,3-pentadiene are preferred, and 1,3-butadiene and isoprene are more preferred.

Other monomers that may be used for the block B include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N -Diethyl-p-aminoethylsulene, N, N-diethyl-p-aminoethylstyrene, vinylpyridine and the like, with styrene and α-methylstyrene being particularly preferred. When the conjugated diene compound and another monomer are copolymerized in the block B, the distribution of the conjugated diene compound may be random, tapered (one in which the monomer component increases or decreases along the molecular chain), or partially block-shaped. Or any combination of these.

The content of the conjugated diene compound in the block B is 50% by weight or more, preferably 60% by weight or more. When the content is less than 50% by weight, the glass transition temperature of the block B increases, and It is not preferable because the mechanical properties and the modifying effect of the polymer are inferior. The vinyl bond content of the conjugated diene compound in the block B is 2
5% by weight or more, preferably 30 to 95% by weight;
If it is less than 5% by weight, after hydrogenation, it exhibits a crystal structure derived from a polyethylene chain, becomes resinous, and the effect of improving the impact resistance of a composition obtained by blending with a thermoplastic resin is reduced.

The hydrogenated block copolymer of the present invention comprises at least (a) a star-shaped block copolymer in which the block structure before hydrogenation is represented by (AB) nX, and (b) a hydrogenated block copolymer before hydrogenation. Is represented by AB, and thus comprises a chain block copolymer having a lower molecular weight than the component (a). In addition, the hydrogenated block copolymer of the present invention, in addition to this,
A block copolymer having a block structure before hydrogenation represented by (AB) ₂ X may be present.

The content of the block A in the block copolymer of the component (a) or (b) is 5 to 60% by weight,
Preferably 5 to 55% by weight, more preferably 10 to 5% by weight.
0% by weight. When the content of the block A is less than 5% by weight, the obtained hydrogenated block copolymer is soft, and when pelletized, the pellets are liable to adhere to each other. The operation and handling will be hindered. Also, when blended with a thermoplastic resin, the resulting composition has poor impact resistance, and when blended with a rubbery polymer, the resulting composition has poor mechanical properties, which is not preferable. On the other hand, when the content of the block A exceeds 60% by weight, the impact resistance of the composition obtained by blending with the thermoplastic resin is lowered, which is not preferable.

The content of the block B is 95-40.
%, Preferably 95 to 45% by weight, more preferably 90 to 50% by weight. When the content of the block B is 9
When the content exceeds 5% by weight, the obtained hydrogenated block copolymer is soft, and when formed into pellets, the pellets are liable to adhere to each other. In producing a composition with a thermoplastic resin, operations such as blending and the like are handled and handled. Cause trouble.
Also, when blended with a thermoplastic resin, the resulting composition has poor impact resistance, and when blended with a rubbery polymer, the resulting composition has poor mechanical properties, which is not preferable. On the other hand, if the content of the block B is less than 40% by weight, the impact resistance of the composition obtained by blending with the thermoplastic resin is undesirably reduced.

The hydrogenated block copolymer of the present invention comprises (a)
The weight ratio of component / (b) is 95/5 to 80/20, preferably 93/7 to 80/20, and more preferably 90.
/ 10 to 80/20. (A) The proportion of the component is 95
If the amount is more than 80% by weight, the fluidity of the obtained hydrogenated block copolymer is reduced. On the other hand, if it is less than 80% by weight, the effect of improving the impact resistance when blended with a thermoplastic resin is reduced.

Further, the hydrogenated block copolymer of the present invention has a total weight average molecular weight of the component (a) and the component (b) of 50,000 to 700,000, preferably 70,000 to 650,000, more preferably 10 to 70,000. 10,000 to 650,000. If it is less than 50,000, the effect of improving the impact resistance when blended with a thermoplastic resin is reduced, and when blended with a rubbery polymer, the resulting composition has poor mechanical properties, which is not preferred. On the other hand, when it exceeds 700,000, the fluidity of the obtained hydrogenated block copolymer decreases, and when blended with a thermoplastic resin, the processability and molding appearance of the obtained composition deteriorate.

The method for producing the hydrogenated block copolymer of the present invention may be any method, and the components (a) and (b) may be separately prepared and blended. Living anion polymerization is performed using an alkali metal compound as an initiator to obtain a linear block copolymer serving as the component (b). After that, a polyfunctional coupling agent is added, and a coupling reaction is performed. It is obtained by performing a hydrogenation reaction after obtaining a block copolymer containing a star-shaped block copolymer to be the component (a) while controlling the content within the range.

As the organic solvent, a hydrocarbon solvent such as pentane, hexane, heptane, octane, methylcyclopentane, cyclohexane, benzene, xylene, and toluene is used. As the organic alkali metal compound as a polymerization initiator, an organic lithium compound is preferable.
As the organic lithium compound, an organic monolithium compound, an organic dilithium compound, and an organic polylithium compound are used. Specific examples of these include ethyl lithium, n-propyl lithium, isopropyl lithium, n
-Butyllithium, sec-butyllithium, t-butyllithium, phenyllithium, hexamethylenedilithium, butadienyllithium, isoprenyldilithium and the like.
Used in an amount of .about.0.4 parts by weight.

The vinyl bond content of the conjugated diene compound in the blocks A and B is adjusted by using a Lewis base such as an ether or an amine, specifically, diethyl ether, tetrahydrofuran, propyl ether, butyl ether, higher ether, ethylene, or the like. Ether derivatives of polyethylene glycol such as glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, and triethylene glycol dimethyl ether; examples of amines include tertiary amines such as tetramethylethylene diamine, pyridine, and tributylamine; Can be

Further, the polymerization reaction is usually carried out at a temperature of -30.degree.
Performed at 150 ° C. Further, the polymerization may be carried out while controlling at a constant temperature, or may be carried out at an elevated temperature without removing heat. Although any method may be used for forming the block copolymer, the block A is first polymerized using the polymerization initiator such as the alkali metal compound in the organic solvent, and then the block B is polymerized. At this time, the boundaries between the blocks need not always be clearly distinguished. A polyfunctional coupling is added to the AB-type linear block copolymer as the component (b) thus obtained, a coupling reaction is performed, and a star-shaped block copolymer as the component (a) is obtained. A block copolymer containing a polymer can be obtained.

Examples of the polyfunctional coupling agent include divinylbenzene, 1,2,4-trivinylbenzene, 1,3-divinylnaphthalene, 1,8-divinylnaphthalene, 1,3,5-trivinylnaphthalene, 2,4
-Divinylphenyl, 3,5,4-trivinylnaphthalene, 1,2-divinyl-3,4-dimethylbenzene,
Polyvinyl aromatic compounds such as 1,5,6-trivinyl-3,7-diethylnaphthalene, epoxidized 1,2-polybutadiene, epoxidized soybean oil, epoxidized linseed oil, 1,2,5,6,9,10 Polyepoxy compounds such as -triepoxydecane, benzene-1,2,4-triisocyanate, naphthalene-1,2,5,7-tetraisocyanate, triphenylmethanetriisocyanate, naphthalene-1,3,7 -Polyisocyanate compounds such as triisocyanate, oxalic acid, malonic acid, succinic acid, adipic acid, suberic acid, itaconic acid, maleic acid, fumaric acid, glutaric acid, pimelic acid, sebacic acid, phthalic acid, terephthalic acid, Diphenic acid, isophthalic acid, naphthalic acid, 1,3,5-benzenetricarboxylic acid, citric acid, trime Polycarboxylic acids such as citric acid and pyromellitic acid and methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, amyl alcohol, hexyl alcohol, octyl alcohol , Alcohols such as benzyl alcohol, or phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-methoxyphenol, m-methoxyphenol, p- Polycarboxylic acid ester compounds derived from phenols such as methoxyphenol, acid halides of the above polycarboxylic acids, pyromellitic dianhydride, 2,3,6,7-naphthalenetetracar Acid dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, polycarboxylic acid dianhydride compounds such as 3,3,4,4-benzophenonetetracarboxylic acid dianhydride, dimethyl carbonate, diethyl carbonate, carbonic acid Carbonate compounds such as diphenyl, 1,
Polyketone compounds such as 3,6-hexanetrione and 2,3-diacetonylcyclohexane, polyaldehyde compounds such as 1,4,7-naphthenetricarboxaldehyde, 1,7,9-anthracentic carboxaldehyde, chloroform, Carbon chloride, bromoform, carbon tetrabromide, iodoform, tetraiodomethane, 1,1,
2-trichloroethane, 1,1,2,2-tetrachloroethane, 1,1,2,2-tetrabromoethane, hexachloroethane, 1,2,3-trichloropropane, 1,
2,3-tribromopropane, 1,2,4-trichloropropane, 1,2,4,5-tetrachlorobenzene,
Polyhalogenated hydrocarbons such as 1,4-bis (trichloromethyl) benzene, trifluorosilane, trichlorosilane, methyltrichlorosilane, ethyltrichlorosilane, butyltrichlorosilane, tetrachlorosilane,
Tetrabutoxysilane, tetraiodosilane, (dichloromethyl) trichlorosilane, (dichlorophenyl) trichlorosilane, 1,2-bis (trichlorosilyl) ethane, hexachlorodisilane, octachlorotrisiloxane, trichloromethyltrichlorosilane, tetramethoxysilane, tetra Silicon compounds such as ethoxysilane, tetrabutoxysilane, trimethoxymethylsilane, triethoxymethylsilane, triethoxychlorosilane, diethoxychloromethylsilane, methyltriacetoxysilane, tetrachlorotin, methyltrichlorotin,
Tin compounds such as butyltrichlorotin and tetramethoxytin, germanium compounds such as tetrachlorogermanium, 2,4,6-tri (azilinyl) -1,3,5
And polyaziridinyl compounds such as triazine, tri (1-aziridinyl) phosphine oxide, and tri (2-methyl-1-aziridinyl) phosphine oxide.

Further, 1,3-dichloro-2-propanone, 2,4-dibromo-3-pentanone, 1,2,4
5-diepoxy-3-pentanone, 1,2,11,12
Compounds having two or more functional groups capable of reacting with a living polymer in the molecule, such as -diepoxy-8-pentadecanone, can also be used as the coupling agent. Particularly preferred among these compounds are:
Divinylbenzene, 1,2,4-trivinylbenzene,
Epoxidized 1,2-polybutadiene, epoxidized soybean oil, epoxidized linseed oil, benzene-1,2,4-triisocyanate, diethyl oxalate, diethyl malonate, diethyl adipate, dioctyl adipate, dimethyl phthalate, Diethyl phthalate, diethyl terephthalate, pyromellitic dianhydride, diethyl carbonate,
1,1,2,2-tetrachloroethane, 1,4-bis (trichloromethyl) benzene, trichlorosilane, methyltrichlorosilane, butyltrichlorosilane, tetrachlorosilane, (dichloromethyl) trichlorosilane, hexachlorodisilane, tetraethoxysilane, Examples thereof include tetrachlorotin and 1,3-dichloro-2-propanone.

The bond content of other monomers in these block copolymers is controlled by the amount of monomer supplied during the polymerization in each stage, and the vinyl bond content of the conjugated diene compound varies with the amount of the above-mentioned microcontroller component. It is adjusted by doing. Further, the weight average molecular weight is adjusted by the addition amount of a polymerization initiator, for example, n-butyllithium. The method for producing the block copolymer used in the present invention will be described more specifically. First, to obtain a block copolymer, for example, an organic lithium compound such as n-butyllithium is used as an initiator under vacuum or high pressure. No.1 under a stream of pure nitrogen
In the first stage, 1,3-butadiene is polymerized using an organic solvent such as benzene or cyclohexane as a polymerization solvent, thereby polymerizing a low vinyl polybutadiene block serving as a block A, followed by a microcontroller such as tetrahydrofuran or diethyl ether and By adding a conjugated diene compound or a conjugated diene compound and another monomer for the second stage, and after completion of polymerization, adding a calculated amount of a polyfunctional coupling agent such as divinylbenzene, and coupling the AB block polymer. , 3 or more (n ≧ 3)
A star block copolymer having the AB block in a branch shape is obtained.

By hydrogenating the block copolymer thus polymerized, a hydrogenated block copolymer of the present invention in which the double bond residue of the conjugated diene portion has been hydrogenated can be obtained. That is, the hydrogenated block copolymer of the present invention is obtained by dissolving the block copolymer thus obtained in an inert solvent, at 20 to 150 ° C. and 1 to 100 kg / cm ^2.
It is obtained by hydrogenation in the presence of a hydrogenation catalyst under pressurized hydrogen of G. Inert solvents used for hydrogenation include hexane, heptane, cyclohexane, benzene,
Examples thereof include hydrocarbon solvents such as toluene and ethylbenzene, and polar solvents such as methyl ethyl ketone, ethyl acetate, ethyl ether, and tetrahydrofuran.

Examples of the hydrogenation catalyst include dicyclopentadienyl titanium halide, cyclopentadienyl titanium halide, nickel organic carboxylate, cobalt organic carboxylate and the like, and organic metal compounds belonging to Groups I to III of the periodic table. And nickel, platinum, palladium, ruthenium, rhenium and rhodium metal catalysts supported on carbon, silica, diatomaceous earth and the like, and metal catalysts such as cobalt, nickel, rhodium and ruthenium complexes. In addition, lithium aluminum hydride, p-
Hydrogenated compounds such as toluenesulfonyl hydrazide, Zr-Ti-Fe-V-Cr alloy, Zr-Ti-
Nb-Fe-V-Cr alloy, also hydrogenation using hydrogen storage alloys such as LaNi ₅ alloys, as a manufacturing method of the hydrogenated block copolymer of the present invention.

The hydrogenation rate of the conjugated diene portion is determined by the hydrogenation catalyst,
It is adjusted by changing the amount of the hydrogenated compound added, the hydrogen pressure during the hydrogenation reaction, and the reaction time. From the hydrogenated block copolymer solution, remove catalyst residues as needed, add an antioxidant such as phenolic or amine type, and easily convert the hydrogenated block copolymer from the polymer solution. Can be isolated. Isolation of the hydrogenated block copolymer, for example, in a hydrogenated block copolymer solution,
The method can be carried out by a method of adding acetone or alcohol to precipitate the solution, a method of putting the polymer solution into hot water with stirring, and removing the solvent by distillation.

The hydrogenated block copolymer of the present invention comprises:
It is also possible to introduce at least one kind of functional group into the hydrogenated block copolymer and use it as a modified hydrogenated block copolymer. Further, in the block copolymer production step before the hydrogenation, a polyepoxy compound, a polyisocyanate compound, a polycarboxylic acid ester compound, a polyketone compound, a polyaldehyde compound, a polyaziridinyl compound, or the like is used as a polyfunctional coupling agent. Thus, a —OH group, a —NH—CO group, a —N
Functional groups such as H groups can also be introduced.

The hydrogenated block copolymer of the present invention (hereinafter also referred to as “(I) hydrogenated block copolymer”) comprises (II)
By blending with a thermoplastic resin and / or a rubbery polymer, a composition excellent in balance of impact resistance, heat resistance, stiffness, processability, molding appearance and the like, and a thermoplastic elastomer composition excellent in mechanical properties are provided. [Hereinafter "composition (I)"
) Can be obtained.

The thermoplastic resin is not particularly limited, but may be polyethylene, high molecular weight polyethylene, high density polyethylene, medium density polyethylene, low density polyethylene,
Non-polar thermoplastic resins such as linear low density polyethylene (LLDPE), polypropylene, polybutene-1, polyisobutylene, high impact polystyrene (HIPS), polystyrene, polymethylene, poly-4-methyl-pentene-1, polyhexene, And ABS resin, acrylic resin, polyacrylamide, polymethacrylamide, polyacrylic acid, polyacrylic acid alkyl esters such as polymethyl acrylate, polyethyl acrylate,
Polymethacrylic acid, polymethyl methacrylate, polymethyl methacrylate, such as polyethyl methacrylate, polyacrylonitrile, polymethacrylonitrile,
Acetal resin, polyoxymethylene, chlorinated polyethylene, cumarone / indene resin, cellulose, cellulose ester, cellulose ether, carboxymethyl cellulose, cellulose ether ester, fluororesin,
Polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, nylon 11, nylon 12,
Aliphatic polyamides such as nylon 6, nylon 6,10, nylon 6,12, nylon 6,6, nylon 4,6, etc., aromatic polyamides such as polyphenylene isophthalamide, polyphenylene terephthalamide, polymetaxylylenediamine, polyimide, polyethylene Terephthalate, polybutylene terephthalate, polyphenylene ether, polyphenylene sulfide, polysulfone,
Polar heat such as polyether sulfone, polysulfonamide, polyether ether ketone, polyamide imide, polyarylate, polycarbonate, polyvinyl alcohol, polyvinyl ester, polyvinyl acetate, polymethyl vinyl ether, polyisobutylene vinyl ether, polyvinyl chloride, polyvinylidene chloride, etc. And a plastic resin. These thermoplastic resins can be used alone or in combination of two or more.

Preferred thermoplastic resins are polyethylene, polypropylene, polystyrene, polyamide, polyacetal, polyethylene terephthalate, polybutylene terephthalate, polyphenylene ether, polyphenylene sulfide, polysulfone, and polycarbonate.

On the other hand, the rubbery polymer is a general term for natural rubber and synthetic rubber. Specific examples of the rubbery polymer include styrene-butadiene rubber and its hydrogenated product, isoprene rubber, nitrile rubber and its hydrogenated product, chloroprene rubber, butyl rubber, ethylene-
Propylene rubber, ethylene-propylene-diene rubber,
Ethylene-butene rubber, ethylene-butene-diene rubber, acrylic rubber, α, β-unsaturated nitrile-acrylate-conjugated diene copolymer rubber, chlorinated polyethylene rubber, fluorine rubber, silicone rubber, urethane rubber,
Typical examples thereof include polysulfide rubber, styrene-butadiene block polymer and hydrogenated product thereof.
Among these rubbery polymers, preferably hydrogenated styrene-butadiene rubber, hydrogenated nitrile rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butene rubber, ethylene-butene-diene rubber, acrylic Rubber, chlorinated polyethylene rubber, fluorine rubber, silicone rubber, urethane rubber, polysulfide rubber, hydrogenated styrene-butadiene block polymer, α, β-unsaturated nitrile-acrylate-conjugated diene copolymer rubber A rubber having a substantially low degree of saturation or unsaturation, and a modified rubber having a functional group added thereto.

In the composition (I) of the present invention, the mixing ratio of (I) the hydrogenated block copolymer and (II) the thermoplastic resin and / or the rubbery polymer is 1 to 99 parts by weight of the component (I). , Preferably 2 to 95 parts by weight, more preferably 3 to 95 parts by weight.
90 parts by weight, 99-1 part by weight of component (II), preferably 9
8 to 5 parts by weight, more preferably 97 to 10 parts by weight (provided that (I) + (II) = 100 parts by weight). (I)
If the amount of the component is less than 1 part by weight, the effect of modifying the component (II) is insufficient. On the other hand, if it exceeds 99 parts by weight, the effect of improving the physical properties in the case of obtaining a thermoplastic elastomer composition is insufficient.

When a thermoplastic elastomer composition is to be obtained by using the (I) hydrogenated block copolymer of the present invention,
Whether a thermoplastic resin, a rubbery polymer, or a mixture of both is used as the component (II) mainly depends on the properties of the hydrogenated block copolymer (I).

More specifically, when the content of the block A in the component (I) is 40% by weight or less, the component (I) exhibits a rubber-like soft property. It is preferable that the resin is blended and designed so as to obtain a well-balanced thermoplastic elastomer composition. (I)
When the content of the block A in the component exceeds 40% by weight,
If it is less than 10% by weight, it is desirable to design a thermoplastic elastomer which is comprehensively balanced by using a thermoplastic resin and a rubbery polymer as the component (II) in combination.
However, the present invention is not necessarily limited to the above. For example, in order to obtain a very soft thermoplastic elastomer, if the content of the block A is 40% by weight or less, the component (I) and the rubbery polymer are blended. You can also.

The content of the combination of the components (I) and (II) is a generalized description of the relationship between the properties of the component (I) and the polymer used as the component (II). The composition obtained by the present invention is not limited to the contents described above, and the contents of the component (II) can be selected according to the purpose. The polymer used as the component (II) may be a mixture of a plurality of thermoplastic resins and / or a plurality of rubbery polymers. In addition, (I
When a thermoplastic resin and a rubbery polymer are used in combination as the components, each of them can be used in an optional ratio depending on the performance of the desired final composition.

Further, in the present invention, the composition can be designed by taking advantage of the inherent property of (I) the hydrogenated block copolymer, that is, the property of acting as a compatibilizer between different polymers. In general, when a block polymer is used as a compatibilizer, it is known that the addition amount of about several weight% is sufficient. The reason why the minimum use amount of the component (I) of the present invention is 1% by weight is to consider the use of the component (I) as a compatibilizer. That is, when component (I) is used as a compatibilizer, (I)
I) Two or more thermoplastic resins, or a thermoplastic resin and a rubbery polymer are used in combination as components.

Here, the component (I) effectively acting as a compatibilizer may be a combination of a specific thermoplastic resin or a combination of a specific thermoplastic resin and a specific rubbery polymer. Can be In this case, as the thermoplastic resin, for example, a polyolefin-based resin such as polyethylene, polypropylene, polybutene-1 or the like having 2 to 8 carbon atoms
And a graft polymer in which another polymer is graft-polymerized to a polymer having α-monoolefin as a main constituent. The rubbery polymer in this case includes ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butene rubber, monoolefin-based copolymer rubber such as ethylene-butene-diene rubber, chlorinated polyethylene rubber, styrene-butadiene rubber. And hydrogenated nitrile rubbers and hydrogenated styrene-butadiene block polymers. Even when the component (I) is used as a compatibilizer, a thermoplastic resin and / or a rubbery polymer other than those described above may be blended.

Next, the (I) hydrogenated block copolymer of the present invention comprises a rubbery polymer as an essential component as a component (II), and a crosslinking agent for the rubbery polymer. When the rubbery polymer is allowed to gel while at least 10% by weight reacts while giving deformation, a composition exhibiting excellent mechanical properties (hereinafter, also referred to as “composition (II)”) is obtained. Here, as the cross-linking agent used, those used for normal cross-linking of rubber, for example, "Cross-linking agent handbook"
(Written by Shinzo Yamashita and Tosuke Kaneko, published by Taiseisha) can be used.

Preferred crosslinking agents include sulfur, sulfur compounds, p-benzoquinone dioxime, p, p'-
Resin cross-linking agents such as dibenzoylquinone dioxime, 4,4'-dithio-bis-dimorpholine, poly-p-dinitrosobenzene, tetrachlorobenzoquinone, alkylphenol-formaldehyde resin, brominated alkylphenol-formaldehyde resin, ammonium benzoate, bis Examples include a maleimide compound, a diepoxy compound, a dicarboxylic acid compound, a diol compound, a diamine compound, an amino resin, an organic metal salt, a metal alkoxide, an organic metal compound, and an organic peroxide.

These crosslinking agents can be used alone or as a mixture. Further, depending on the type of the cross-linking agent, cross-linking may proceed more efficiently by using it in combination with another compound. In particular, when sulfur or a sulfur compound is used as a crosslinking agent,
It is desirable to use a vulcanization accelerator, a vulcanization acceleration aid, and an activator for promoting a sulfur crosslinking reaction, and an appropriate combination and an amount to be used can be determined by utilizing, for example, the aforementioned literature. When an organic peroxide is used as a crosslinking agent, a method in which a crosslinking aid is used in combination is preferable.

Examples of the crosslinking assistant include sulfur, sulfur compounds such as dipentamethylenethiuram pentasulfide and mercaptobenzothiazole, oxime nitroso compounds, ethylene glycol dimethacrylate, aryl methacrylate, triaryl cyanurate, diaryl phthalate, and polyethylene glycol dimethacrylate. Monomers such as methacrylate, divinyl adipate, maleic anhydride, bismaleimide compound, trimethylolpropane trimethacrylate, divinylbenzene, liquid polybutadiene, liquid styrene-butadiene copolymer, 1,2-
Examples include polymers such as polybutadiene.

The cross-linking agent to be used is desirably determined in consideration of the properties of the rubbery polymer in the component (II). That is, the (I) hydrogenated block copolymer of the present invention can be regarded as a substantially saturated polymer consisting essentially of an α-monoolefin. Therefore, if the rubbery polymer in the component (II) has a high degree of unsaturation, select a crosslinking agent which is effective for a highly unsaturated rubber, such as a usual sulfur vulcanizing system or a resin crosslinking agent. By doing so, the rubbery polymer can be preferentially crosslinked.

However, when the rubbery polymer in the component (II) is an essentially saturated polymer, especially a copolymer rubber composed of α-monoolefin, or a polymer having a low degree of unsaturation, the crosslinking agent Depending on the type and amount used, not only crosslinking of the rubbery polymer but also crosslinking of (I) the hydrogenated block copolymer may occur. For example, when an organic peroxide is used in a large amount as a crosslinking agent, (I)
The components may also be crosslinked and the resulting composition may be insoluble.

In such a case, the problem can be solved by sufficiently examining the amount of the crosslinking agent to be used, but there is a limit that the degree of crosslinking of the rubbery polymer cannot be sufficiently increased. The fundamental solution is that the rubbery polymer used has functional groups such as carboxy, acid anhydride, hydroxy, epoxy, halogen, amino, isocyanate, sulfonyl or sulfonate groups. Is used, and a component which reacts with the functional group is used as a crosslinking agent. Examples of the rubbery polymer having a functional group include a method of copolymerizing a monomer having a functional group, and a method of introducing the monomer into the rubbery polymer by a known graft reaction. In this case, the component used as the cross-linking agent is a polyfunctional substance that undergoes a substitution reaction with a functional group in the rubbery polymer, and may be a low molecular weight substance or a high molecular weight substance.

Specifically, the rubbery polymer containing a carboxy group can be easily crosslinked with a diamino compound, a bisoxazoline, a diepoxy compound, a diol compound and the like. In the rubbery polymer having maleic anhydride as a functional group, a diamino compound is effective as a crosslinking agent. Further, when the rubbery polymer contains an unsaturated bond, a dithiol compound or bismaleimide can be used as a crosslinking agent. Further, when an acrylic rubber or an acrylate ester is used as a main component as the rubbery polymer, a diamino compound is effective. Further, when a chlorinated polymer such as chlorinated polyethylene is used as the rubbery polymer, a dithiol compound is effective as a crosslinking agent.

The amount of these crosslinking agents to be used can be appropriately determined depending on the performance required for the desired final composition. It is desirable to select an appropriate cross-linking system and the amount to be used with reference to the above-mentioned literature and the like. Usually, 0.1 to 8 parts by weight of a crosslinking agent, 0.1 to 10 parts by weight of a vulcanization accelerator, and 0.1% by weight of a vulcanization accelerator are used per 100 parts by weight of the rubbery polymer.
It is suitably used in the range of 5 to 10 parts by weight, 0.5 to 10 parts by weight of an activator, and 0.1 to 10 parts by weight of a crosslinking aid.
It is necessary that the rubbery polymer in the component is gelled at least 10% by weight, preferably 30% by weight or more, more preferably 40% by weight or more. If it is less than 10% by weight, the mechanical properties are improved by crosslinking. Is insufficient and is not preferred.

Here, the gel content of the rubbery polymer is measured as follows:
Under the conditions for preparing the composition (II), a cross-linking test was performed on only the rubbery polymer, and the value was obtained by substituting the gel content of the cross-linked rubbery polymer. This gel content measurement is usually performed by extracting cyclohexane as a solvent at 70 ° C. for 4 hours and calculating the gel content. When the rubbery polymer used is insoluble in cyclohexane, the gel content of the rubbery polymer is calculated. Use a good solvent.

Next, the composition containing the hydrogenated block copolymer (I) of the present invention contains the components (I) to (II) as described above. In the case of a composition containing 10% by weight or more of a plastic resin, the components (I) and (II) are reacted while imparting shear deformation in the presence of a crosslinking agent capable of crosslinking the component (I). When at least 10% by weight of the total amount of the rubbery polymer and the component (I) is gelled, a composition exhibiting excellent mechanical properties (hereinafter also referred to as “composition (III)”) is obtained.

In the composition (III), the composition containing at least 10% by weight of the thermoplastic resin as the component (II) of the composition (I) crosslinks the component (I) and the rubbery polymer. The component (I) and at least 10% by weight of the rubbery polymer are gelled by undergoing shear deformation (heat melting and mixing) in the presence of the component. That is, the composition (III) is characterized in that the component (I) of the present invention is used as a rubber component.

In the composition (III), it is essential to use a thermoplastic resin as the component (II), and the amount used is at least 10% by weight, preferably 10 to 80% by weight in the component (II). %, More preferably 15 to 70% by weight, and if it is less than 10% by weight, the resulting composition loses thermoplasticity and is inferior in processability, which is not preferable.

Preferred as the thermoplastic resin used in the composition (III) are polyethylene, polypropylene,
An olefinic crystalline thermoplastic polymer such as polybutene-1, and a crystalline thermoplastic polymer such as polyamide, polyester, polyamide elastomer, and polyester elastomer. The crosslinking agent used here can be appropriately selected from the crosslinking agents used in the composition (II).

In the composition (III), the component (I), which is an essentially saturated olefinic block polymer, is used as the rubber component. Therefore, the crosslinking agent is an organic peroxide and a crosslinking aid. The system consisting of As the organic peroxide, those having a one-minute half-life temperature of 150 ° C. or more are preferable. For example, 2,5-di-methyl-2,5
-Di-benzoyl-peroxyhexane, n-butyl-
4,4-di-t-butylperoxyvalerate, dicumyl peroxide, t-butylperoxybenzoate, di-t-butylperoxy-di-isopropylbenzene, t-butylcumyl peroxide, 2,5- Jee
Methyl-2,5-di-t-butylperoxyhexane,
Di-t-butyl peroxide, 2,5-di-methyl-
Preferred examples include 2,5-di-t-butylperoxyhexine-3.

The crosslinking aid used is preferably a radically polymerizable monomer or a radically crosslinkable polymer. Examples of the crosslinking aid include divinylbenzene, bismaleimide, trimethylolpropane triacrylate, trimethylolpropane methacrylate, pentaerythritol triacrylate, aluminum acrylate, aluminum methacrylate, zinc methacrylate, zinc acrylate, magnesium acrylate, magnesium methacrylate, and triallyl isocyanate. Nurate, triallyl cyanurate, triallyl trimellitate, diallyl phthalate, diallyl chlorendate, liquid polybutadiene, liquid 1,2-polybutadiene are preferred examples.

The amounts of the organic peroxide and the crosslinking aid used are as follows:
The amount of oxygen in the organic peroxide is calculated to be 0.001 to 0.1 mol based on 100 parts by weight of the component (I) or the total of the component (I) and the other rubbery polymer in the composition. It is preferable that the addition is less than 0.001 mol, because sufficient cross-linking does not take place. On the other hand, even if it exceeds 0.1 mol, further cross-linking cannot be expected, and it is not economical. This is not preferred because it tends to cause undesirable side reactions such as decomposition of the polymer.

The amount of the crosslinking aid used is such that the amount of unsaturated double bonds in the crosslinking aid is １ ／ to 40 times the amount of active oxygen in the added organic peroxide. It is desirable to use it selectively. If it is less than 1/4 equivalent, it cannot be expected much from the viewpoint of improvement in crosslinking efficiency due to the addition of a crosslinking aid, and it is not preferable because sufficient crosslinking is not performed. Cannot be expected, and is not economical.

The gel component in the rubbery polymer in the component (I) or the component (I) and the component (II) is mixed with the component (I) or the component (I) under the conditions for preparing the composition (III). (II) A crosslinking test of only the rubbery polymer in the component may be performed, and the gel component may be substituted. Here, the gel content is usually measured by extracting cyclohexane as a solvent at 70 ° C. for 4 hours to calculate the gel content. When the rubbery polymer used at the same time is insoluble in cyclohexane, cyclohexane is used. After removing the soluble component of the component (I) by using the same, a good solvent for the rubbery polymer is used and extraction is performed again to calculate the gel content.

In producing the above-mentioned compositions (compositions (I) to (III)) containing the components (I) and (II) of the present invention, a usual kneading apparatus, for example, a rubber mill or a Brabender mixer is used. , A Banbury mixer, a pressure kneader, a twin screw extruder, or the like can be used, but a closed type or an open type that can be replaced with an inert gas is preferable.

The kneading temperature is a temperature at which all the components to be mixed are melted, and is usually in the range of 140 to 300 ° C., preferably 160 to 280 ° C.
Further, the kneading time depends on the type and amount of the constituent components and the kneading device, and therefore is not generally discussed. However, when a pressure kneader, a Banbury mixer, or the like is used as the kneading device, it is usually about 5 minutes. It is about 40 minutes. further,
Upon kneading, each component may be kneaded at once,
Alternatively, a multi-stage kneading method may be employed in which any components are kneaded, and then the remaining components are added and kneaded.

The composition (I) to (III) using the (I) hydrogenated block copolymer or the components (I) to (II) of the present invention may contain various additives, for example, antiaging. Agents, heat stabilizers, ultraviolet absorbers, stabilizers such as copper damage inhibitors, silica, talc, carbon, calcium carbonate, magnesium carbonate, glass fiber, carbon fiber, metal fiber, glass beads, mica, potassium titanate whisker, A filler such as aramid fiber, wood powder, cork powder, cellulose powder, rubber powder and the like can be compounded and used. The amount of these fillers is preferably 200 parts by weight or less, more preferably 1 to 150 parts by weight, based on 100 parts by weight of (I) hydrogenated block copolymer or compositions (I) to (III). Particularly preferably, it is 5 to 100 parts by weight. Also,
In the compositions (I) to (III), a softener such as a plasticizer, an oil or a low molecular weight polymer may be blended together with the above additives.

[0058]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples. However, unless the gist of the present invention is exceeded, the present invention
It is not limited by such an embodiment. In the examples, parts and percentages are by weight unless otherwise specified. Various measurements in the examples were based on the following methods.

Vinyl Bond Content The vinyl bond content of the conjugated diene was calculated by the Hampton method using infrared analysis. Hydrogenation rate The hydrogenation rate of the conjugated diene was 10% in ethylene tetrachloride as a solvent.
Calculated from ⁰ MHz, ¹ H-NMR spectrum. Weight average molecular weight The weight average molecular weight (hereinafter also referred to as “molecular weight”) is determined by gel permeation chromatography [GPC, column;
It was determined in terms of polystyrene using GMH _HR- H manufactured by Tosoh Corporation. Weight ratio between component (a) and component (b) The weight ratio between component (a) and component (b) was calculated from the peak area ratio of component (a) and component (b) obtained by GPC.

Melt flow rate The melt flow rate (MFR) is determined according to JIS K7210.
And a load of 10 kg (Examples 1 to 9, Comparative Examples 1 to 10) or 2.16 kg (Examples 10 to 1).
9, Comparative Examples 11 to 23). Pellets Blocking Pellets of hydrogenated block copolymer (hereinafter also referred to as “hydrogenated polymer”) were obtained by a strand cut method at a resin temperature of 230 ° C. using a 55 mmφ uniaxial extruder. The obtained pellets were tested for blocking property under a load of 30 g / cm ² in a thermostat at 50 ° C.
The pellets after the time were ranked as follows. ◎: hardly hardened, easily falling apart. ；: It hardens slightly, but can be relatively easily unraveled. ×: Hardened and difficult to loosen.

Izod impact strength Measured according to JIS K7110. Flexural modulus was measured according to JIS K7203. Heat distortion temperature was measured according to ASTM D648. Molding appearance The molding appearance was visually evaluated according to the following criteria. A: Very good appearance. ；: Good appearance. ×: Poor appearance phenomena such as pearl luster, flow mark, and rough surface are observed. Tensile strength, elongation at break, elongation at 100% elongation, and hardness were measured in accordance with JIS K6301.

Example 1 (Production of hydrogenated block copolymer) 5 kg of degassed and dehydrated cyclohexane and 200 g of 1,3-butadiene were placed in an autoclave having an internal volume of 10 liters.
Was added, and 0.25 g of tetrahydrofuran and 1.95 g of n-butyllithium were added.
The isothermal polymerization was carried out at a constant C. After the conversion reached almost 100%, the reaction solution was cooled to 40 ° C., 8.5 g of tetrahydrofuran and 800 g of 1,3-butadiene were added, and the temperature was elevated by polymerization. After the polymerization was completed, 1.04 g of tetrachlorosilane was added and the reaction was carried out for about 20 minutes. After the reaction was completed, the amount of living Li was measured and found to be 4.6 mmol. In this system, 0.84 g of benzophenone
Was added to the autoclave and stirred for 10 minutes. From the change in the color of the polymer liquid, it was confirmed that there was no living lithium terminal lithium as a living anion.

Next, 3.22 g of benzophenone and n-butyllithium in 20 ml of cyclohexane were dissolved.
A reaction product obtained by reacting 10 g in advance in a nitrogen atmosphere for 10 minutes was charged, and 0.52 g of bis (cyclopentadienyl) titanium dichloride and 1.51 g of diethylaluminum chloride dissolved in 10 ml of toluene were further charged in a nitrogen atmosphere. The components premixed below were charged into an autoclave and stirred. 8 hydrogen gas
The mixture was supplied at a pressure of kg / cm ² G, and a hydrogenation reaction was performed at 90 ° C. for 1.5 hours.

The hydrogenation rate of the obtained hydrogenated polymer was 98%,
The weight average molecular weight of the component (a) is 206,000, the weight average molecular weight of the component (b) is 66,000, and the components (a) and (b)
The total weight average molecular weight of the components is 196,000, and the weight ratio of component (a) / component (b) is 80/20, 230 ° C., 10 k
The MFR measured under a g load was 7.4 g / 10 minutes.
In addition, the 1,3-butadiene block 1,2 measured at the end of the first-stage 1,3-butadiene block polymerization was 1,2.
-The vinyl bond content was 15%, and the second stage was the result of calculation from the 1,2-vinyl bond content measured at the end of the polymerization of 1,3-butadiene in the second stage and the vinyl bond content in the first stage. The 1,2-vinyl bond content of the 1,3-butadiene block was 40%. This hydrogenated block copolymer is designated as H-1.

Examples 2 to 9 In the same manner as in Example 1, the monomer species, the monomer content, the catalyst content, the coupling agent species, and the coupling were obtained so as to obtain the hydrogenated block copolymers shown in Tables 1 and 2. It was prepared by changing the amount of the agent, the polymerization temperature, the polymerization time and the like. Tables 1 and 2 show these results.

Comparative Examples 1 to 10 In the same manner as in Example 1, the monomer species, the monomer content, the catalyst content, the coupling agent species, and the coupling were obtained so as to obtain the hydrogenated block copolymers shown in Tables 3 and 4. It was prepared by changing the amount of the agent, the polymerization temperature, the polymerization time and the like. Tables 3 and 4 show these results.

K-1 and K-2 are the hydrogenated block copolymers of Example 1 wherein the 1,2-vinyl bond content of block A and the vinyl bond content of block B are within the scope of the present invention, respectively. Is outside. K-3, K-
4 is a hydrogenated polymer which does not contain the block A or the block B in the hydrogenated block copolymer of Example 2. K-5 and K-6 are those of the hydrogenated block copolymer of Example 4 whose weight average molecular weight is out of the range of the present invention. K-7 is a hydrogenated block copolymer consisting of only the component (b). K-8 is (a) component / (b)
This is an example in which the weight ratio of the components is out of the range of the present invention. K
-9 is an example in which bifunctional 1,2-dibromoethane is used as the coupling agent, and is an example that does not include the star-shaped hydrogenated block copolymer of the component (a). K-10 is the hydrogenated block copolymer of Example 5 in which the degree of hydrogenation was out of the range of the present invention.

Examples 1 to 9 are the hydrogenated block copolymers of the present invention, which do not cause blocking between the pellets in pelletization, and as shown in Examples 10 and on, when blended with other resins. Thus, the desired reforming effect of the present invention is obtained. In contrast, Comparative Example 1,
Nos. 4 and 10 cause blocking between the pellets.
Further, Comparative Examples 5 to 7 are not preferable because pelletization is impossible. Further, Comparative Examples 2, 3, 8, and 9 do not cause blocking between the pellets, but as shown in Comparative Examples 11 and later, compared with the hydrogenated block copolymer of the present invention in blends with other resins. It is not preferable because the reforming effect is inferior.

Examples 10-19 H-1 to 9 obtained in the above Examples 1 to 9, polypropylene resin (PP-1), talc, ethylene-propylene copolymer; EP [Nippon Synthetic Rubber Co., Ltd. Made, EP02P]
Using a 4-liter Banbury-type kneader, Table 5
6 were mixed at the weight ratio shown in FIG. The mixed composition was formed into a sheet, cut into square pellets, and injection molded to prepare test pieces for evaluating physical properties. Table 5 shows the results of the physical property evaluation.
6 is shown. Each of these examples is a composition using the hydrogenated block copolymer of the present invention, and is excellent in balance between workability, impact resistance, rigidity, heat resistance, and molded appearance.

Comparative Examples 11 to 20 In the same manner as in Example 10, K-1 to K-1 shown in Tables 3 and 4 were used.
Using 10 hydrogenated block copolymers, injection molded articles were prepared, and each physical property was evaluated. The results are shown in Tables 7 and 8. A composition using a hydrogenated block copolymer which does not satisfy the requirements of the present invention lacks the balance of processability, impact resistance, rigidity, heat resistance, and molded appearance.

Comparative Examples 21 to 23 In Example 10, instead of the hydrogenated block copolymer, an ethylene-propylene copolymer; EP (manufactured by Nippon Synthetic Rubber Co., Ltd., EP02P), ethylene-butene-1 copolymer EBM [manufactured by Japan Synthetic Rubber Co., Ltd., EBM2041]
P], a hydrogenated product of a styrene-butadiene-styrene triblock copolymer; an injection-molded product was prepared in the same manner except that SEBS (manufactured by Shell Co., Ltd., Kraton G1650) was used, and each physical property was measured. Was done. Table 9 shows the results. From these comparisons, it can be seen that the conventionally used ethylene-
Compared with the hydrogenated block copolymer (SEBS) of propylene copolymer (EP), ethylene-butene-1 copolymer (EBM) and styrene-butadiene-styrene triblock copolymer, the hydrogenated block copolymer of the present invention is The composition used was processable,
It can be seen that the balance of impact resistance, rigidity, heat resistance, and appearance of the molded product is excellent.

Examples 20 to 24 and Comparative Examples 24 to 27 Using a formulation shown in Tables 10 to 11, a hydrogenated block copolymer, a thermoplastic resin and a rubber Add coalescence and add 10 at 80 rpm
Mix for minutes. The mixture was discharged, formed into a sheet with a hot roll, press-formed into a square plate having a side of 10 cm, and cut out with a dumbbell cutter to obtain a test piece for measurement. In addition, when adding a crosslinking agent, it was added after the hydrogenated block copolymer, thermoplastic resin, and rubbery polymer were completely melted. In this case, after adding the crosslinking agent, 80 rpm
The mixing was continued at m, the shaft torque was observed with a torque meter attached to the Labo Plastmill, and the mixing was continued for 3 minutes from the time when the maximum torque value was shown, followed by discharging.

Examples 20 to 24 are examples using the hydrogenated block copolymer of the present invention, and it can be seen that all of the compositions reflect the excellent properties of the hydrogenated block copolymer. On the other hand, Comparative Examples 24 to 26 are examples in which the hydrogenated block copolymer of the present invention was not used, and had low elongation at break, high hardness, and poor permanent elongation. Comparative Example 2
No. 7 is an example using a hydrogenated block copolymer outside the range of the present invention, and has high hardness and poor permanent elongation.

[0074]

[Table 1]

[0075]

[Table 2]

[0076]

[Table 3]

[0077]

[Table 4]

[0078]

[Table 5]

[0079]

[Table 6]

[0080]

[Table 7]

[0081]

[Table 8]

[0082]

[Table 9]

[0083]

[Table 10]

* 1) Polyethylene Z, manufactured by Mitsubishi Yuka Co., Ltd.
F-51 * 2) Made by Mitsubishi Yuka Corporation, polypropylene MA-7

[0085]

[Table 11]

[0086]

According to the present invention, excellent properties such as heat resistance, weather resistance, fluidity, etc., and as a modifier for other thermoplastic resins, impact resistance, heat resistance, rigidity, workability, A pelletized hydrogenated block copolymer is obtained, which is excellent in improving the appearance such as a molded appearance and can be blended with a rubbery polymer to obtain a thermoplastic elastomer having excellent mechanical properties. Further, the composition of the present invention comprising (I) a hydrogenated block copolymer and (II) a thermoplastic resin and / or a rubbery polymer as main components is prepared by injection molding, extrusion molding,
Used as various molded products by vacuum molding etc., taking advantage of its excellent properties, automotive interior and exterior materials, various electric and electronic parts, housing, industrial parts, stationery, medical materials, film and sheet products, adhesives and adhesives It can be used widely.

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasuhiko Takemura 2--11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (56) References JP-A-7-268174 (JP, A) JP-A Heisei JP-A-4-3422752 (JP, A) JP-A-4-2555734 (JP, A) JP-A-4-236249 (JP, A) JP-A-3-247646 (JP, A) A) JP-A-3-128957 (JP, A) JP-A-1-266156 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 53/00

Claims (1)

(57) [Claims] (1) A polymer containing polymer blocks A and B in the molecule (where A has a 1,2-vinyl bond content of 2)
A polybutadiene block of less than 5% by weight, B represents a conjugated diene polymer block containing at least 50% by weight of a conjugated diene compound and having a vinyl bond content of at least 25% by weight of the conjugated diene compound) and having a block structure of ( A-
B) A star-shaped block copolymer represented by nX (where n is an integer of 3 or more and X represents a coupling agent residue), wherein the content of the polymer block A is 5 to 60% by weight. %,
A star-shaped hydrogenated block copolymer in which the content of the polymer block B is 95 to 40% by weight (A + B = 100% by weight) and 80% or more of the double bond residue of the conjugated diene portion is hydrogenated. And (b) polymer blocks A and B in the molecule (where A and B are the same as in (a) above),
And a block structure is a linear block copolymer represented by AB, wherein the content of the polymer block A is 5-6.
0% by weight, the content of the polymer block B is 95 to 40% by weight (A + B = 100% by weight), and 80% or more of the double bond residue of the conjugated diene portion is hydrogenated linear. It comprises a hydrogenated block copolymer, the weight ratio of (a) / (b) is 95/5 to 80/20, and the total weight average molecular weight of the component (a) and the component (b) is 50,000 to 700,000. A hydrogenated block copolymer, characterized in that: