JPH07268174A - Hydrogenated block copolymer composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition capable of giving compositions excellent in the balance between impact resistance, heat resistance, rigidity, processability and appearance after molded or thermoplastic elastomers excellent in mechanical properties. CONSTITUTION:This composition comprises (I) 1-99 pts.wt. of a hydrogenated block copolymer obtained by hydrogenating a block copolymer made up of at least two kinds of components: (a) (A-B)nX and (b) A-B [A is a polybutadiene block <25wt.% in 1,2-vinyl link content; B is a (co)polymer block containing >=50-wt.% of a conjugated diene compound and >=25wt.% in the vinyl link content of the conjugated diene segment; (n) is >=3; X is a coupling agent residue] and (II) 99-1 pt.wt. of a thermoplastic resin and/or a rubbery polymer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention provides a hydrogenated block copolymer obtained by hydrogenating a block copolymer having a star structure and a thermoplastic and / or rubbery polymer, thereby blending The present invention relates to a composition having an excellent balance of impact resistance, heat resistance, rigidity, processability, molding appearance, and the like, and a hydrogenated block copolymer composition which is a thermoplastic elastomer composition having excellent mechanical properties.

[0002]

2. Description of the Related Art A diene copolymer having a double bond in the polymer is inferior in thermal 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 this hydrogenation method include JP-B-45-39275, JP-B-45-3555, and JP-A-56-62.
No. 805, JP-A-59-133203 and the like. Hydrogenated polymers obtained by these methods,
Since it shows expected heat resistance, weather resistance and ozone resistance, it is often used for resin modification applications. Also,
Ethylene-α-olefin copolymers and the like are known as polymers having excellent thermal stability and weather resistance. 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 molding appearance.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art. The hydrogenated block copolymer obtained by hydrogenating a block copolymer containing a star structure and a heat By blending with a plastic resin and / or a rubbery polymer, a composition having an excellent balance of impact resistance, heat resistance, rigidity, processability, molding appearance, etc., and a thermoplastic elastomer composition having excellent mechanical properties can be obtained. An object of the present invention is to provide a hydrogenated block copolymer composition comprising

[0004]

The present invention provides (I) (a)
Containing polymer blocks A and B in the molecule (however,
A is a polybutadiene block having a 1,2-vinyl bond content of less than 25% by weight, and B is a conjugated diene compound at 50% by weight.
A conjugated diene polymer block containing the above and having a vinyl bond content of the conjugated diene compound of 25% by weight or more) and having a block structure of (AB) nX (provided that n is
Is an integer of 3 or more, X is a coupling agent residue) and is a star-shaped block copolymer having a content of the polymer block A of 5 to 60% by weight, A star-type hydrogenated block copolymer having a content of 95 to 40% by weight (however, A + B = 100% by weight), and 80% or more of double bond residues of a conjugated diene moiety is hydrogenated, and (b ) A linear block copolymer containing polymer blocks A and B in the molecule [where A and B are the same as in (a) above] and having a block structure represented by AB. The content of the polymer block A is 5 to 60% by weight, and the content of the polymer block B is 95 to 40% by weight (however, A
+ B = 100% by weight), consisting of a linear hydrogenated block copolymer in which 80% or more of the double bond residues in the conjugated diene moiety are hydrogenated, and the weight ratio of (a) / (b) is Is 100 /
0-5 / 95, hydrogenated block copolymer 1 having a total weight average molecular weight of components (a) and (b) of 50,000 to 700,000
To 99 parts by weight and (II) thermoplastic resin and / or rubbery polymer 99 to 1 parts by weight [where (I) + (II) =
100 parts by weight] is provided as a main component of the hydrogenated block copolymer composition.

The hydrogenated block copolymer used in the present invention contains polymer blocks A and B in the molecule in both the component (a) and the component (b). Of these, block A is
1,2-vinyl bond content before hydrogenation is less than 25% by weight, preferably 20% by weight or less, more preferably 18% by weight
The following is the polybutadiene block segment. Block A is a standard low density polyethylene (LD
It becomes a crystalline block segment showing a structure similar to PE). When the 1,2-vinyl bond content of the block A is 25% by weight or more, the obtained hydrogenated block copolymer is soft, and when formed into pellets, the pellets are likely to adhere to each other. During manufacturing, it will hinder the operation such as blending and handling. 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, which is not preferable.

The block B contains 50% by weight or more of the conjugated diene compound before hydrogenation, and the vinyl bond content of the conjugated diene compound (wherein the vinyl bond is 1,2-
Bonds and 3,4-bonds are collectively referred to as 25% by weight or more and are conjugated diene polymer block segments. Block B is a conjugated diene polymer or a copolymer of another monomer and a conjugated diene compound, and is similar to a rubber-like ethylene-butene copolymer or other monomer-ethylene-butene copolymer by hydrogenation. It becomes a block segment showing the structure of.

The conjugated diene compound used in the block B is 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, but in order to obtain a hydrogenated block copolymer which can be industrially used and has excellent physical properties. , 1,3-Butadiene, isoprene and 1,3-pentadiene are preferable, and 1,3-butadiene and isoprene are more preferable.

Other monomers which may be used in the block B include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N. -Diethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene, vinyl pyridine and the like can be mentioned, and styrene and α-methylstyrene are particularly preferable. In the block B, when the conjugated diene compound and another monomer are copolymerized, the distribution of the conjugated diene compound is random, tapered (in which the monomer component increases or decreases along the molecular chain), or partially block-shaped. , Or any combination thereof.

The content of the conjugated diene compound in the block B is 50% by weight or more, preferably 60% by weight or more. If the content is less than 50% by weight, the glass transition temperature of the block B is increased and the hydrogenated block obtained is It is not preferable because the mechanical properties and modification effect of the polymer are poor. The vinyl bond content of the conjugated diene compound in block B is 25
25% by weight or more, preferably 30 to 95% by weight, 25
If it is less than 10% by weight, after hydrogenation, it shows a crystalline structure derived from a polyethylene chain and has a resin-like property, and the effect of improving the impact resistance of the composition obtained by blending with a thermoplastic resin decreases.

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

The content of the block A in the block copolymer of the component (a) or the component (b) is 5 to 60% by weight,
Preferably 5-55% by weight, more preferably 10-5
It is 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 formed into pellets, the pellets are likely to adhere to each other, and a blend with a thermoplastic resin is used in the production of the composition. It will interfere with the operation and handling. Further, when blended with a thermoplastic resin, the impact resistance of the resulting composition is lowered, and when blended with a rubbery polymer, the mechanical properties of the obtained composition are inferior, which is not preferable. On the other hand, if the content of the block A exceeds 60% by weight, the impact resistance of the composition obtained by blending with the thermoplastic resin decreases, 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. Block B content is 9
When it exceeds 5% by weight, the resulting hydrogenated block copolymer is soft, and when pelletized, adhesion between pellets is likely to occur, and when manufacturing a composition with a thermoplastic resin, operations such as blending and handling are performed. Interfere with.
Further, when blended with a thermoplastic resin, the impact resistance of the resulting composition is lowered, and when blended with a rubbery polymer, the mechanical properties of the obtained composition are inferior, 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 decreases, which is not preferable.

The hydrogenated block copolymer used in the present invention has a weight ratio of component (a) / component (b) of 100 / 0-5.
/ 95, preferably 95/5 to 20/80, and more preferably 95/5 to 40/60. When the proportion of the component (a) is less than 5% by weight, the impact resistance improving effect of the composition obtained by blending with the thermoplastic resin decreases, and the composition obtained by blending with the rubber polymer. Is unfavorable because of poor mechanical properties.

Further, the hydrogenated block copolymer used in the present invention has a total weight average molecular weight of the components (a) and (b) of 50,000 to 700,000, preferably 70,000 to 650,000. It is preferably 100,000 to 650,000. When it is less than 50,000, the impact resistance improving effect when blended with a thermoplastic resin is lowered, and when it is blended with a rubbery polymer, the mechanical properties of the resulting composition are inferior, which is not preferable. On the other hand, 7
If it exceeds 0,000, the fluidity of the hydrogenated block copolymer obtained will decrease, and when blended with a thermoplastic resin, the processability and molding appearance of the resulting composition will deteriorate.

The hydrogenated block copolymer of the present invention may be produced by any method, and the components (a) and (b) may be separately produced and blended. Living anion polymerization using an alkali metal compound as an initiator to obtain a linear block copolymer as the component (b) is followed by addition of a polyfunctional coupling agent to cause a coupling reaction, and the coupling rate is the above. It is obtained by controlling the range to obtain a block copolymer containing the star block copolymer as the component (a), and then performing a hydrogenation reaction.

As the organic solvent, hydrocarbon solvents such as pentane, hexane, heptane, octane, methylcyclopentane, cyclohexane, benzene, xylene and toluene are used. As the organic alkali metal compound that is a polymerization initiator, an organic lithium compound is preferable.
As this organic lithium compound, an organic monolithium compound, an organic dilithium compound, or an organic polylithium compound is used. Specific examples of these include ethyl lithium, n-propyl lithium, isopropyl lithium, and n.
-Butyllithium, sec-butyllithium, t-butyllithium, phenyllithium, hexamethylenedilithium, butadienyllithium, isoprenyldilithium, etc., and 0.02 per 100 parts by weight of the monomer.
Used in an amount of ~ 0.4 parts by weight.

Further, the vinyl bond content of the conjugated diene compound in the blocks A and B can be adjusted by Lewis bases such as ethers and amines, specifically diethyl ether, tetrahydrofuran, propyl ether, butyl ether, higher ethers, and ethylene. Polyethylene glycol ether derivatives 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 tetramethylethylenediamine, pyridine, and tributylamine. To be

Further, the polymerization reaction is usually carried out at -30 ° C to +
It is carried out 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 heat removal. Any method may be used as the method for forming the block copolymer, but generally, in the organic solvent, the block A is first polymerized using the polymerization initiator such as the alkali metal compound, and then the block B is polymerized. At this time, the boundaries of the respective blocks do not necessarily have to be clearly distinguished. A multifunctional coupling is added to the thus obtained AB type linear block copolymer which is the component (b) and a coupling reaction is carried out to obtain a star block copolymer which is the component (a). 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 formic acid, 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 acid dianhydride, 2,3,6,7-naphthalene tetracarb Polycarboxylic acid dianhydride compounds such as acid dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 3,3,4,4-benzophenonetetracarboxylic acid dianhydride, dimethyl carbonate, diethyl carbonate, carbonic acid Carbonic acid ester compounds such as diphenyl, 1,
Polyketone compounds such as 3,6-hexanetrione and 2,3-diacetonylcyclohexane, polyaldehyde compounds such as 1,4,7-naphthenetricarboxaldehyde and 1,7,9-anthracentricarboxaldehyde, chloroform and tetra- 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, and methyltriacetoxysilane, tetrachlorotin, methyltrichlorotin,
Butyltrichlorotin, tin compounds such as tetramethoxytin, germanium compounds such as tetrachlorogermanium, 2,4,6-tri (azirinyl) -1,3,5
Examples thereof include 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
A compound having two or more kinds of functional groups capable of reacting with the living polymer in the molecule such as -diepoxy-8-pentadecanone can also be used as the coupling agent. Among these compounds, particularly preferable 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 the other monomer in these block copolymers is controlled by the amount of the monomer supplied during the polymerization in each stage, and the vinyl bond content of the conjugated diene compound varies with the components of the above micro-regulator. It is adjusted by Furthermore, 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, in order to obtain the block copolymer, for example, an organolithium compound such as n-butyllithium is used as an initiator under vacuum or at a high temperature. First under a stream of pure nitrogen
By polymerizing 1,3-butadiene using an organic solvent such as benzene or cyclohexane as a polymerization solvent in the stage, a low vinyl polybutadiene block to be the block A is polymerized, and then a micro-conditioning agent such as tetrahydrofuran or diethyl ether and By adding the conjugated diene compound for the second stage or the conjugated diene compound and another monomer, and after completing the polymerization, adding a polyfunctional coupling agent such as divinylbenzene in a calculated amount and coupling the AB block polymer. 3 or more (n ≧ 3)
As a result, a star-shaped block copolymer having A-B blocks in the form of branches can be obtained.

By hydrogenating the block copolymer polymerized as described above, a hydrogenated block copolymer used in the present invention in which the double bond residue of the conjugated diene moiety is hydrogenated is obtained. To be That is, the hydrogenated block copolymer used in the present invention is prepared by dissolving the block copolymer thus obtained in an inert solvent,
It is obtained by hydrogenating in the presence of a hydrogenation catalyst under pressurized hydrogen of -100 kg / cm ² G. Examples of the inert solvent used for hydrogenation include hydrocarbon solvents such as hexane, heptane, cyclohexane, benzene, toluene and ethylbenzene, and polar solvents such as methyl ethyl ketone, ethyl acetate, ethyl ether and tetrahydrofuran.

As the hydrogenation catalyst, dicyclopentadienyl titanium halides, cyclopentadienyl titanium halides, nickel organic carboxylates, cobalt organic carboxylates and the like and organometallic compounds of Groups I to III of the periodic table are used. And a metal catalyst such as nickel, platinum, palladium, ruthenium, rhenium, rhodium metal catalyst, cobalt, nickel, rhodium, ruthenium complex supported by carbon, silica, diatomaceous earth and the like. Also, 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, or the reaction time. If necessary, the catalyst residue is removed from the hydrogenated block copolymer solution, and an antioxidant such as a phenol-based or amine-based agent is added to facilitate the hydrogenation block copolymer from the polymer solution. It can be isolated. Isolation of the hydrogenated block copolymer, for example, in the hydrogenated block copolymer solution,
Acetone or alcohol may be added to cause precipitation, or the polymer solution may be poured into hot water with stirring to remove the solvent by distillation.

The hydrogenated block copolymer of the present invention is
It is also possible to introduce at least one functional group into the hydrogenated block copolymer and use it as a modified hydrogenated block copolymer. In the block copolymer production step before 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, in the center of the molecular chain, -OH group, -NH-CO group, -N
It is also possible to introduce functional groups such as H groups.

The hydrogenated block copolymer used in the present invention (hereinafter also referred to as "(I) hydrogenated block copolymer") is
(II) By blending with a thermoplastic resin and / or a rubbery polymer, a composition having a good balance of impact resistance, heat resistance, rigidity, processability, molding appearance, etc. and a thermoplastic having excellent mechanical properties An elastomer composition (hereinafter also referred to as "composition (I)") can be obtained.

The thermoplastic resin is not particularly limited, but 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 polyacrylic acid alkyl ester such as ABS resin, acrylic resin, polyacrylamide, polymethacrylamide, polyacrylic acid, methyl polyacrylate, ethyl polyacrylate,
Polymethacrylic acid, polymethylmethacrylate, polymethacrylic acid alkyl esters such as polyethylmethacrylate, polyacrylonitrile, polymethacrylonitrile,
Acetal resin, polyoxymethylene, chlorinated polyethylene, coumarone / indene resin, cellulose, cellulose ester, cellulose ether, carboxymethyl cellulose, cellulose ether ester, fluororesin,
Polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, nylon 11, nylon 12,
Nylon 6, Nylon 6,10, Nylon 6,12, Nylon 6,6, Nylon 6,6 and other aliphatic polyamides, Polyphenylene isophthalamide, Polyphenylene terephthalamide, Polymetaxylylenediamine and other aromatic polyamides, Polyimide, Polyethylene Terephthalate, polybutylene terephthalate, polyphenylene ether, polyphenylene sulfide, polysulfone,
Polar heat such as polyethersulfone, polysulfonamide, polyetheretherketone, polyamideimide, polyarylate, polycarbonate, polyvinyl alcohol, polyvinyl ester, polyvinyl acetate, polymethyl vinyl ether, polyisobutylene vinyl ether, polyvinyl chloride, polyvinylidene chloride A plastic resin may be used. These thermoplastic resins may 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, more preferably polyethylene and polypropylene.

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 hydrogenated products thereof, isoprene rubber, nitrile rubber and hydrogenated products thereof, chloroprene rubber, butyl rubber, ethylene-
Propylene rubber, ethylene-propylene-diene rubber,
Ethylene-butene rubber, ethylene-butene-diene rubber, acrylic rubber, α, β-unsaturated nitrile-acrylic acid ester-conjugated diene copolymer rubber, chlorinated polyethylene rubber, fluororubber, silicone rubber, urethane rubber,
Typical examples thereof include polysulfide rubber, styrene-butadiene block polymer and hydrogenated products thereof.
Among these rubber polymers, preferably hydrogenated products of styrene-butadiene rubber, hydrogenated products of 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 product of styrene-butadiene block polymer, α, β-unsaturated nitrile-acrylic acid ester-conjugated diene copolymer rubber, etc. , Rubbers which are essentially saturated or unsaturated, and modified rubbers having functional groups added thereto.

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

In the case of using the hydrogenated block copolymer (I) of the present invention to obtain a thermoplastic elastomer composition,
Whether a thermoplastic resin is used as the component (II), a rubbery polymer, or a mixture of both is used mainly depending on the properties of the hydrogenated block copolymer (I).

More specifically, usually, when the block A of the component (I) is 40% by weight or less, the component (I) exhibits a rubber-like flexible property, and therefore, the thermoplastic resin as the component (II) is used. Is preferably blended and designed to obtain a well-balanced thermoplastic elastomer composition. When the content of the block A in the component (I) is more than 40% by weight and not more than 60% by weight, the thermoplastic resin and the rubbery polymer are used together as the component (II) to achieve a comprehensive balance. It is desirable to design it as a thermoplastic elastomer. However, it is not necessarily limited to the above, and for example, in order to obtain a very soft thermoplastic elastomer, the component (I) having a content of the block A of 40% by weight or less is blended with the rubber polymer. You can also

Regarding the contents of the combination of the component (I) and the component (II), the relationship between the properties of the component (I) and the polymer used as the component (II) is generalized. Thus, the composition obtained by the present invention is not limited to the above contents, 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 rubber polymers. Furthermore, (I
When a thermoplastic resin and a rubbery polymer are used in combination as the component (I), each of them can be used in an arbitrary ratio depending on the desired performance of the final composition.

Further, in the present invention, the composition can be designed by utilizing the inherent property of (I) hydrogenated block copolymer, that is, the property of acting as a compatibilizing agent between different kinds of polymers. In general, when a block polymer is used as a compatibilizer, it is known that the addition amount thereof is about several% by weight. The minimum amount of component (I) used in the present invention is 1% by weight because it is considered to use component (I) as a compatibilizer. That is, when the component (I) is used as a compatibilizer, (I)
As component (I), two or more kinds of thermoplastic resins or a combination of thermoplastic resin and rubbery polymer is used.

Here, the component (I) effectively acts as a compatibilizer because it is a combination of specific thermoplastic resins,
Alternatively, a combination of a specific thermoplastic resin and a specific rubbery polymer may be used. In this case, for example, as the thermoplastic resin, polyethylene, polypropylene,
Polyolefin resin such as polybutene-1, carbon number 2
The graft polymer etc. which the graft polymerization of the other polymer was carried out to the polymer which makes the (alpha) -mono olefin of (8) a main constituent substance. Further, as the rubbery polymer in this case, monoolefin copolymer rubber such as ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butene rubber, ethylene-butene-diene rubber, chlorinated polyethylene rubber, styrene-butadiene rubber And hydrogenated products of nitrile rubber, styrene-butadiene block polymer, and the like. Even when the component (I) is used as a compatibilizer, a thermoplastic resin and / or a rubbery polymer other than the above may be blended.

Next, the (I) hydrogenated block copolymer of the present invention comprises a rubbery polymer as the (II) component as an essential component, and a cross-linking agent for the rubbery polymer. By reacting while giving deformation to cause at least 10% by weight of the rubbery polymer to gel, a composition having mechanically excellent properties (hereinafter also referred to as "composition (II)") is obtained. Here, the cross-linking agent used is one used for cross-linking ordinary rubber, for example, "Cross-linking agent handbook".
(Shinzo Yamashita, Tosuke Kaneko, published by Taiseisha) and the like can be used.

As the preferable cross-linking agent, sulfur, sulfur compounds, p-benzoquinone dioxime, p, p'-
Resin crosslinking 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 thereof include maleimide compounds, diepoxy compounds, dicarboxylic acid compounds, diol compounds, diamine compounds, amino resins, organic metal salts, metal alkoxides, organic metal compounds and organic peroxides.

These cross-linking agents can be used alone or as a mixture. Further, depending on the type of the cross-linking agent, the cross-linking may proceed more efficiently by using it in combination with other compounds. Especially when sulfur or a sulfur compound is used as a crosslinking agent,
It is desirable to use together a vulcanization accelerator, a vulcanization acceleration aid, and an activator that accelerate the sulfur crosslinking reaction, and the appropriate combination and the amount to be used can be determined, for example, by utilizing the above-mentioned documents. Moreover, when using an organic peroxide as a crosslinking agent, the method of using a crosslinking auxiliary together is preferable.

Examples of the crosslinking aid include sulfur, sulfur compounds such as dipentamethylene thiuram pentasulfide, mercaptobenzothiazole, oxime nitroso compounds, ethylene glycol dimethacrylate, aryl methacrylate, triaryl cyanurate, diaryl phthalate, polyethylene glycol diethylene. 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 preferably determined in consideration of the properties of the rubbery polymer in the component (II), but it should be determined in consideration of the following points. That is, the (I) hydrogenated block copolymer of the present invention can be regarded as a substantially saturated polymer essentially consisting of α-monoolefin. Therefore, if the rubber polymer in the component (II) has a high degree of unsaturation, select a crosslinking agent effective for highly unsaturated rubbers, such as ordinary sulfur vulcanizing system and resin crosslinking agent. By doing so, the rubbery polymer can be preferentially crosslinked.

However, when the rubber-like 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, a crosslinking agent is used. Depending on the type and amount used, not only the rubbery polymer but also the hydrogenated block copolymer (I) may be crosslinked. For example, when a large amount of organic peroxide is used as a crosslinking agent, (I)
There is a risk that the components may also be crosslinked and the resulting composition may become insoluble.

In such a case, it can be solved by thoroughly studying the amount of the crosslinking agent used, but there is a limit that the degree of crosslinking of the rubbery polymer cannot be made sufficiently high. As a fundamental solution to this, as a rubbery polymer to be used, functional groups such as carboxy group, acid anhydride group, hydroxy group, epoxy group, halogen group, amino group, isocyanate group, sulfonyl group or sulfonate group, etc. And a component that reacts with the functional group is used as a crosslinking agent. Examples of the rubbery polymer containing a functional group include a method of copolymerizing a monomer having a functional group, a method of introducing the monomer into the rubbery polymer by a known graft reaction, and the like. 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 or the like. In the rubbery polymer having maleic anhydride as a functional group, a diamino compound is effective as a crosslinking agent. Furthermore, when the rubbery polymer contains an unsaturated bond portion, a dithiol compound or bismaleimide can be used as a crosslinking agent. Furthermore, when an acrylic rubber or one having an acrylic ester as a main constituent is used as the rubber-like polymer, a diamino compound is effective. Furthermore, when a chlorinated polymer such as chlorinated polyethylene is used as the rubbery polymer, a dithiol compound is effective as a cross-linking agent.

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

Here, the gel content of the rubbery polymer is measured by
Under the conditions for preparing the composition (II), a cross-linking test was conducted only on the rubbery polymer, and the gel content of the cross-linked rubbery polymer was used as a substitute. This gel content is usually calculated by using cyclohexane as a solvent and extracting at 70 ° C. for 4 hours to calculate the gel content. When the rubber polymer used is insoluble in cyclohexane, the gel content of the rubber polymer is 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 in the presence of a crosslinking agent capable of crosslinking the component (I) while applying shear deformation, and By gelling at least 10% by weight of the total amount of the rubbery polymer and the component (I), a composition having mechanically excellent properties (hereinafter also referred to as "composition (III)") is obtained.

In the composition (III), a composition containing 10% by weight or more of a thermoplastic resin as the component (II) in the composition (I) crosslinks the component (I) and the rubbery polymer. At least 10% by weight of the component (I) and the rubbery polymer are gelled by being subjected to shear deformation (heat-melt mixing) in the presence of the component. That is, the composition (III) is characterized by using the component (I) of the present invention 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 less than 10% by weight, the composition obtained loses thermoplasticity and is inferior in processability, which is not preferable.

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

In the composition (III), since the component (I) which is essentially a saturated olefinic block polymer is used as the rubber component, the crosslinking agent is an organic peroxide and a crosslinking aid. Systems consisting of are preferred. As the organic peroxide, one having a one-minute half-life temperature of 150 ° C. or higher is 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- The-
Methyl-2,5-di-t-butylperoxyhexane,
Di-t-butyl peroxide, 2,5-di-methyl-
2,5-di-t-butylperoxyhexyne-3 and the like are preferable examples.

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

The amounts of the organic peroxide and the crosslinking aid used are
Calculated so that the amount of oxygen of the organic peroxide is 0.001 to 0.1 mol with respect to 100 parts by weight of the total of the component (I) or the component (I) and other rubbery polymer in the composition. If it is used in an amount of less than 0.001 mol, it is not preferable because sufficient crosslinking cannot be achieved. On the other hand, if it is used in an amount of more than 0.1 mol, further crosslinking cannot be expected and it is not economical. Unfavorable side reactions such as decomposition of the polymer are likely to occur, which is not preferable.

The amount of the crosslinking aid used is such that the amount of unsaturated double bond in the crosslinking aid is 1/4 to 40 times equivalent of the amount of active oxygen in the added organic peroxide. It is desirable to select and use. If it is less than 1/4 times the equivalent, it cannot be expected from the point of improvement of the crosslinking efficiency due to the addition of the crosslinking aid, and it is not preferable because sufficient crosslinking cannot be achieved. Cross-linking is not expected and is not economical.

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

In the production of the above-mentioned compositions (compositions (I) to (III)) containing the components (I) and (II) of the present invention, a conventional kneading machine such as 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, which can be replaced by an inert gas, is preferable.

The kneading temperature is a temperature at which all the components to be mixed are melted, and is usually 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 cannot be generally discussed. However, when a pressure kneader, a Banbury mixer or the like is used as the kneading device, the kneading time is usually about 5 It takes about 40 minutes. further,
When kneading, each component may be kneaded together,
It is also possible to employ a multi-stage divided kneading method in which after kneading arbitrary components, the remaining components are added and kneading.

In the compositions (I) to (III) using the components (I) to (II) of the present invention, various additives such as an antiaging agent, a heat stabilizer, an ultraviolet absorber, and Stabilizers such as copper damage inhibitors, silica, talc, carbon, calcium carbonate, magnesium carbonate, glass fiber, carbon fiber, metal fiber, glass beads, mica, potassium titanate whiskers, aramid fiber, wood powder, cork powder, cellulose A filler such as powder or rubber powder can be mixed and used. The blending amount of these fillers is from composition (I) to
It is preferably 200 parts by weight or less, more preferably 1 to 150 parts by weight, and particularly preferably 5 to 100 parts by weight, relative to 100 parts by weight of (III). In addition, the compositions (I) to (II
In I), a plasticizer, an oil, a softening agent such as a low molecular weight polymer, and the like may be blended together with the above-mentioned additives and used. When a softening agent is added, it is preferably 1 to 400 parts by weight with respect to 100 parts by weight of the total amount of the components (I) to (II),
More preferably 5 to 300 parts by weight, particularly preferably 1
It is 0 to 200 parts by weight.

A preferred embodiment of the present invention is as follows.
It is as follows. The thermoplastic resin as the component (II) is at least one selected from the group consisting of polyolefin, polystyrene, polyamide, polyacetal, polyester, polyphenylene ether, polyphenylene sulfide, polysulfone, and polycarbonate. The rubber polymer of the component (II) includes nitrile rubber, hydrogenated nitrile rubber, hydrogenated styrene-butadiene rubber, ethylene-propylene- (diene) rubber, ethylene-butene rubber, acrylic rubber, and styrene-conjugated polymer. It is at least one selected from the group of hydrogenated products of diene block copolymers.

Component (I) and a rubbery polymer as component (II) are contained, and a cross-linking agent for the rubbery polymer is added, and the mixture is reacted under shear deformation to give at least the rubbery polymer. A thermoplastic elastomer composition obtained by gelling 10% by weight. At least one of the component (I) and the rubbery polymer is prepared by reacting the component (I) with the component (II) containing 10% by weight or more of a thermoplastic resin in the presence of a crosslinking agent while applying shear deformation.
A thermoplastic elastomer composition obtained by gelling 0% by weight. In the above item, a thermoplastic elastomer composition comprising the crosslinking agent in an amount of 0.1 to 8 parts by weight based on 100 parts by weight of the component (II). In the above item, the crosslinking agent is 0.001 to 100 parts by weight of the component (II) as an oxygen amount of the organic peroxide.
A thermoplastic elastomer composition containing 0.1 mol.

A composition containing 1 to 150 parts by weight of a filler based on 100 parts by weight of the total amount of the components (I) to (II). Based on 100 parts by weight of the total amount of the components (I) to (II),
A composition containing 1 to 400 parts by weight of a softening agent.

[0061]

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to the above unless the gist of the present invention is exceeded.
The present invention is not limited to this example. Parts and% in the examples are by weight unless otherwise specified. In addition, 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 is 10 with ethylene tetrachloride as the solvent.
It was calculated from 0 MHz and ¹ H-NMR spectrum. Weight average molecular weight The weight average molecular weight (hereinafter, also referred to as “molecular weight”) is measured by gel permeation chromatography [GPC, column;
It was calculated in terms of polystyrene by using GMH _HR- H] manufactured by Tosoh Corporation. Weight ratio of component (a) and component (b) The weight ratio of component (a) and component (b) was calculated from the peak area ratio of component (a) and component (b) obtained by GPC.

Melt Flow Rate Melt flow rate (MFR) is defined by JIS K7210.
According to the above, it was measured at 230 ° C. and a load of 2.16 kg. Izod impact strength Measured according to JIS K7110. Flexural modulus was measured according to JIS K7203.

The heat distortion temperature was measured according to ASTM D648. Molding appearance The molding appearance was visually evaluated according to the following criteria. A: The appearance is extremely good. ◯: Appearance is good. X: Poor appearance, such as pearly luster, flow marks, and rough surface. Tensile strength, elongation at break, 100% elongation and permanent elongation, hardness were measured according to JIS K6301.

Reference Example 1 (Production of Hydrogenated Block Copolymer) 5 kg of deaerated and dehydrated cyclohexane and 150 g of 1,3-butadiene were placed in an autoclave having an internal volume of 10 liters.
Was added, 0.25 g of tetrahydrofuran and 2.00 g of n-butyllithium were added, and the polymerization temperature was adjusted to 80
Isothermal polymerization was carried out at a constant temperature of ° C. After the conversion reached about 100%, the reaction solution was cooled to 40 ° C., and tetrahydrofuran (8.5 g) and 1,3-butadiene (850 g) were added to carry out temperature rising polymerization. After the polymerization was completed, 0.93 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 7.8 mmol. In this system, 1.42 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 polymer terminal lithium as a living anion.

Then, 2.64 g of benzophenone dissolved in 20 ml of cyclohexane and 0.
90 g of a reaction product obtained by reacting 90 g in a nitrogen atmosphere in advance 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 charged in a nitrogen atmosphere. The components previously mixed below were charged into an autoclave and stirred. 8 hydrogen gas
It was supplied at a pressure of kg / cm ² G and a hydrogenation reaction was carried out 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 49,000, the weight average molecular weight of the component (b) is 196,000, and the components (a) and (b) are
The total weight average molecular weight of the components was 182,000, and the weight ratio of component (a) / component (b) was 70/30. Further, the 1,2-butadiene bond content of the 1,3-butadiene block measured at the end of the first stage 1,3-butadiene block polymerization was 15%, and the completion of the second stage 1,3-butadiene polymerization. 1,2-vinyl bond content and first measured at time point
As a result of calculation from the vinyl bond content at the second stage, the 1,2-vinyl bond content of the 1,3-butadiene block at the second stage was 40%. This hydrogenated block copolymer is
Set to 1.

Reference Examples 2 to 9 By the same method as in Reference Example 1, monomer species, monomer amount, catalyst amount, coupling agent species, coupling were obtained so as to obtain each hydrogenated block copolymer in Tables 1 and 2. It was prepared by varying the amount of agent, the polymerization temperature, the polymerization time, and the like. The results are shown in Tables 1-2.

Reference Examples 10 to 18 By the same method as in Reference Example 1, monomer species, monomer amount, catalyst amount, coupling agent species, coupling were obtained so as to obtain each hydrogenated block copolymer in Tables 3 to 4. It was prepared by varying the amount of agent, the polymerization temperature, the polymerization time, and the like. The results are shown in Tables 3-4.

In the hydrogenated block copolymer of Reference Example 1, K-1 and K-2 have a 1,2-vinyl bond content of block A and a vinyl bond content of block B within the range of the present invention. It is the outside. K-3, K-
4 is the hydrogenated block copolymer of Reference Example 2 which does not contain block A or block B. K-5 and K-6 are the hydrogenated block copolymers of Reference Example 4 having a weight average molecular weight outside the range of the present invention. K-7 is an example of the hydrogenated block copolymer of Reference Example 4 in which the coupling reaction was not performed. K-8 is a bifunctional 1,2 as a coupling agent.
-This is an example using dibromoethane and does not include the star-shaped hydrogenated block copolymer of the component (a). K-9 is
In the hydrogenated block copolymer of Reference Example 5, the hydrogenation rate was out of the range of the present invention.

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

Comparative Examples 1 to 9 In the same manner as in Example 1, K-1 to 9 shown in Tables 3 to 4 were used.
An injection-molded product was produced using the hydrogenated block copolymer of Example 1 and each physical property was evaluated. The results are shown in Tables 7-8. The composition using the hydrogenated block copolymer that does not satisfy the requirements of the present invention lacks the balance of processability, impact resistance, rigidity, heat resistance, and molding appearance.

Comparative Examples 10 to 12 In Example 1, instead of the hydrogenated block copolymer,
Ethylene-propylene copolymer; EP [manufactured by Japan Synthetic Rubber Co., Ltd., EP02P], ethylene-butene-1 copolymer; EBM [manufactured by Japan Synthetic Rubber Co., Ltd., EBM2041
P], hydrogenated product of styrene-butadiene-styrene triblock copolymer; injection molded product was prepared by the same method except that SEBS [Crayton G1650 manufactured by Shell Co., Ltd.] was used, and measurement of each physical property was performed. I went. The results are shown in Tables 8-9. From these comparisons, conventionally used ethylene-propylene copolymer (EP), ethylene-butene-1
Compared with the copolymer (EBM) and the hydrogenated product of the styrene-butadiene-styrene triblock copolymer (SEBS), the composition using the hydrogenated block copolymer of the present invention has processability, impact resistance, It can be seen that the balance of rigidity, heat resistance and molding appearance is excellent.

Examples 11 to 15 and Comparative Examples 13 to 16 Using the formulation shown in Tables 10 to 11, a hydrogenated block copolymer, a thermoplastic resin, and a rubber-like polymer were added to a Laboplast mill whose temperature was adjusted to 190 ° C. Add coalescence, 10 at 80 rpm
Mix for minutes. The mixture was discharged, formed into a sheet with a hot roll, and then press-formed into a square plate with a side of 10 cm, which was cut out with a dumbbell cutter to give a test piece for measurement. When the cross-linking agent was added, it was added after the hydrogenated block copolymer, the thermoplastic resin and the rubbery polymer were completely melted. In this case, after adding the crosslinking agent, 80 rp
The mixing was continued at m, the shaft torque was observed with the torque meter attached to the Labo Plastomill, and the mixing was continued for 3 minutes from the time when the maximum torque value was shown, and the mixture was discharged.

Examples 11 to 15 are examples using the hydrogenated block copolymer of the present invention, and it can be seen that all are compositions reflecting the excellent properties of the hydrogenated block copolymer. On the other hand, Comparative Examples 13 to 15 are examples in which the hydrogenated block copolymer of the present invention is not used, and have low elongation at break, high hardness, and poor permanent elongation. Comparative Example 1
No. 6 is an example using a hydrogenated block copolymer outside the scope of the present invention, which has high hardness and poor permanent elongation.

[0076]

[Table 1]

[0077]

[Table 2]

[0078]

[Table 3]

[0079]

[Table 4]

[0080]

[Table 5]

[0081]

[Table 6]

[0082]

[Table 7]

[0083]

[Table 8]

[0084]

[Table 9]

[0085]

[Table 10]

* 1) Polyethylene Z manufactured by Mitsubishi Petrochemical Co., Ltd.
F-51 * 2) Polypropylene MA-7 manufactured by Mitsubishi Petrochemical Co., Ltd.

[0087]

[Table 11]

[0088]

According to the present invention, a hydrogenated block copolymer obtained by hydrogenating a block copolymer having a star structure is blended with a thermoplastic resin and / or a rubbery polymer. It is possible to obtain a composition having an excellent balance of impact resistance, heat resistance, rigidity, processability, molding appearance, and a hydrogenated block copolymer composition which is a thermoplastic elastomer composition having excellent mechanical properties. it can. The composition of the present invention is used as various molded articles by injection molding, extrusion molding, vacuum molding, and the like, making use of its excellent characteristics,
Automotive interior and exterior materials, various electrical and electronic parts, housings,
Industrial parts, stationery, medical materials, film / sheet products,
It can be widely used for adhesives and adhesives.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasuhiko Takemura 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd.

Claims (2)

[Claims] 1. A polymer block A in a molecule of (I) (a).
And B (where A is a polybutadiene block having a 1,2-vinyl bond content of less than 25% by weight, B is a conjugated diene compound of 50% by weight or more, and the vinyl bond content of the conjugated diene compound is 25% by weight). % Or more), and the block structure is (AB) nX (where n is an integer of 3 or more and X is a coupling agent residue) Block copolymer having a content of polymer block A of 5 to 60% by weight and a content of polymer block B of 95 to 40% by weight
(However, A + B = 100% by weight), and a star-shaped hydrogenated block copolymer in which 80% or more of the double bond residues of the conjugated diene portion are hydrogenated, and (b) the polymer block A in the molecule.
And B (where A and B are the same as those in (a) above), and the block structure is a linear block copolymer represented by AB, and the polymer block A is contained. 5 to 60% by weight, the content of the polymer block B is 95 to 4
0% by weight (however, A + B = 100% by weight), consisting of a linear hydrogenated block copolymer in which 80% or more of the double bond residues of the conjugated diene moiety are hydrogenated, and (a) /
1 to 99 parts by weight of a hydrogenated block copolymer having a weight ratio of (b) of 100/0 to 5/95 and a total weight average molecular weight of the components (a) and (b) of 50,000 to 700,000, And (I
I) Thermoplastic resin and / or rubbery polymer 99-1
A hydrogenated block copolymer composition containing parts by weight [however, (I) + (II) = 100 parts by weight] as a main component. 2. The thermoplastic resin is polypropylene and / or
Alternatively, the hydrogenated block copolymer composition according to claim 1, which is polyethylene.