JPH0260948A - Composite composition - Google Patents

Abstract

PURPOSE:To make it possible to improve the mechanical strengths, abrasion resistance, weathering resistance, impact resistance and kneadability by mixing a specified hydrogenated polymer with a flexible elastomer. CONSTITUTION:A functional group-modified hydrogenated diene polymer (A) is obtained by effecting an addition reaction of 100 pts.wt. hydrogenated diene polymer formed by hydrogenating a diene (co)polymer of a vinylaromatic compound content <=50wt.%, a number-average MW of 5000-1000000, an MW distribution Mw/Mn<10 and a vinyl bond content of the diene part >=10% so that at least 70% of the olefinically unsaturated bonds may be hydrogenated with 0.01-30 pts. wt. unsaturated compound having at least one kind of a functional group selected from among carboxyl, amino, hydroxyl and epoxy groups. 5-95wt.% component A is mixed with 95-5wt.% at least one flexible elastomer (B) selected from among a 1,2-butadiene polymer, a vinylaromatic compound/ conjugated diolefin block copolymer, a natural rubber, a (non)dienic synthetic rubber and an ethylene/vinyl acetate copolymer, each having a vinyl bond content >=70%, a crystallinity >=5% and an intrinsic viscosity (in toluene at 30 deg.C) >=0.5dl/g.

Description

DETAILED DESCRIPTION OF THE INVENTION a. Industrial Application Field The present invention relates to a composite composition having excellent mechanical strength, abrasion resistance, weather resistance, impact resistance, and kneading processability.

b. Prior Art Natural rubber and general-purpose synthetic rubber (styrene-butadiene rubber, butadiene rubber, nitrile rubber, etc.) have poor weather resistance and have limited uses.

On the other hand, it is known that general-purpose plastics such as polypropylene and polyethylene, which can be extruded and injection molded, have relatively good weather resistance and are widely used in the molding field.
These materials lack rubber elasticity and have problems with impact resistance, which limits their use.

Many thermoplastic elastomers, which are located between rubber and plastic, have been developed in recent years, but they have deficiencies in mechanical strength, abrasion resistance, weather resistance, impact resistance, and kneading processability. has not yet been reached.

Problems to be solved by the C0 invention The inventors of the present invention have focused on the lack of excellent materials that satisfy mechanical strength, abrasion resistance, weather resistance, impact resistance, and kneading processability. Hydrogenated diene polymer and 1,2-
Polybutadiene (hereinafter abbreviated as RB), block copolymer of vinyl aromatic compound and conjugated diolefin (hereinafter referred to as TR)
By using soft elastomers such as natural rubber, diene-based synthetic rubber, non-diene-based synthetic rubber, and ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVA).
We have found that problem 1 can be solved, and have arrived at the present invention based on this knowledge.

Means for solving the d8 problem The gist of the present invention is that modified hydrogenated diene polymers (A) 5 to 9
5% market weight, natural rubber, synthetic rubber, 1,2-polybutadiene, vinyl aromatic-conjugated diene block copolymer,
and 95 to 5% by weight of a soft elastomer such as an ethylene-vinyl acetate copolymer.

The modified hydrogenated diene polymer (A) is at least one conjugated diene polymer or a diene copolymer containing at least one conjugated diene and a vinyl aromatic compound at 50% by weight or less. ) The number average molecular weight of the polymer is 5,000 to 1.000.000, and the vinyl bond content of the diene part is 10% or more. Carboxyl groups or their anhydrides, amino groups, hydroxyl groups, and epoxy groups are added to 100 parts by weight of a hydrogenated diene polymer in which at least 70% of the olefinic unsaturated bonds in the (co)polymer are hydrogenated. A modified hydrogenated diene polymer prepared by reacting 0.05 to 20 parts by weight of an unsaturated compound containing at least one functional group selected from the group is preferred.

The modified hydrogenated diene polymer (A) is at least one conjugated diene polymer or a random or block copolymer of at least one conjugated diene and a vinyl aromatic compound, preferably a random diene copolymer. The hydrogenated diene polymer obtained by partially or completely hydrogenating the diene portion contains at least one functional group selected from the group consisting of a carboxyl group or its anhydride, an amino group, a hydroxyl group, and an epoxy group. It is a copolymer made by reacting unsaturated compounds.

Here, examples of the conjugated diene compound include butadiene,
Examples include isoprene, pentadiene, and 2,3-dimethylbutadiene. Examples of aromatic vinyl compounds include styrene, paramethylstyrene, and α-methylstyrene.

Furthermore, among the unsaturated compounds having a functional group, examples of unsaturated compounds having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, and fumaric acid. You can also use Examples of the unsaturated compound having an amino group include tertiary amino group-containing monomers such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and dibutylaminoethyl (meth)acrylate.

Furthermore, examples of unsaturated compounds having a hydroxyl group include 1-hydroxypropyl (meth)acrylate, 2-
Examples include hydroxypropyl (meth)acrylate and hydroxyethyl (meth)acrylate. Furthermore, examples of the unsaturated compound having an epoxy group include glycidyl (meth)acrylate, allyl glycidyl ether, vinyl glycidyl ether, and the like.

These unsaturated compounds having functional groups can be used alone or in combination of two or more. In addition, other unsaturated compounds that can be copolymerized include:
Mention may be made of polyfunctional unsaturated compounds. Specific examples of these include compounds having two or more functional groups, preferably two copolymerizable double bonds, and specifically non-conjugated divinyl compounds such as divinylbenzene, divinylxylene, and divinyl ether; Polyvalent (meth) such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate
Examples include acrylate compounds, unsaturated carboxylic acid esters such as vinyl (meth)acrylate, isopropenyl (meth)acrylate, and divinyl phthalate.

The content m of these other copolymerizable unsaturated compounds in the rubbery copolymer is 0 to 10% by weight, preferably 0.
．． The amount is 1 to 5% by weight, and is added as necessary. On the other hand, if it exceeds 10% by weight, the degree of crosslinking of the rubbery copolymer becomes too large, resulting in a decrease in the mechanical strength of the resulting composition.

In the microstructure of the modified hydrogenated diene polymer (A) before modification and hydrogenation, the amount of vinyl bonds a such as 1.2-3.4- is 10% or more, preferably 20-80%. %, particularly preferably 20 to 50%. If it is less than 10%, the hydrogenated diene polymer will take on resinous properties, the impact resistance of the resin composition will deteriorate, and the object of the present invention will not be met.

Further, the content of the aromatic vinyl compound in the diene polymer before modification and hydrogenation of the modified hydrogenated diene copolymer (A) is 50% by weight or less, preferably 35 to 5% by weight. When the amount exceeds 50% by weight, the hydrogenated diene polymer takes on resinous properties, the impact resistance of the resin composition deteriorates, and the object of the present invention is not achieved. The diene polymer is preferably a 1 random copolymer in which aromatic vinyl compounds are randomly bonded, and Corsof I: 1. M.Kolt
hoff, J.

Po1y+++er Sci,, Vol, l, P4
The U content of the block-shaped polyvinyl aromatic compound obtained by the method of 29 (194B):l is preferably 10% by weight or less, more preferably 5% by weight or less based on the total bonded vinyl aromatic compound.

The diene polymer may be either a linear polymer or a branched polymer, but branched polymers are preferred for improving processability and cold flow.

The molecular weight of the modified hydrogenated diene polymer (A) before modification and hydrogenation is 5,000 to 1.000.0 in terms of number average molecular weight.
00, preferably 30.000 to 300.000. If it is less than 5,000, the hydrogenated diene polymer will not become rubber-like but will become liquid, and if it exceeds 1,000,000, processability tends to decrease.

Further, the molecular weight distribution (M w / M n ) is preferably 10 or less, more preferably 5 or less, particularly preferably 1.1 to 3. The hydrogenation rate of olefinic unsaturated bonds in the modified hydrogenated diene polymer (A) before modification is 70% or more, preferably 90% or more.

If the hydrogenation rate is less than 70%, the effect of improving the weather resistance and heat resistance of the polymer will be insufficient, and the purpose of the present invention will not be achieved.

The monomer (unsaturated compound) having the functional group in the modified hydrogenated diene polymer (A) is preferably 0.01 to 30% by weight based on 100% by weight of the hydrogenated diene polymer. is 0.1 to 5% by weight26, and if it is less than 0.01% by weight, the resulting composite composition will have poor weather resistance and impact resistance, while if it exceeds 30% by weight, the modified hydrogenated diene polymer (A )
When mixed with the soft elastomer (B), the dispersion state deteriorates, resulting in poor mechanical strength and abrasion resistance.

The modified hydrogenated diene polymer (A) before modification and hydrogenation can be obtained, for example, by anionic living polymerization in a hydrocarbon solvent using an organolithium initiator. Further, the branched polymer can be obtained by adding a required amount of a trifunctional or more functional coupling agent at the end of the polymerization to perform a coupling reaction.

1. To control the amount of vinyl bonds such as 2-13,4-bonds, ether, tertiary amine compounds, sodium,
Alkoxides, phenoxides, and sulfonates of alkali metals such as potassium are used.

#As the lithium initiator, n-butyllithium, 5
ec-butyllithium, tert-butyllithium, etc. are used. Hydrocarbon solvents include hexane, heptane, methiphonoclopentane, cyclohexane, benzene, toluene, quinrene, 2-methylbutene-1,2-
Methylbutene 2 and the like are used.

The polymerization may be carried out in a batch manner or in a continuous manner, and the polymerization temperature is usually in the range of 0 to 120°C and the polymerization time is in the range of 10 minutes to 3 hours. The coupling agent is a trifunctional or more functional coupling agent, and examples thereof include tetrachlorosilicon, butyltrichlorosilicon, tetrachlorotin, butyltrichlorotin, tetrachlorogermanium, bis(
Trichlorosilyl)ethane, divinylbenzene, adipic acid diester, epoxidized liquid polybutadiene, epoxidized soybean oil, epoxidized linseed oil, tolylene diisocyanate, diphenylmethane diisocyanate, 1,2
．． Examples include 4-benzenetriisocyana=1.

By hydrogenating the diene polymer thus polymerized, the hydrogenated diene polymer (A) of the present invention can be obtained.

The hydrogenation reaction of the hydrogenated diene polymer before modification of the present invention is as follows:
Dissolving the conjugated diene polymer in a hydrocarbon solvent,
1kg/cJ to 100kg/at 20 to 150°C
The reaction is carried out under pressurized hydrogen of ca in the presence of a hydrogenation catalyst.

Hydrogenation catalysts include catalysts in which noble metals such as palladium, ruthenium, rhodium, and platinum are supported on silica, carbon, and diatom, complex catalysts such as rhodium, ruthenium, and platinum, and organic carbonic acids and organic aluminum such as cobalt and nickel. or a catalyst consisting of organolithium,
Titanium compounds such as dicyclopentadienyl titanium dichloride, dicyclopentadienyl diphenyl titanium, dicyclopentajenyl titanium ditolyl, dicyclopentadienyl titanium dibenzyl, lithium, aluminum,
A hydrogenation catalyst consisting of a metal compound consisting of magnesium is used.

A radical generator such as an organic peroxide is usually used in the reaction of modifying the hydrogenated diene polymer with a functional group-containing unsaturated compound.

The organic peroxide used as the functional group addition aid is 2,5-dimethyl-2°5-di(t-
butylperoxy)hexane-3,2,5-dimethyl-
2,5-di(t-butylperoxy)hexane, 2.2
'-bis(t-butylperoxy)p-diisopropylbenzene, dicumyl peroxide, di(-butylperoxide, t-butylperoxybenzoate, 1,
Examples include 1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 2,4-dichlorobenzoyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, but more preferably dialkyl Peroxides are selectively used.

6 The amount of peroxide added is 1 part hydrogenated diene polymer.
0.01 to 1.5 parts by weight, preferably 0.1 to 1.0 parts by weight.

If the amount of peroxide added is less than 0.01 part by weight, the grafting yield of the functional group will be low, and if it exceeds 1.5 parts by weight, the crosslinking density of the hydrogenated diene polymer will increase, resulting in a soft elastomer (B). The dispersion state deteriorates when blended with the material, resulting in poor mechanical strength and abrasion resistance.

The grafting reaction of functional groups to hydrogenated diene polymers is as follows:
Using pre-heated roll mills, Banbury mixers, closed kneaders such as pressure kneaders, and extruders,
This can be carried out by melt-mixing a hydrogenated diene polymer and an unsaturated compound having a functional group, and simultaneously adding U-type peroxide to cause a graft reaction of the functional group to the hydrogenated diene polymer.

It can also be carried out by copolymerizing a monomer having a functional group in a conjugated diene unit in the rubber, and then hydrogenating the copolymer.

The amount of component (A) used is 5 to 95% by weight, preferably 5%.
~80% by weight, more preferably 5~60% by weight, particularly preferably 10~50% by weight.

If it is less than 5% by weight, the weather resistance will be impaired, and if it exceeds 95% by weight, the abrasion resistance will be poor.

The 1,2-butadiene polymer which is component (B) of the present invention has a vinyl bond-a content of 70% or more, preferably 85% or more, and a crystallinity of 5% or more, preferably 10 to 40%.
．． 2-PBD. It should be noted that when the amount of vinyl alloy 'lTT is less than 70%, mechanical strength and wear resistance are significantly reduced. Moreover, if the degree of crystallinity is less than 5%, the mechanical strength and abrasion resistance that are the objectives of the present invention cannot be obtained. Although the molecular weight can be selected over a wide range, in order to obtain a composite composition with excellent mechanical strength and wear resistance, which is the objective of the present invention, the above [η] (measured at 30°C in toluene) is required.
is 0.5CM! /g or more. [η
] is more preferably 1.0 to 3°0 cif! /g.

The vinyl aromatic-conjugated diene block copolymer which is component (B) of the present invention is, for example, a block copolymer represented by the following formula (%).

” - component (A') has an aromatic vinyl compound content of 7 to obtain appropriate hardness and cushioning properties.
% or more and 90% or less, more preferably 10%
-70% or less, and the molecular weight is 10.000 or more 1
,000,000 or less, more preferably from 70,000 to 300,000, it is possible to obtain much better mechanical strength and wear resistance, which are the objectives of the present invention.

Examples of the aromatic vinyl compound include styrene, α-methylstyrene, ortho-, meta-, and rose-substituted methylstyrene, ethylstyrene, methoxystyrene, dimethylaminostyrene, isopropylstyrene, and pt-butylstyrene. Among these, styrene,
Paramethylstyrene and α-methylstyrene are preferred.

Examples of the polymer include a polymer of only one type of these monomers, or a block or random copolymer of two or more of these monomers in combination.

The content of aromatic vinyl compounds varies depending on the use and molecular weight, and is not particularly limited, but it should not exceed 7%.
% or less is preferable. More preferably 10% or more and 50%
It is as follows.

Conjugated diene (co)polymers or hydrogenated polymers of conjugated diene (co)polymers include butadiene, isoprene,
A single polymer of piperylene, a block or random copolymer of two or more types of piperylene, a copolymer in which partially aromatic vinyl compounds are arranged in a random or tapered block pattern, and a hydrogenated polymer of these conjugated diene polymers. I can list many things.

Examples of the natural rubber, diene-based synthetic rubber, and non-diene-based synthetic rubber that are component (B) of the present invention include natural rubber (NR
), polyisoprene rubber (IR), styrene-butadiene rubber (SBR), polybutadiene rubber (BR),
Diene-based synthetic rubbers such as acrylonitrile butadiene rubber (NBR) and chloroprene rubber (CR), ethylene-propylene rubber (EPR), ethylene-propylene-nonconjugated diene rubber (EPDM), and acrylic rubber (A
Examples include non-diene synthetic rubbers such as CMSANM) and fluororubber. Among these, NR and IR are preferable.
, 5BRSBRSEPR.

The ethylene-vinyl acetate copolymer (EVA) which is the component (B) of the present invention is a copolymer of ethylene and vinyl acetate obtained by a known production method, and preferably MI
(190℃, 2160grSg/l 0m1n) 0
．． It is a copolymer of 5 to 30. Component (B) is preferably RBSTR, NR, or EPR.

It is EVA.

The amount of component (B) used is 95 to 5% by weight, preferably 95% by weight.
~20% by weight, more preferably 95-40% by weight, particularly preferably 90-50% by weight. If it is less than 5% by weight, mechanical strength and abrasion resistance will be impaired, and if it exceeds 95% by weight, weather resistance will be poor.

A composition consisting of the above (A) and (B) is claimed in claim (1).
A more practical composition can be obtained by blending the following (C), (D), (E), and (F) into the composition.

Examples of the softening agent (C) used in the present invention include the following.

Aromatic, naphthenic, and paraffinic process oils, petroleum asphalts such as straight asphalt and blown asphalt, lubricating oils, petroleum softeners such as paraffin, liquid paraffin, and petrolatum; coal tar-based products such as coal tar and coal tar pitch. Softeners include fatty oil-based softeners such as castor oil, linseed oil, rapeseed oil, and coconut oil; waxes such as beeswax, carnauba wax, and lanolin; tall oil, and subs.

These can be used alone or in combination of two or more. A preferred softening agent is a process oil.

The blending amount of the softener of component (C) is as follows: component [(A) + (B)
The amount is 1 to 100 parts by weight, preferably 3 to 80 parts by weight, and more preferably 5 to 50 parts by weight per 100 parts by weight. If it is less than 1 part by weight, the kneading processability will be poor, and if it exceeds 100 parts by weight, the abrasion resistance, mechanical strength, and weather resistance will be poor.

Inorganic fillers as component (D) used in the present invention include, for example, light calcium carbonate, heavy calcium carbonate, various surface-treated calcium carbonates, as well as talc, magnesium hydroxide, mica, barium clay sulfate, and natural silicic acid. , synthetic silicic acid (white carbon), titanium oxide, various carbon blacks, etc. can be used. Among these inorganic fillers, heavy calcium carbonate is preferable because it is economically advantageous.

The blending amount of the inorganic filler is component [(A) + (B)] 10
1 to 500 parts by weight, preferably 5 to 500 parts by weight based on parts of 0Ii'
The amount is 200 parts by weight, more preferably 10 to 100 parts by weight. If it is less than 1 part by weight, kneading properties will be poor, and if it exceeds 500 parts by weight, impact resistance, abrasion resistance, and mechanical strength will be poor.

Examples of the crosslinking agent (E) used in the present invention include sulfur and various organic peroxides.

Specific examples of organic peroxides include dicumyl peroxide, 1,1-bis(t-butylperoxy)-3,3,
5-trimethylcyclohexane, t-butylperoxybenzoate, 2,5-dimethyl-2,5-bis(t-
butylperoxy)hexane, t-butylperoxyisopropyl carbonate, and the like.

In the case of sulfur vulcanization, various vulcanization accelerators are added at the same time to effect crosslinking. Specific examples of vulcanization accelerators include dibenzothiazyl disulfide (MBTS), 2-methylcaptobenzothiazole (MBT), and N-cyclohexyl-2-
Benzothiazyl sulfenamide (CBS), N-
Oxydiethylene 2-benzothiazylsulfenamide (DBS), tetramethylthiuram disphite (T
M TD), tetramethylthiuram monosulfide (T
MTM) etc.

The blending amount of the crosslinking agent is the component [((A)+(B)]110
1-50 for 0 weight! Parts of Tf, preferably 2 to 3
The amount is preferably 0 parts by weight, more preferably 2 to 20 parts by weight. 1
If it is less than 50 parts by weight, mechanical strength and abrasion resistance will be poor, and if it exceeds 50 parts by weight, kneading processability will be poor.

As the blowing agent (E) used in the present invention, known inorganic or monoorganic blowing agents can be used.

It is also possible to use them together. Specific examples of blowing agents include sodium bicarbonate, ammonium bicarbonate, sodium carbonate, ammonium carbonate, azodicarbonamide (
ADCA), dinitrosopentamethylenetetramine (
DNPT), dinitrosoterephthalamide, azobisisobutyronitrile, barium azodicarboxylate, sulfonyl hydrazide, toluenesulfonyl hydrazide, and the like. These foaming agents may be used in combination with known foaming aids such as urea and urea derivatives.

The amount of blowing agent used is Component [(A) + (B)] 11
1 to 50 parts by weight, preferably 5 parts by weight based on 00 weight.
~40 parts by weight. If the blowing agent is less than 1 part by weight, only a foam with a low expansion ratio will be obtained, and if it exceeds 50 parts by weight, a large amount of gas will be generated due to the decomposition of the blowing agent, making it impossible to obtain a foam with a good appearance. .

Further, in addition to the above-mentioned additives, crosslinking aids, antioxidants, processing aids, plasticizers, adhesives, and the like may be appropriately added as needed.

The following (1) and (8) have been shown as how to use this patent, but for example, the following (2), (3), (4),
It can also be used in methods (5), (6), and (7).

(11 (A) + (B) method (2) (A) + (B) + (C) (3) (
A) +(B) + (D)(4+ (A) +(B
) +(E)(5] (A)+ (B)+ (C)+
(D) (6) (A) + (B) + (C)
10(E)(7) (A)+ (B)+ (D)+ (
E) (81(A) +(B) + (C) +(D)
+(E) There are no particular restrictions on the method of mixing other compounding agents in (1) to (8) above, and it can be used for general rubber compounds such as Banbury-type mixers, pressure kneaders, and open rolls. This is possible with the mixing method that is used.

The uncrosslinked mixture thus obtained is formed, for example, into a sheet shape, if necessary, and then subjected to crosslinking and foaming in a heating medium.

In the non-crosslinking field, the rubber composition of the present invention can be applied to all thermoplastic resin molding methods such as extrusion molding, film molding, blow molding, vacuum molding, and injection molding, and can be used as films, film modifiers, and sheets. and sheet modifier,
There are profile extrusions, molded products, and foams of these products.
In the field of daily necessities, industrial products, automobile parts, footwear, cushioning materials, packaging materials, etc., and in the crosslinking field, all crosslinked material molding methods such as extrusion molding, injection molding, press molding, hot air molding, etc. are possible, and solid Molded products and foam molded products can be obtained, and can be used in a wide variety of rubber products. For example, it is suitably used for daily necessities, audio parts, electrical products, industrial goods, automobile parts, footwear materials, cushioning materials, packaging materials, and the like.

e. Examples Next, the present invention will be specifically explained with reference to Examples and Comparative Examples, but the present invention is not limited as long as it does not go beyond the gist of the present invention.

In Examples and Comparative Examples, tensile strength at break (Tb) and tensile elongation at break (Eb) are based on JIS K6301, and Williams wear amount is based on Br1tish st'd 903.
For weather resistance, tensile elongation at break (Eb) of 60% or more after 20 hours in the sunshine weather test (black panel 63°C rain cycle is 18 minutes/120 minutes) is judged as (○), and less than 60% is judged as (×). ). Impact resistance (isot impact) was determined in accordance with ASTM D-256 notched, and 50 kg*cm/cm or more was evaluated as (○), and less than 50 kg-cm/cm was evaluated as (x).

The kneading processability was determined by cohesiveness, winding property, or extrusion cross-dispersibility in a 32-pressure kneader and a 10-inch open roll. If the cohesiveness is within 5 minutes, the wrapping property is good, or the extrusion cross-wire dispersion is good (○) judgment,
If the cohesiveness exceeded 5 minutes, the wrapping property was poor, or the extrusion cross-dispersion property was poor, it was judged as (×).

The method of mixing the resin composition of the present invention is not particularly limited, but
For example, modified hydrogenated diene copolymers (A) and (B), (C
), (D), (E), and (F) are mixed using a mixer such as a roll, Banbury mixer, or intermixer, or the modified hydrogenated diene copolymer (A) is mixed in advance into pellets or crumbs. Or make it into powder, (B), (C
), (D), (E), and (F) are tri-blended using a mixer such as a Henschel mixer tumbler, and then melt-mixed using a mixer such as an extruder.
In any case, it is sufficient to select an apparatus under conditions such that each component is sufficiently dispersed and mixed.

Sample 1: (After charging 2500 g of degassed and dehydrated cyclohexane, 150 g of styrene, and 350 g of 1°3-butadiene into a 115fi autoclave, 2.0 g of tetrahydrofuran was added.
5 g and 0.34 g of n-butyllithium were added, and temperature-rising polymerization was carried out at a polymerization temperature of 30 to 80°C. After almost 100% conversion, 5iCE40.14. g was added. Thereafter, 2,6-tert-butylcatechol was added, the solvent was removed by a steam stripping method, and the mixture was dried with a hot roll at 120° C. to obtain a polymer. The styrene-butadiene copolymer thus obtained had a vinyl bond content of 30%, a styrene content of 30% by weight, and a branched polymer having three or more branches of 56% by weight. The number average molecular weight by GPC analysis was 200.0.00, and Mw/Mn was 1.5.

(2) The conjugated diene copolymer polymerized in (1) is
The mixture was placed in a ℃ autoclave to form a 15% cyclohexane solution. After purging the system with nitrogen, a solvent solution of nickel 20-butyl lithium naphthenate:tetrahydrofuran-1:8:20 (mole ratio) prepared in advance in a separate container was added to 2000 moles of the olefin portion as nickel.
I prepared it to be mole. Thereafter, hydrogen was introduced into the reaction system, and a hydrogenation reaction was carried out at 70°C. After controlling the hydrogenation rate based on the amount of hydrogen absorbed and consumed, the hydrogen in the system was replaced with nitrogen, and the anti-aging agent 2,6-di-tert-butyl para-cresol was added by IPIIR. After repeating decolorization and coagulation, roll drying was performed by a conventional method to obtain a hydrogenated diene copolymer with a hydrogenation rate of 95%.

Sample 2: Same as sample 1 (1) except that no coupling reaction was performed, vinyl bond amount was 30% by weight, styrene content was 3.
A 0% by weight styrene-butadiene copolymer was obtained. This was carried out in the same manner as in (2) of Sample 1 to obtain a hydrogenated diene copolymer with a hydrogenation rate of 98%.

Samples 3 to 4: Hydrogenated diene copolymers shown in Table 1 were obtained in the same manner.

Margin below The analytical values in the above table were determined as follows.

- The bound styrene content was determined from a calibration curve using an infrared method based on the absorbing pair of the phenyl group at 679 cm.

・The amount of vinyl bonded gold was determined by an infrared method (Morello method).

・Molecular weight, molecular weight distribution, and coupling efficiency (C/E) are determined by gel permeation chromatography (GPC).
I asked for it from

- The hydrogenation rate was calculated from the spectral decrease of the unsaturated bond in the +H-NMR spectrum of 100 Mllz measured at a concentration of 15% using ethylene tetrachloride as a solvent.

Example 1.2.4.9 Component (A) in Example 1.2 used sample 3 in Table 1 above, and component (A) in Example 4.9 used sample 4 in Table 1 above. It was manufactured according to the following procedure.

That is, partially hydrogenated diene copolymer 1 in Table 1 above
00 parts to 190℃:A adjusted mixer (IIAAKIE
Manufactured by BLICIILEIN, IIAAKE RIIE
OCORD 5YST Open 40RIIEO Old X MIXE
R600) 1.1 m of injected, 2 minutes later, 7 L of anhydride/2.5 parts of inic acid was added, and after melting and mixing, organic peroxide [2,
By adding 0.15 parts of 5-dimethyl-2,5-di(t-butylperoxy)hexane; Perhexa 25B, manufactured by NOF ■, and continuing kneading for an additional 5 minutes, (A
) ingredients were obtained.

As shown in Table 2, these were kneaded in a 70°C atmosphere in a 3°C pressure kneader, then formed into a sheet with an open roll, and crosslinked at 160°C for 20 minutes, and the obtained product was evaluated. The evaluation results are shown in Table-2.

Example 3.5.6.7.8 Component (A) in Example 3.5.6 used Sample 2 in Table 1 above, and Component (A) in Example 7.8 used Sample 1 in Table 1 above. was used. The other ingredients shown in Table 2 were kneaded using an extruder, the extrudates were cut, and each was molded using the molding method shown in Table 2. The evaluation results are shown in Table 2.

Comparative Example 1.3.6 Component (A) in Comparative Example 1.3.6 was a composition outside the scope of the present patent claims obtained by the same processing method as Example 1 using Sample 4 in Table 1 above. It is. The evaluation results are shown in Table-2.

Comparative Example 2.4.5 Component (A) in Comparative Example 2.4.5 was a composition outside the scope of the present patent claims obtained by the same processing method as Example 3 using Sample 2 of Table 1 above. It is. The evaluation results are shown in Table-2.

Comparative Example 7.8 As component (A), emulsion polymerization 5BR1502 and hydrogenated block copolymer Kraton G1650 (manufactured by Shell Chemical Co., Ltd.)
A composition was obtained in the same manner as in Example 1 except that . The evaluation results are shown in Table-2.

From Table 2, it is clear that the examples falling within the scope of the present patent claim exhibit superior performance satisfying all evaluation items compared to the comparative examples falling outside the scope of the present patent claim.

f8 Effects of the Invention The composition of the present invention is highly balanced in mechanical strength, abrasion resistance, weather resistance, impact resistance, and kneading processability, and can be arbitrarily selected from crosslinked, non-crosslinked, foamed, and non-foamed. It is an excellent composition that can be extruded, film-molded, blow-molded, vacuum-formed, and press-molded, and its uses include rubber products, daily necessities, audio parts, industrial products, transportation parts, automobile parts, It can be used in a wide range of applications such as footwear materials, cushioning materials, and packaging materials, and has extremely high industrial value.

Claims (4)

[Claims] (1) 50% by weight of at least one conjugated diene polymer or at least one conjugated diene and a vinyl aromatic compound
A copolymer with the following, the (co)polymer consisting of 5 to 95% by weight of a hydrogenated diene polymer (A) modified with a functional group and 95 to 5% by weight of a soft elastomer (B). Characteristic composite composition. (2) Soft elastomer (B) has a vinyl bond content of 70
% or more, a crystallinity of 5% or more and an intrinsic viscosity [η] (measured at 30°C in toluene) of 0.5 dl/g or more, a vinyl aromatic compound and a conjugated diolefin. Claim (1) is at least one selected from block copolymers, natural rubber, diene-based synthetic rubbers, non-diene-based synthetic rubbers, and ethylene-vinyl acetate copolymers.
) composite composition. (3) The modified hydrogenated diene polymer (A) has a number average molecular weight of 5,000 to 1,000,000, and the molecular weight distribution M
Hydrogenating a diene (co)polymer with w/Mn<10 and a vinyl bond content in the diene portion of 10% or more to obtain at least 70% of the olefinically unsaturated bonds in the (co)polymer. An unsaturated compound having at least one functional group selected from the group of carboxyl group, acid anhydride group, amino group, hydroxyl group and epoxy group is added to the hydrogenated diene polymer. The composite composition according to claim 1, wherein the amount is 0.01 to 30 parts by weight based on 100 parts by weight of the polymer. (4) The sum of 5 to 95% by weight of the polymer (A) of claim (1) and 95 to 5% by weight of the polymer (B) of claim (1) [
(A) + (B)] 100 parts by weight, softener (C)
A composite composition comprising 1 to 100 parts by weight of an inorganic filler (D), 1 to 500 parts by weight of a crosslinking agent (E), and 1 to 50 parts by weight of a blowing agent (F). .