JP2003277520A - Dynamically crosslinked hydrogenated copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dynamically crosslinked hydrogenated copolymer or a dynamically crosslinked hydrogenated copolymer composition which excels in abrasion resistance, scratch resistance, and oil resistance. <P>SOLUTION: The dynamically crosslinked hydrogenated copolymer or dynamically crosslinked hydrogenated copolymer composition is obtained by dynamically vulcanizing a hydrogenated copolymer or a hydrogenated copolymer composition to be constituted of (1) 90-100 pts.wt. hydrogenated copolymer of a copolymer which is composed of a conjugated diene and a vinyl aromatic compound and meets the conditions such that (a) the content of the vinyl aromatic compound is more than 50 wt.% to not more than 90 wt.%; (b) the amount of the vinyl aromatic compound polymer block in the copolymer is not more-than 40 wt.%; (c) the weight average molecular weight is 50,0001,000,000, (d) not less than 10% double bonds based on the conjugated diene compound in the copolymer is hydrogenated; and (f) substantially no crystallization peak is present in the temperature range of-50 to 100°C in the differential scanning calorimetry (DSC) and (2) 10-0 pt.wt. thermoplastic resin and/or rubbery polymer in the presence of a vulcanizing agent. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a dynamically crosslinked hydrogenated copolymer or a dynamically crosslinked hydrogenated copolymer composition having improved abrasion resistance, scratch resistance, and oil resistance, and more specifically, a specific Dynamic cross-linking hydrogen co-polymer obtained by dynamically vulcanizing a hydrogenated copolymer or a hydrogenated copolymer composition composed of a specific hydrogenated copolymer and a thermoplastic resin in the presence of a vulcanizing agent. It relates to a coalesced or dynamically crosslinked hydrogenated copolymer composition.

[0002]

2. Description of the Related Art In recent years, thermoplastic elastomers, which are rubber-like soft materials and do not require a vulcanization step and have the same moldability as thermoplastic resins, are used in automobile parts, home electric appliances parts, wire coating materials and medical parts. It is used in fields such as, sundries, and footwear. Among these, a block copolymer comprising a conjugated diene and a vinyl aromatic compound having a relatively low vinyl aromatic compound content as a thermoplastic elastomer, for example, a vinyl aromatic compound content of about 30% by weight, and a block copolymer thereof Hydrogenated products are preferably used because they show properties similar to vulcanized rubber. However, such block copolymers and hydrogenated products thereof have insufficient oil resistance. In order to improve such a problem, a method of partially crosslinking such a block copolymer or a hydrogenated product thereof is disclosed in JP-A-59-131613, and further improvement has been desired.

[0003]

SUMMARY OF THE INVENTION The present invention is directed to wear resistance,
It is intended to provide a dynamically crosslinked hydrogenated copolymer or a dynamically crosslinked hydrogenated copolymer composition having excellent scratch resistance and oil resistance.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that the content of the vinyl aromatic compound polymer block is specific and the content of the vinyl aromatic compound polymer block is Is a hydrogenated copolymer of a copolymer of a conjugated diene and a vinyl aromatic compound having a specific range, or a hydrogenated copolymer composed of the hydrogenated copolymer and a thermoplastic resin. It has been found that the above problems can be effectively solved by dynamically vulcanizing the composition in the presence of a vulcanizing agent, and the present invention has been completed.

That is, in the present invention, a copolymer comprising a conjugated diene and a vinyl aromatic compound is a hydrogenated product (1) satisfying the following (a) to (f), and (a) containing a vinyl aromatic compound: The amount exceeds 50% by weight and 90% by weight or less, (b)
The amount of the vinyl aromatic compound polymer block in the copolymer is 40% by weight or less, and (c) the weight average molecular weight is 50,000 to 100.
10% or more of the double bond based on the conjugated diene compound in the copolymer (d) is hydrogenated, (f) in a differential scanning calorimetry (DSC method), a temperature of -50 to 100 ° C. Hydrogenated copolymer (1) having substantially no crystallization peak in the range of 10 to 100 parts by weight, and a hydrogenated copolymer composed of 90 to 0 parts by weight of a thermoplastic resin and / or a rubbery polymer (2). A dynamically crosslinked hydrogenated copolymer or a dynamically crosslinked hydrogenated copolymer composition obtained by dynamically vulcanizing a polymer or a hydrogenated copolymer composition in the presence of a vulcanizing agent (hereinafter, dynamically crosslinked water Referred to as an additive copolymer).

The present invention will be described in detail below. In the present invention, the content of the vinyl aromatic compound in the hydrogenated copolymer is more than 50% by weight and 90% by weight or less, preferably more than 60% by weight and 88% by weight or less, more preferably 62 to 86.
% By weight. It is necessary to use the vinyl aromatic compound having a content within the range specified in the present invention in order to obtain the composition intended by the present invention. In the present invention, the content of the vinyl aromatic compound in the hydrogenated copolymer is
It may be grasped by the content of the vinyl aromatic compound in the copolymer before hydrogenation.

In the hydrogenated copolymer used in the present invention,
The content of the vinyl aromatic compound polymer block is 40% by weight or less, preferably 3 to 40% by weight, more preferably 5%.
~ 35% by weight. In the present invention, when it is desired to obtain a composition having good flexibility, the content of the vinyl aromatic compound polymer block is less than 10% by weight, preferably less than 8% by weight, more preferably less than 5% by weight. Recommended. Further, in obtaining the composition of the present invention, when a hydrogenated copolymer having excellent blocking resistance is preferred, the content of the vinyl aromatic compound polymer block is 10 to 40% by weight, preferably 13 to 37. % By weight, more preferably 1
It is recommended to be 5 to 35% by weight. The content of the vinyl aromatic compound polymer block is measured by, for example, a method of oxidatively decomposing the copolymer before hydrogenation with tert-butyl hydroperoxide using osmium tetroxide as a catalyst (IM KOLTHOFF, et al., J.
Polym. Sci. 1,429 (1946)) to obtain the weight of the vinyl aromatic hydrocarbon polymer block component (excluding the vinyl aromatic hydrocarbon polymer component having an average degree of polymerization of about 30 or less). It can be obtained from the following equation. Block weight of vinyl aromatic hydrocarbon (% by weight) = (weight of vinyl aromatic hydrocarbon polymer block in copolymer before hydrogenation / weight of copolymer before hydrogenation) × 100

In the present invention, the block ratio of the vinyl aromatic compound in the hydrogenated copolymer (the block ratio is
(It means the ratio of the content of vinyl aromatic compound polymer block to the total amount of vinyl aromatic compound in the copolymer)
Is less than 50% by weight, preferably 20% by weight or less, more preferably 18% by weight or less, in order to obtain a composition having better flexibility.

The weight average molecular weight of the hydrogenated copolymer used in the present invention is 5 to 1,000,000, preferably 100,000 to 800,000, and more preferably 13 to 500,000. When a hydrogenated copolymer having a vinyl aromatic compound polymer block content of 10 to 40% by weight is used, its weight average molecular weight exceeds 100,000 and less than 500,000, preferably 130,000 to 400,000, and more preferably Is recommended to be 150,000 to 300,000. When the weight average molecular weight is less than 50,000, the mechanical strength is poor, and 100
When it exceeds 10,000, it is not preferable because the moldability is poor.
In the present invention, the molecular weight distribution of the hydrogenated copolymer is preferably 1.5 to 5.0, more preferably 1.6 to 4.5, still more preferably 1.8 to 4 from the viewpoint of molding processability. Is recommended.

The hydrogenated copolymer or the like used in the present invention is a hydrogenated product of a copolymer composed of a conjugated diene and a vinyl aromatic compound, which is an unsaturated double bond based on the conjugated diene compound in the copolymer. The total hydrogenation rate is 10% or more, preferably 20% or more, more preferably 30% or more. When obtaining a composition with particularly excellent weather resistance, the hydrogenation rate is 75
% Or more, preferably 85% or more, more preferably 90%
The above is recommended. Further, in order to obtain a vulcanized composition having good vulcanizate properties, it is recommended that the hydrogenation rate is 98% or less, preferably 95% or less, more preferably 90% or less. Further, in the hydrogenated copolymer or the like used in the present invention, in order to obtain a composition particularly excellent in thermal stability, the hydrogenation rate of vinyl bond is 85% or more, preferably 90% or more, more preferably 95%. The above is recommended. Here, the hydrogenation rate of vinyl bond is
It refers to the proportion of hydrogenated vinyl bonds in the vinyl bonds in the conjugated diene incorporated in the copolymer before hydrogenation. The hydrogenation rate of the aromatic double bond based on vinyl aromatic hydrocarbon in the copolymer is not particularly limited, but the hydrogenation rate is 50% or less, preferably 30% or less, more preferably 20%. The following is preferable.

The hydrogenated copolymer and the like used in the present invention are -50 to 100 in the differential scanning calorimetry (DSC method).
It is a hydrogenated product having substantially no crystallization peak in the temperature range of ° C. Here, the crystallization peak is substantially absent in the temperature range of −50 to 100 ° C.
Even if a peak due to crystallization does not appear in this temperature range or a peak due to crystallization is observed, the crystallization peak calorific value due to the crystallization is 3 J /
less than g, preferably less than 2 J / g, more preferably 1 J
/ G, and particularly preferably, there is no crystallization peak calorific value.

In the present invention, the structure of the hydrogenated copolymer is not particularly limited, and any structure can be used,
Particularly recommended is a hydrogenated product of a copolymer having at least one structure selected from the following general formulas 1 to 5. The hydrogenated copolymer used in the present invention may be any mixture of hydrogenated copolymers having a structure represented by the following general formula. Further, a vinyl aromatic compound polymer may be mixed with the hydrogenated copolymer. 1 B 2 B-A 3 B-A-B 4 (B-A) _m- X 5 (B-A) _n- X-A _p (where B is a random copolymer of a conjugated diene and a vinyl aromatic compound). A polymer block, A is a vinyl aromatic compound polymer block, m is an integer of 2 or more, and n
And p are integers of 1 or more. X represents a coupling agent residue. )

In the general formula, the vinyl aromatic hydrocarbons in the random copolymer block B may be distributed uniformly or in a taper shape. In the copolymer block B, a plurality of portions in which vinyl aromatic hydrocarbons are uniformly distributed and / or a plurality of portions in which taper distribution is formed may coexist. Further, m is an integer of 2 or more, preferably 2 to 10, and n and p are 1 or more, preferably an integer of 1 to 10.

In the present invention, the difference between the maximum value and the minimum value of the vinyl bond content in the copolymer chain before hydrogenation is less than 10%, preferably 8% or less, more preferably 6%.
% Or less is recommended. The vinyl bonds in the copolymer chain may be evenly distributed or tapered. Here, the difference between the maximum value and the minimum value of the vinyl bond content is the polymerization condition, that is, the type of the vinyl amount adjusting agent,
It is the maximum and minimum values of the vinyl amount determined by the amount and the polymerization temperature.

The difference between the maximum value and the minimum value of the vinyl bond content in the co-conjugated diene polymer chain should be controlled by, for example, the polymerization temperature during the polymerization of the conjugated diene or the copolymerization of the conjugated diene and the vinyl aromatic compound. You can For a given type and amount of vinyl modifier such as a tertiary amine compound or ether compound, the vinyl bond content incorporated into the polymer chain during polymerization depends on the polymerization temperature. Therefore,
The polymer polymerized isothermally becomes a polymer in which vinyl bonds are evenly distributed. On the other hand, the polymers polymerized at elevated temperatures have different vinyl bond contents, such as a high vinyl bond content in the initial stage (polymerization at low temperature) and a low vinyl bond content in the latter half (polymerization at high temperature). .

In the present invention, the content of the vinyl aromatic compound can be known by using an ultraviolet spectrophotometer, an infrared spectrophotometer, a nuclear magnetic resonance apparatus (NMR) or the like. In addition, the amount of the vinyl aromatic compound polymer block is the same as the above-mentioned KO.
It can be known by the method of LTHOFF. The vinyl bond content based on the conjugated diene in the copolymer before hydrogenation is
It can be known by using an infrared spectrophotometer (for example, Hampton method) or a nuclear magnetic resonance apparatus (NMR).

The hydrogenation rate of the hydrogenated copolymer can be known by using an infrared spectrophotometer, a nuclear magnetic resonance apparatus (NMR) or the like. Further, in the present invention, the molecular weight of the hydrogenated copolymer is determined by gel permeation chromatography (G
Calibration curve obtained from the measurement of commercially available standard polystyrene (prepared using the peak molecular weight of standard polystyrene)
Is the weight average molecular weight determined by using. Similarly, the molecular weight distribution of the hydrogenated copolymer can be determined from the measurement by GPC. By adding hydrogen to the copolymer having such a structure, a hydrogenated copolymer having a specific structure can be obtained.

In the present invention, the conjugated diene is a diolefin having a pair of conjugated double bonds, for example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene) and 2,3-dimethyl-1. , 3-Butadiene, 1,3
-Pentadiene, 2-methyl-1,3-pentadiene,
1,3-hexadiene and the like, but particularly common ones include 1,3-butadiene and isoprene. These may be used alone or in combination of two or more. Examples of vinyl aromatic compounds include styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl- Examples thereof include p-aminoethylstyrene and the like, and not only one kind but also two or more kinds may be used.

In the present invention, the microstructure of the conjugated diene moiety (cis, trans,
The ratio of vinyl) can be arbitrarily changed by using a polar compound described later and is not particularly limited. Generally, when 1,3-butadiene is used as the conjugated diene, the 1,2-vinyl bond content is 5 to 80%, preferably 10%.
-60%, when isoprene is used as the conjugated diene or when 1,3-butadiene and isoprene are used in combination, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds is generally 3 to 75%, It is recommended to be preferably 5 to 60%. In the present invention, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds (however, when 1,3-butadiene is used as the conjugated diene,
2-vinyl bond amount) is hereinafter referred to as vinyl bond.

In the present invention, the copolymer before hydrogenation is obtained, for example, by anion living polymerization using an initiator such as an organic alkali metal compound in a hydrocarbon solvent. Examples of the hydrocarbon solvent include n-butane, isobutane, n-pentane, n-hexane, n-heptane, n
-Aliphatic hydrocarbons such as octane, cyclohexane,
Alicyclic hydrocarbons such as cycloheptane and methylcycloheptane, and aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene.

Further, as the initiator, an aliphatic hydrocarbon alkali metal compound, an aromatic hydrocarbon alkali metal compound, which is generally known to have anionic polymerization activity for a conjugated diene compound and a vinyl aromatic compound, Organic amino alkali metal compounds and the like are included, and the alkali metal is lithium, sodium, potassium, or the like. Suitable organic alkali metal compounds are aliphatic and aromatic hydrocarbon lithium compounds having 1 to 20 carbon atoms, 1
A compound containing one lithium in the molecule, a dilithium compound containing a plurality of lithium in one molecule, a trilithium compound, and a tetralithium compound are included.

Specifically, n-propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium, n-hexyllithium, benzyllithium, phenyllithium, tolyllithium, diisopropenylbenzene. Reaction product of sec-butyllithium, divinylbenzene and se
Examples include reaction products of c-butyllithium and a small amount of 1,3-butadiene.

Further, 1- (t-butoxy) propyllithium disclosed in US Pat. No. 5,708,092 and a lithium compound having 1 to several molecules of isoprene monomer inserted therein for improving the solubility thereof, 1- (t disclosed in British Patent 2,241,239
-Butyldimethylsiloxy) hexyllithium and other siloxy group-containing alkyllithium, US Pat. No. 5,527,7
Amino lithiums such as the amino group-containing alkyl lithium, lithium diisopropylamide and lithium hexamethyldisilazide disclosed in the specification of No. 53 can also be used.

In the present invention, when a conjugated diene compound and a vinyl aromatic compound are copolymerized with an organic alkali metal compound as a polymerization initiator, a vinyl bond (1, 2, or 3, resulting from the conjugated diene compound incorporated in the polymer is obtained. A tertiary amine compound or an ether compound may be added as an adjusting agent in order to adjust the content of (4 bonds) and the random copolymerizability of the conjugated diene compound and the vinyl aromatic compound. The tertiary amine compound is a compound of the general formula R1R2R3N (wherein R1, R2 and R3 are hydrocarbon groups having 1 to 20 carbon atoms or hydrocarbon groups having a tertiary amino group).

For example, trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N-ethylpiperidine, N-methylpyrrolidine,
N, N, N ', N'-tetramethylethylenediamine,
N, N, N ', N'-tetraethylethylenediamine,
1,2-dipiperidinoethane, trimethylaminoethylpiperazine, N, N, N ′, N ″, N ″ -pentamethylethylenetriamine, N, N′-dioctyl-p-phenylenediamine and the like.

The ether compound is selected from linear ether compounds and cyclic ether compounds, and the linear ether compound is dimethyl ether, diethyl ether, diphenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether. And diethylene ether dialkyl ether compounds such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether.

As the cyclic ether compound, tetrahydrofuran, dioxane, 2,5-dimethyloxolane, 2,2,5,5-tetramethyloxolane, 2,2
-Bis (2-oxolanyl) propane, an alkyl ether of furfuryl alcohol, and the like.

In the present invention, the method of copolymerizing the conjugated diene compound and the vinyl aromatic compound using the organic alkali metal compound as a polymerization initiator may be batch polymerization, continuous polymerization, or a combination thereof. Good. In particular, a continuous polymerization method is recommended in order to adjust the molecular weight distribution within a preferable appropriate range. The polymerization temperature is generally 0 ° C to 180 ° C, preferably 30 ° C to 150 ° C. The time required for the polymerization varies depending on the conditions, but is usually within 48 hours, and particularly preferably 0.1 to 10 hours.

The atmosphere of the polymerization system is preferably an inert gas atmosphere such as nitrogen gas. The polymerization pressure is not particularly limited as long as it is within the range of the above-mentioned polymerization temperature and is a pressure sufficient to maintain the monomer and the solvent in the liquid phase. Further, it is necessary to take care so that impurities such as water, oxygen, carbon dioxide gas, etc. which inactivate the catalyst and the living polymer are not mixed in the polymerization system. In the present invention, a coupling reaction can be carried out by adding a necessary amount of a bifunctional or higher functional coupling agent at the end of the polymerization. The bifunctional coupling agent may be any known one and is not particularly limited. Examples thereof include dihalogen compounds such as dimethyldichlorosilane and dimethyldibromosilane, and acid esters such as methyl benzoate, ethyl benzoate, phenyl benzoate, and phthalates. The trifunctional or higher polyfunctional coupling agent may be any known one and is not particularly limited.

For example, trihydric or higher polyalcohols, epoxidized soybean oil, polyhydric epoxy compounds such as diglycidyl bisphenol A, and general formula R _4-n SiX _n (where R is a hydrocarbon having 1 to 20 carbon atoms). Group, X is halogen, n is 3
Or a silicon halide compound represented by 4), such as methylsilyl trichloride, t-butylsilyl trichloride, silicon tetrachloride and their bromides, etc.
_4-n SnX _n (wherein R is a hydrocarbon group having 1 to 20 carbon atoms, X is halogen, and n is 3 or 4), for example, a tin halide compound such as methyltin trichloride, t-butyltin trichloride, tetrachloride Examples include polyvalent halogen compounds such as tin. Dimethyl carbonate or diethyl carbonate can also be used.

In the present invention, a modified copolymer having a polar group-containing atomic group bonded to at least one polymer chain of the polymer can be used as the copolymer. As the polar group-containing atomic group, for example, hydroxyl group, carboxyl group, carbonyl group, thiocarbonyl group, acid halide group, acid anhydride group, carboxylic acid group, thiocarboxylic acid group, aldehyde group, thioaldehyde group, carboxylic acid ester group , Amide group, sulfonic acid group, and sulfonic acid ester group.

Further, phosphoric acid group, phosphoric acid ester group, amino group, imino group, nitrile group, pyridyl group, quinoline group, epoxy group, thioepoxy group, sulfide group, isocyanate group, isothiocyanate group, silicon halide group, An atomic group containing at least one polar group selected from a silanol group, an alkoxy silicon group, a tin halide group, an alkoxy tin group, a phenyl tin group and the like can be mentioned. The modified copolymer can be obtained by reacting a compound having these polar group-containing atomic groups at the end of polymerization of the copolymer. As the compound having a polar group-containing atomic group, specifically, the modification treatment agent described in JP-B-4-39495 can be used.

By hydrogenating the copolymer obtained above, the hydrogenated copolymer used in the present invention can be obtained.
The hydrogenation catalyst is not particularly limited, and conventionally known metals (1) such as Ni, Pt, Pd and Ru are carbon,
A supported heterogeneous hydrogenation catalyst supported on silica, alumina, diatomaceous earth, etc., (2) Organic acid salts such as Ni, Co, Fe and Cr or transition metal salts such as acetylacetone salts and reducing agents such as organic aluminum. And a so-called Ziegler type hydrogenation catalyst, and (3) a homogeneous hydrogenation catalyst such as a so-called organometallic complex such as an organometallic compound such as Ti, Ru, Rh and Zr.

As a specific hydrogenation catalyst, Japanese Patent Publication No. 42-870
Hydrogenation catalysts described in Japanese Patent Publication No. 4, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-37970, Japanese Patent Publication No. 1-53851, and Japanese Patent Publication No. 2-9041. Can be used. Preferred hydrogenation catalysts include mixtures with titanocene compounds and / or reducing organometallic compounds.

As the titanocene compound, Japanese Patent Application Laid-Open No. 8-1
The compounds described in JP-A-09219 can be used, and specific examples thereof include (substituted) cyclopentadienyl skeletons such as biscyclopentadienyl titanium dichloride and monopentamethylcyclopentadienyl titanium trichloride, indenyl skeletons, or Examples thereof include compounds having at least one ligand having a fluorenyl skeleton. Examples of the reducing organic metal compound include organic alkali metal compounds such as organic lithium, organic magnesium compounds, organic aluminum compounds, organic boron compounds and organic zinc compounds.

In the present invention, the hydrogenation reaction is generally 0 to
It is carried out in a temperature range of 200 ° C, more preferably 30 to 150 ° C. The pressure of hydrogen used in the hydrogenation reaction is 0.1
To 15 MPa, preferably 0.2 to 10 MPa, more preferably 0.3 to 5 MPa is recommended. Also,
The hydrogenation reaction time is usually 3 minutes to 10 hours, preferably 10 minutes to 5 hours. The hydrogenation reaction can be used as a batch process, a continuous process, or a combination thereof.

The solution of the hydrogenated copolymer obtained as described above can be separated from the solution by removing the catalyst residue if necessary. As a method for separating the solvent, for example, a method in which a polar solvent which is a poor solvent for the hydrogenated copolymer such as acetone or alcohol is added to the reaction solution after hydrogenation to precipitate and recover the polymer, and the reaction solution is stirred Examples thereof include a method in which the solvent is removed by steam stripping to remove the solvent, and a method in which the polymer solution is directly heated to distill off the solvent. still,
The hydrogenated copolymer of the present invention includes various phenolic stabilizers,
Stabilizers such as phosphorus-based stabilizers, sulfur-based stabilizers, and amine-based stabilizers can be added.

The hydrogenated copolymer used in the present invention is α, β.
It may be modified with unsaturated carboxylic acids or their derivatives, for example their anhydrides, their esters, their amidates, their imidates. Specific examples of α, β-unsaturated carboxylic acid or its derivative include maleic anhydride, maleic anhydride imide, acrylic acid or its ester, methacrylic acid or its ester, endo-cis-bicyclo [2,2,1 ]
-5-heptene-2,3-dicarboxylic acid or its anhydride and the like can be mentioned. The addition amount of the α, β-unsaturated carboxylic acid or its derivative is generally 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of the hydrogenated polymer.

In the present invention, the hydrogenated copolymer may be used in combination with a thermoplastic resin. The thermoplastic resin used as the component (2) is not particularly limited, but is a styrene resin, an olefin resin, polycarbonate, polyethylene terephthalate, polyester such as polybutylene terephthalate, polyphenylene ether (PPE), polyphenylene sulfide (PPS). And the like, polyamides such as 6.6 nylon and 6 nylon, methacrylic resins, acrylic resins, ethylene vinyl acetate copolymer (EVA), and the like.

As the styrene resin, polystyrene, rubber-reinforced polystyrene (high impact polyester),
Block copolymer resin of conjugated diene compound and vinyl aromatic compound and hydrogenated product thereof, styrene / methacrylic acid ester such as acrylonitrile / styrene copolymer (AS resin), styrene / methyl methacrylate copolymer (MS resin) Copolymer, acrylonitrile-butadiene-styrene terpolymer (ABS resin), rubber reinforced M
S resin, maleic anhydride / styrene terpolymer, maleic anhydride / acrylonitrile / styrene terpolymer, acrylonitrile / α-methylstyrene terpolymer, methacrylonitrile / styrene copolymer, methacrylic acid Examples thereof include methyl / acrylonitrile / styrene terpolymer.

Examples of the olefin resin include homopolymers such as polyethylene (PE) and polypropylene (PP),
And blocks such as butene, hexene and octene, random copolymers, polymethylpentene, polybutene-1,
Examples thereof include propylene / butene-1 copolymer, chlorinated polyolefin, ethylene / methacrylic acid and its ester copolymer, styrene / acrylic acid and its ester copolymer, ethylene / propylene copolymer (EPR) and the like. .

Examples of the methacrylic resin include polymethylmethacrylate (PMMA), methylmethacrylate / methacrylic acid copolymer and the like. You may use these thermoplastic resins in mixture of 2 or more types. In the present invention, the hydrogenated copolymer may be used in combination with a rubbery polymer. The rubber-like polymer used as the component (2) is not particularly limited, but butadiene rubber and its hydrogenated product, styrene-butadiene rubber and its hydrogenated product (however, different from the hydrogenated copolymer of the present invention). ), Isoprene rubber, acrylonitrile-butadiene rubber and hydrogenated products thereof, chloroprene rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butene-diene rubber, ethylene-butene rubber, ethiene-hexene rubber, ethylene-octene rubber, and other olefins. An elastomer can be used.

Further, butyl rubber, acrylic rubber, fluororubber, silicone rubber, chlorinated polyethylene rubber, epichlorohydrin rubber, α, β-unsaturated nitrile-acrylic acid ester-conjugated diene copolymer rubber, urethane rubber,
Styrene type elastomers such as polysulfide rubber, styrene-butadiene block copolymer and hydrogenated product thereof, styrene-isoprene block copolymer and hydrogenated product thereof,
Natural rubber etc. are mentioned. These rubbery polymers are
A modified rubber having a functional group may be used. These can be used alone or in combination.

Particularly preferred as component (2) are polyethylene, polypropylene, polystyrene, ABS,
PMMA, styrene-butadiene-methyl methacrylate terpolymer (MBS), styrene-butadiene block copolymer (SBS), styrene-isoprene block copolymer (SIS), and hydrogenated products thereof such as styrene-ethylene. -Butylene block polymer (SEB
S), styrene-ethylene-propylene block polymer (SEPS), styrene-butadiene rubber (SBR),
Examples thereof include EPDM and butyl rubber.

The amount of the thermoplastic resin and / or the rubber-like polymer of the component (2) used is 10/90 to 100/0, preferably 20/80, in the weight ratio of the component (1) / component (2).
To 90/10, more preferably 30/70 to 80/20
Is. When the amount of the component (2) used exceeds 90 parts by weight, the flexibility of the dynamically crosslinked hydrogenated copolymer and the like is deteriorated, and thus the unfavorable thermoplastic resin and / or the rubber-like polymer of the component (2) is a hydrogenated copolymer. It may be dynamically vulcanized in the presence of a vulcanizing agent together with the coalescent compound, or the component (2) may be blended and used after the hydrogenated copolymer is dynamically crosslinked.

The dynamic vulcanization referred to in the present invention is a method in which various compounds are kneaded in a molten state under a temperature condition in which a vulcanizing agent reacts to cause dispersion and crosslinking simultaneously.
A. Y. Coran et al. (Rub. Chem. An.
d Technol. vol. 53.141- (198
0)). A kneading machine for dynamic vulcanization is usually a Banbury mixer, a closed kneading machine such as a pressure kneader, a single-screw or twin-screw extruder, or the like. The kneading temperature is usually 130 to 300 ° C, preferably 150 to 250.
℃. The kneading time is usually 1 to 30 minutes. As a vulcanizing agent for dynamic vulcanization, an organic peroxide or a phenol resin cross-linking agent is often used.

Specific examples of the organic peroxide include dicumyl peroxide, di-tert-butylperoxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane and 2,5- Dimethyl-2,5-di-
(Tert-Butylperoxy) hexyne-3,1,3-
Bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy)-
3,3,5-Trimethylcyclohexane, n-butyl-
4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, ter
Examples thereof include t-butyl perbenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide and tert-butyl cumyl peroxide.

Among these, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane and 2,5-dimethyl-2,5-from the viewpoint of odor and scorch stability.
Di- (tert-butylperoxy) hexyne-3,1,
3-bis (tert-butylperoxyisopropyl)
Benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, di-ter-butylperoxide and the like are preferable. .

When the above organic peroxide is used for crosslinking, sulfur, p-quinonedioxime, p, p'-dibenzoylquinonedioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene. , Diphenylguanidine,
Trimethylolpropane-N, N'-m-phenylenedimaleimide and other peroxy crosslinking aids, divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate , Polyfunctional methacrylate monomers such as allyl methacrylate, vinyl
A polyfunctional vinyl monomer such as rubutyrate or vinyl stearate can be used in combination.

The amount of the vulcanizing agent used in the present invention is usually a hydrogenated copolymer or a hydrogenated copolymer composition comprising a hydrogenated copolymer and a thermoplastic resin and / or a rubber-like polymer. It is used in a proportion of 0.01 to 15 parts by weight, preferably 0.04 to 10 parts by weight, relative to 100 parts by weight. The composition of the present invention contains, if necessary, a softener, a heat stabilizer, an antistatic agent, a weather stabilizer, an antiaging agent, a filler, a colorant, a lubricant, etc. within a range that does not impair the object of the present invention. Additives can be added. As a softening agent that can be blended as needed to adjust the hardness and fluidity of the product, specifically, a paraffin-based, naphthene-based, aroma-based process oil, a mineral oil-based softening agent such as liquid paraffin, etc. Various types such as castor oil, linseed oil, etc. are used. These softening agents may be added at the time of kneading or may be contained in the copolymer in advance at the time of producing the hydrogenated copolymer (so-called oil-extended rubber). The addition amount of the softening agent is usually 0 to 200 parts by weight, preferably 10 to 15 parts by weight based on 100 parts by weight of the hydrogenated copolymer.
0 parts by weight, more preferably 20 to 100 parts by weight is preferred.

Specific examples of the filler include calcium carbonate, talc, clay, calcium silicate, magnesium carbonate, magnesium hydroxide and the like. The amount of these fillers added is 100% by weight of the hydrogenated copolymer. The amount is usually 0 to 200 parts by weight, preferably 10 to 150 parts by weight, more preferably 20 to 100 parts by weight. In the present invention, a dynamically crosslinked hydrogenated copolymer or a dynamically crosslinked hydrogenated copolymer composition obtained by dynamically vulcanizing the hydrogenated copolymer or the hydrogenated copolymer composition in the presence of a vulcanizing agent. Has a gel content (however, insoluble components such as insoluble materials such as inorganic fillers are not included therein) of 5 to 80% by weight, preferably 10 to 70% by weight,
More preferably, it is recommended to vulcanize so as to be 20 to 60% by weight.

Here, the gel content means that 1 g of a dynamically crosslinked hydrogenated copolymer or a dynamically crosslinked hydrogenated copolymer composition (sample) is refluxed for 10 hours with a Soxhlet extractor using boiling xylene and left. The product is filtered through a wire mesh of 80 mesh, and it is expressed as a ratio (% by weight) of the dry weight (g) of the insoluble matter remaining on the mesh to 1 g of the sample.

[0053]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below with reference to Examples. In the following examples, the properties and physical properties of polymers were measured as follows. 1. Characteristics of copolymer 1) Styrene content It was measured using an ultraviolet spectrophotometer (manufactured by Shimadzu Corporation, UV-2450). 2) Polystyrene block content Using a polymer before hydrogenation, I. M. Kolthoff, et al. J.
Polym. Sci. It was measured by the method described in 1,429 (1946). 3) Vinyl bond amount and hydrogenation rate Nuclear magnetic resonance apparatus (BRUXER, DPX-400)
Was measured using.

4) Molecular weight and molecular weight distribution GPC [apparatus manufactured by Waters] was used. Tetrahydrofuran was used as a solvent, and the measurement conditions were a temperature of 35 ° C. The molecular weight is a weight average molecular weight obtained by using a calibration curve (prepared by using the peak molecular weight of standard polystyrene) obtained by measuring the standard polystyrene of the chromatogram. The molecular weight when there are a plurality of peaks in the chromatogram means the average molecular weight obtained from the molecular weight of each peak and the composition ratio of each peak (obtained from the area ratio of each peak in the chromatogram). The molecular weight distribution is the ratio of the obtained weight average molecular weight and number average molecular weight.

5) Crystallization peak and crystallization peak calorific value: Measured by DSC [manufactured by Mac Science Co., Ltd., DSC3200S]. The temperature was raised from room temperature to 150 ° C. at a temperature rising rate of 30 ° C./min, then the temperature was lowered to −100 ° C. at a temperature lowering rate of 10 ° C./min, and the crystallization curve was measured to confirm the presence or absence of a crystallization peak. When there is a crystallization peak, the temperature at which the peak appears is taken as the crystallization peak temperature, and the crystallization peak calorie is measured.

2. Preparation of hydrogenated copolymer A hydrogenated copolymer was prepared by the following method. The hydrogenation catalyst used in the hydrogenation reaction in the following examples was prepared by the following method. A reaction vessel purged with nitrogen was charged with 1 liter of dried and purified cyclohexane, 100 mmol of bis (η ⁵ -cyclopentadienyl) titanium dichloride was added, and an n-hexane solution containing 200 mmol of trimethylaluminum was sufficiently stirred. Add
The reaction was carried out at room temperature for about 3 days.

Continuous polymerization was carried out using two tank-type reactors each having an internal volume of 10 L and an L / D4 stirrer. From the bottom of the first reactor, the butadiene concentration is 2
A 4 wt% cyclohexane solution was supplied at a feed rate of 4.51 L / hr, a cyclohexane solution having a styrene concentration of 24 wt% at a feed rate of 5.97 L / hr, and n-butyllithium was added to 100 g of the monomer. 2.0 L of cyclohexane solution adjusted to a concentration of 0.077 g
/ Hr, and a cyclohexane solution of N, N, N ', N'-tetramethylethylenediamine is further fed at a feed rate of 0.44 mol per mol of n-butyllithium, It was continuously polymerized at ℃.

The reaction temperature was adjusted by the jacket temperature. The temperature near the bottom of the reactor was about 88 ° C, and the temperature near the top of the reactor was about 90 ° C. The average residence time in the polymerization reactor was about 45 minutes, and the conversion of butadiene was about 10
The conversion rate was 0% and the styrene conversion rate was 99%. The polymer solution discharged from the first unit was supplied from the bottom of the second unit, and at the same time, a cyclohexane solution having a styrene concentration of 24% by weight was supplied to the bottom of the second unit at a supply rate of 2.38 L / hr.
Continuous polymerization was carried out at 90 ° C. The conversion rate of styrene at the outlet of the second unit was 98%.

Analysis of the polymer obtained by continuous polymerization revealed that the styrene content was 67% by weight, the block styrene content was 20% by weight, and the vinyl bond content in the butadiene part was 1%.
It was 4% by weight. From the analysis values of the styrene content and the block styrene content, the block ratio of styrene was 30%. Next, 100 pp of the above hydrogenation catalyst was added to the polymer obtained by continuous polymerization as Ti per 100 parts by weight of the polymer.
The hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C.

The resulting hydrogenated copolymer (Polymer 1) is
Molecular weight 220 million, molecular weight distribution 1.9, styrene content 67% by weight, block styrene amount 20% by weight, vinyl bond content of butadiene part 14% by weight, hydrogenation rate 8
It was 0%. From the analysis values of the styrene content and the block styrene content, the block ratio of styrene was 30%.
Further, in the measurement of the crystallization temperature and the crystallization peak calorie by the DSC method, Polymer 1 did not show a crystallization peak in the temperature range of -50 to 100 ° C, and the crystallization peak calorie was zero.

3. Components Used for Preparation of Dynamically Crosslinked Hydrogenated Copolymer Composition Each component other than the hydrogenated copolymer is shown below.・ Polypropylene resin: Sun Allomer PC600S
(Manufactured by Monterey E-Sunrise Co., Ltd.) Paraffin oil: Diana Process Oil P
W-380 (manufactured by Idemitsu Kosan Co., Ltd.)-Calcium carbonate: calcium carbonate surface-treated with higher fatty acid ester-Organic peroxide: Perhexa 2,5B (manufactured by NOF Corporation) -Vulcanization accelerator: divinylbenzene-antioxidant : Irganox 1010 (manufactured by Ciba Specialty Chemicals)

4. Physical Properties of Dynamically Crosslinked Hydrogenated Copolymer and Dynamically Crosslinked Hydrogenated Copolymer Composition 1) Hardness According to JIS K6253, 1 by durometer type A
The value after 0 seconds was measured. 2) Tensile strength, elongation at break According to JIS K6251, measurement was performed with a No. 3 dumbbell and a crosshead speed of 500 mm / min.

3) Scratch resistance Gakushin type friction tester (AB-3, manufactured by Tester Sangyo Co., Ltd.)
01 type), the surface of the molded sheet (glossy mirror surface) was rubbed 100 times with a friction cloth Kanakin No. 3 cotton and a load of 500 g, and the change in glossiness before and after rubbing was measured with a gloss meter. It was judged. ◎: Change in glossiness is within 0 to -5 ○: 〃 -5 over -10 within △: 〃 -10 over -50 within ×; 〃 -50 over

4) Abrasion resistance dynamic vibration type friction tester (AB-3, manufactured by Tester Sangyo Co., Ltd.)
01 type), the surface of the molded sheet (textured surface),
Friction cloth Kanakin No. 3 cotton was rubbed with a load of 500 g, and the volume reduction amount after rubbing was used to make a judgment according to the following criteria. ◎: Volume reduction amount is 0.01 ml or less after 10,000 times of friction ○: 〃 0.01 or more and 0.05 ml or less △; 〃 0.05 or more and 0.10 ml or less ×; 〃 0.1 ml or more What I did

5) Oil resistance No. 1 specified in JIS K6301. 3 test oils (lubricating oil) are used, 70 ° C for 2 hours, 50 mm x 50 mm x 2 mm
The test piece having the thickness was dipped and the weight change (%) before and after the dipping was determined.

[0066]

[Example] Polymer 1 was used as a raw material rubber, each component was mixed with a Henschel mixer according to the compounding recipe shown in Table 1, and it was mixed with a 30 mm diameter twin-screw extruder at 190 to 230 ° C.
The compound before melt-kneading and dynamic crosslinking is obtained under the conditions of (1st step). A vulcanizing agent is added to this compound, and the mixture is melt-kneaded in a twin-screw extruder having a diameter of 30 mm under the conditions of 190 to 230 ° C. to obtain a dynamically crosslinked hydrogenated copolymer composition (second step). Eye). The obtained composition is injection-molded and various physical properties are measured. The obtained composition is a composition having excellent abrasion resistance, scratch resistance, and oil resistance.

[0067]

[Table 1]

[0068]

The kinematic crosslinked hydrogenated copolymer or the kinematic crosslinked hydrogenated copolymer composition of the present invention is excellent in abrasion resistance, scratch resistance and oil resistance. The dynamically crosslinked hydrogenated copolymer or the dynamically crosslinked hydrogenated copolymer composition of the present invention can be molded by a commonly used molding machine for thermoplastic resin, a sheet, a film,
It can be used as various molded products such as injection molded products, hollow molded products, compressed air molded products, vacuum molded products and extrusion molded products of various shapes. These molded products can be used as food packaging materials, medical device materials, home electric appliances and parts thereof, materials for automobile parts / industrial goods / daily miscellaneous goods / toys, footwear materials and the like.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4F070 AA08 AA15 AB09 AC56 AC76                       AE08 GA05 GA06 GB08                 4J002 AC01X AC03X AC06X AC07X                       AC09X BB03X BB10X BB12X                       BB15X BB16X BB18X BB24X                       BC01W BC03X BC05W BC05X                       BC06X BC07X BC09W BC10W                       BD12X BG04X BG05X BN15X                       BP01W BP01X BP02X CK02X                       CP03X GB00 GC00 GN00                       GQ00

Claims (4)

[Claims] 1. A copolymer comprising a conjugated diene and a vinyl aromatic compound is a hydrogenated product (1) satisfying the following (a) to (f), and the content of the (a) vinyl aromatic compound is 50: More than 90% by weight, (b) the amount of the vinyl aromatic compound polymer block in the copolymer is 40% by weight or less, (c) the weight average molecular weight is 50,000 to 1,000,000, and (d) both 10% or more of the double bond based on the conjugated diene compound in the polymer is hydrogenated, (f) -5 in the differential scanning calorimetry (DSC method)
From 100 to 100 parts by weight of a hydrogenated copolymer (1), a thermoplastic resin and / or a rubbery polymer (2), which has substantially no crystallization peak in a temperature range of 0 to 100 ° C., from 0 to 0 parts by weight. A kinematic crosslinked hydrogenated copolymer or a kinematic crosslinked hydrogenated copolymer composition obtained by dynamically crosslinking the hydrogenated copolymer or the hydrogenated copolymer composition thus constituted in the presence of a vulcanizing agent. 2. The dynamically crosslinked hydrogenated copolymer or the dynamically crosslinked polymer according to claim 1, wherein the amount of the vinyl aromatic compound polymer block in the hydrogenated copolymer as the component (1) is less than 10% by weight. Hydrogenated copolymer composition. 3. The kinematic crosslinked hydrogenated copolymer or the kinematic crosslinked hydrogenated copolymer according to claim 1, wherein the amount of the vinyl aromatic compound polymer block in the hydrogenated copolymer of the component (1) is 10 to 40% by weight. Crosslinked hydrogenated copolymer composition. 4. The catalyst according to claim 1, wherein the hydrogenated copolymer as the component (1) is a hydrogenated product of a copolymer having at least one structure selected from the following general formulas. Crosslinked hydrogenated copolymer or dynamically crosslinked hydrogenated copolymer composition. 1 B 2 B-A 3 B-A-B 4 (B-A) _m- X 5 (B-A) _n- X-A _p (where B is a random copolymer of a conjugated diene and a vinyl aromatic compound). A polymer block, A is a vinyl aromatic compound polymer block, m is an integer of 2 or more, and n
And p are integers of 1 or more. X represents a coupling agent residue. )