JP2650348B2 - Composite composition - Google Patents

Description

The present invention relates to a composite composition having excellent mechanical strength, abrasion resistance, weather resistance, impact resistance and kneading processability of a material.

b. Conventional technology Natural rubber, general-purpose synthetic rubber (styrene butadiene rubber,
Butadiene rubber, nitrile rubber, etc.) have poor weather resistance and their applications are limited.

On the other hand, general-purpose plastics such as extrusion-moldable and injection-moldable polypropylene and polyethylene have relatively excellent weather resistance,
It is known that they are widely used in the field of molding and processing, but they lack rubber elasticity and have a problem in impact resistance, and their applications are limited.

In recent years, many thermoplastic elastomers located between rubber and plastic have been developed.However, there is a defect in any of mechanical strength, abrasion resistance, weather resistance, impact resistance, kneading workability, and it is satisfactory. Has not been reached.

c.Problems to be solved by the invention The present inventors have conducted extensive research focusing on the absence of excellent materials satisfying mechanical strength, abrasion resistance, weather resistance, impact resistance, kneading workability, Modified hydrogenated diene polymer and 1,2-
Polybutadiene (hereinafter abbreviated as RB), block copolymer of a vinyl aromatic compound and a conjugated diolefin (hereinafter abbreviated as TR), natural rubber, diene-based synthetic rubber, non-diene-based synthetic rubber, ethylene-vinyl acetate copolymer (Hereinafter abbreviated as EVA)
It has been found that the above problems can be solved by using a soft elastomer such as this, and the present invention has been achieved based on such findings.

d. Means for Solving the Problems The gist of the present invention is to provide a modified hydrogenated diene polymer (A)
95% by weight and 95 to 5% by weight of a soft elastomer such as a natural rubber, a synthetic rubber, 1,2-polybutadiene, a vinyl aromatic-conjugated diene-based block copolymer, and an ethylene-vinyl acetate copolymer. In the composition.

The modified hydrogenated diene polymer (A) is at least one conjugated diene polymer or a diene copolymer of at least one conjugated diene and 50% by weight or less of a vinyl aromatic compound. A) an olefin of the (co) polymer obtained by hydrogenating a diene (co) polymer having a number average molecular weight of 5,000 to 1,000,000 and a vinyl bond content of the diene portion of 10% or more. Hydrogenated diene polymer 10 in which at least 70% of the unsaturated unsaturated bonds are hydrogenated
0 parts by weight, carboxyl group or its anhydride,
Unsaturated compound containing at least one functional group selected from the group consisting of amino group, hydroxyl group and epoxy group
A modified hydrogenated diene polymer obtained by reacting 0.05 to 20 parts by weight 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. A carboxyl group or an anhydride thereof to a hydrogenated diene polymer obtained by partially or completely hydrogenating the diene portion,
It is a copolymer obtained by reacting an unsaturated compound containing at least one functional group selected from the group consisting of an amino group, a hydroxyl group and an epoxy group.

Here, examples of the conjugated diene compound include butadiene, isoprene, pentadiene, and 2,3-dimethylbutadiene. As the aromatic vinyl compound,
For example, styrene, paramethylstyrene, and α-methylstyrene can be mentioned.

Further, among the unsaturated compounds having a functional group, examples of the unsaturated compound having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, and fumaric acid. Among these, dicarboxylic acids are acid anhydrides. Can also be used. Examples of the unsaturated compound having an amino group include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate,
Examples include tertiary amino group-containing monomers such as dibutylaminoethyl (meth) acrylate. Furthermore, examples of the unsaturated compound having a hydroxyl group include 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and hydroxyethyl (meth) acrylate. Furthermore, examples of unsaturated compounds having an epoxy group include glycidyl (meth) acrylate, allyl glycidyl ether, vinyl glycidyl ether and the like.

These unsaturated compounds having a functional group can be used alone or in combination of two or more. Other unsaturated compounds that can be further copolymerized include polyfunctional unsaturated compounds. Specific examples of these include two or more functional groups, preferably 2
Compounds having two copolymerizable double bonds, specifically, non-conjugated divinyl compounds such as divinylbenzene, divinylxylene, divinylether, ethylene glycol methacrylate, diethylene glycol dimethacrylate, trimethylolpropatrimethacrylate, and trimethylolpropane. Multivalent (meth) such as triacrylate
Examples thereof include acrylate compounds, vinyl (meth) acrylate, isopropenyl (meth) acrylate, and unsaturated carboxylic acid esters such as divinyl phthalate.

The content of these other copolymerizable unsaturated compounds in the rubbery copolymer is from 0 to 10% by weight, preferably from 0.1 to 10% by weight.
It is 1 to 5% by weight, and is added as needed. Meanwhile, 1
If the amount exceeds 0% by weight, the degree of crosslinking of the rubbery copolymer becomes too large, and the mechanical strength of the obtained composition decreases.

The microstructure of the modified hydrogenated diene-based polymer (A) before modification and at the time of hydrogenation has a vinyl bond content of 1,2-, 3,4-, etc. of 10% or more, preferably 20 to 80%. %, Particularly preferably 20 to 50%. If it is less than 10%, the hydrogenated diene-based polymer takes on resinous properties, and the impact resistance of the resin composition deteriorates, which does not meet the object of the present invention.

The content of the aromatic vinyl compound in the diene polymer before modification and before hydrogenation of the modified hydrogenated diene copolymer (A) is 50% by weight or less, and preferably 35 to 5% by weight. If the content exceeds 50% by weight, the hydrogenated diene polymer takes on resinous properties, and the impact resistance of the resin composition deteriorates, which does not meet the object of the present invention. Further, the diene-based polymer is preferably a random copolymer in which aromatic vinyl compounds are randomly bonded, and Korsoff [IM Kolthoff, J. Polymer S
ci., Vol. 1, P429 (1946)], the content of the block-shaped polyvinyl aromatic compound is preferably 10% by weight or less, more preferably 5% by weight or less, of the total bound vinyl aromatic compound. is there.

The diene polymer may be either a linear polymer or a branched polymer, but a branched polymer is preferred from the viewpoint of improving processability and cold flow.

The molecular weight of the modified hydrogenated diene polymer (A) before modification and before hydrogenation is 5,000 to 1,000,000, preferably 30,000 to 300,000 in number average molecular weight. If it is less than 5,000, the hydrogenated diene polymer does not become rubbery and becomes liquid, and if it exceeds 1,000,000, processability tends to decrease.

Further, the molecular weight distribution (Mw / Mn) is preferably 10 or less, more preferably 5 or less, particularly preferably 1.1 or less.
~ 3. The hydrogenation rate of the olefinically unsaturated bond of the modified hydrogenated diene polymer (A) before modification is 70% or more, preferably 90% or more. If the degree of hydrogenation is less than 70%, the effect of improving the weather resistance and heat resistance of the polymer is insufficient, and thus the object of the present invention is not met.

The monomer having a functional group (unsaturated compound) in the modified hydrogenated diene polymer (A) is 0.01 to 30% by weight, preferably 0.1 to 30% by weight, based on 100% by weight of the hydrogenated diene polymer.
If it is less than 0.01% by weight, the weather resistance and impact resistance of the obtained composite composition are inferior. If it exceeds 30% by weight, the modified hydrogenated diene polymer (A) and the soft elastomer (B) ), The dispersion state is deteriorated, and the mechanical strength and abrasion resistance are poor.

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

Ethers, tertiary amine compounds, alkali metal alkoxides such as sodium and potassium, phenoxides, and sulfonates are used to control the amount of vinyl bonds such as 1,2- and 3,4-bonds.

As the organic lithium initiator, n-butyl lithium,
For example, sec-butyllithium, tert-butyllithium, or the like is used. As the hydrocarbon solvent, hexane, heptane, methylcyclopentane, cyclohexane, benzene,
Toluene, xylene, 2-methylbutene-1,2-methylbutene-2 and the like are used.

The polymerization may be a batch system or a continuous system, and the polymerization temperature is usually in the range of 0 to 120 ° C, and the polymerization time is in the range of 10 to 3 hours. The coupling agent is a coupling agent having three or more functions, such as tetrachlorosilicon, butyltrichlorosilicon, tetrachlorotin, butyltrichlorotin, tetrachlorogermanium, bis (trichlorosilyl) ethane, divinylbenzene, and adipic acid. Examples include diester, epoxidized liquid polybutadiene, epoxidized soybean oil, epoxidized linseed oil, tolylene diisocyanate, diphenylmethane diisocyanate, and 1,2,4-benzenetriisocyanate.

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

The hydrogenation reaction of the hydrogenated diene polymer before modification of the present invention is performed by dissolving the conjugated diene polymer in a hydrocarbon solvent, and curing the solution at 20 to 150 ° C. at 1 kg / cm ^{2 to} 100 kg / cm ² . Under pressurized hydrogen,
It is carried out in the presence of a hydrogenation catalyst.

Examples of hydrogenation catalysts include catalysts in which noble metals such as palladium, ruthenium, rhodium, and platinum are supported on silica, carbon, and diatomaceous earth; complex catalysts such as rhodium, ruthenium, and platinum; organic carboxylic acids such as cobalt and nickel; and organic aluminum. Or a catalyst comprising organic lithium, dicyclopentadienyl titanium dichloride, dicyclopentadienyl diphenyl titanium, dicyclopentadienyl titanium ditolyl, titanium compound such as dicyclopentadienyl titanium dibenzyl and lithium, aluminum, magnesium A hydrogenation catalyst comprising an organometallic compound is used.

In the reaction for modifying the hydrogenated diene polymer with a functional group-containing unsaturated compound, a radical generator such as an organic peroxide is usually used. Organic peroxides used as these functional group addition aids include:
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-t-butyl peroxide, t-butylperoxybenzoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane And 2,4-dichlorobenzoyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, and the like, and more preferably, a dialkyl peroxide is selected and used.

The amount of organic peroxide to be added depends on the hydrogenated diene polymer
0.01 to 1.5 parts by weight, preferably 0.1 to 1.5 parts by weight per 100 parts by weight
1.0 parts by weight.

When the amount of the organic perosicide is less than 0.01 part by weight, the grafting yield of the functional group is low, and when it exceeds 1.5 parts by weight, the crosslink density of the hydrogenated diene polymer becomes high, and the dispersion state at the time of blending with the soft elastomer (B) is increased. Deteriorated, mechanical strength,
It becomes inferior in abrasion resistance.

The grafting reaction of the functional group onto the hydrogenated diene polymer is performed using a pre-heated closed kneader such as a roll mill, a Banbury mixer, or a pressure kneader, or an extruder. Simultaneous melting and mixing of the saturated compound can be carried out by adding an organic peroxide and causing a graft reaction of a functional group to the hydrogenated diene polymer.

It can also be carried out by a method of copolymerizing a monomer having a functional group in the conjugated diene unit part in the rubber and further hydrogenating the copolymer.

Component (A) is used in an amount of 5 to 95% by weight, preferably 5 to 95% by weight.
It is 80% by weight, more preferably 5 to 60% by weight, particularly preferably 10 to 50% by weight. If it is less than 5% by weight, weather resistance is impaired, and if it exceeds 95% by weight, abrasion resistance is poor.

The 1,2-butadiene polymer which is the component (B) of the present invention has a vinyl bond content of 70% or more, preferably 85% or more, and a crystallinity of 5% or more, preferably 10 to 40%. -PBD. When the vinyl bond content is less than 70%,
Mechanical strength and wear resistance are significantly reduced. When the crystallinity is less than 5%, the mechanical strength, which is the object of the present invention,
Abrasion resistance cannot be obtained. Although the molecular weight can be selected over a wide range, in order to obtain a composite composition excellent in mechanical strength and abrasion resistance, which is the object of the present invention, the above [η]
(Measured in toluene at 30 ° C.) should be at least 0.5 dl / g. [Η] is more preferably 1.0 to 3.0 dl / g.

The vinyl aromatic-conjugated diene block copolymer which is the component (B) of the present invention is, for example, a compound represented by the following formula (A'-B ') nA', (A'-B ') n or ｛(A'-B'). ) N｝ mC ' Is a block copolymer represented by

The component (A ') has an aromatic vinyl compound content of 7 in order to obtain appropriate hardness and cushioning properties.
% Or more, preferably 90% or more, more preferably 10% or more
70% or less, the molecular weight is 10,000 or more and 1,000,000 or less,
More preferably, by using 70,000 or more and 300,000 or less, much more excellent mechanical strength and wear resistance, which are objects of the present invention, can be obtained.

As the aromatic vinyl compound, styrene, α-methylstyrene, ortho, meta, para-substituted methylstyrene,
Examples include ethylstyrene, methoxystyrene, dimethylaminostyrene, isopropylstyrene, pt-butylstyrene, and the like. Of these, styrene, paramethylstyrene and α-methylstyrene are preferred. Examples of the polymer include a polymer of only one of these monomers or a block or random copolymer obtained by combining two or more of these monomers.

The content of the aromatic vinyl compound varies depending on the application and molecular weight, and is not particularly limited, but is 7% or more and 90% or more.
The following is preferred. More preferably, it is 10% or more and 50% or less.

Examples of the conjugated diene (co) polymer or the hydrogenated polymer of the conjugated diene (co) polymer include a block polymer or a random copolymer or a partially aromatic or mono-polymer of butadiene, isoprene, and piperylene. Copolymers in which group III vinyl compounds are arranged randomly or in a tapered block, and hydrogenated polymers of these conjugated diene polymers can be mentioned.

Examples of the natural rubber, diene-based synthetic rubber, and non-diene-based synthetic rubber as the component (B) of the present invention include natural rubber (N
R), polyisoprene rubber (IR), styrene-butadiene rubber (SBR), polybutadiene rubber (BR), acrylonitrile butadiene rubber (NBR), chloroprene rubber (C
R) and other non-diene synthetic rubbers such as ethylene-propylene rubber (EPR), ethylene-propylene-non-conjugated diene rubber (EPDM), acrylic rubber (ACM, ANM), and fluoro rubber. Of these, NR, IR, SBR, BR and EPR are preferred.

The ethylene-vinyl acetate copolymer (EVA) as the component (B) of the present invention is a copolymer of ethylene and vinyl acetate obtained by a known production method, and is preferably MI (190)
(° C, 2160 gr, g / 10 min) 0.5 to 30.
(B) The component is preferably RB, TR, NR, EPR, or EVA.

Component (B) is used in an amount of 95 to 5% by weight, preferably 95 to 5% by weight.
It is 20% by weight, more preferably 95-40% by weight, particularly preferably 90-50% by weight. If less than 5% by weight, mechanical strength,
Abrasion resistance is impaired, and if it exceeds 95% by weight, weather resistance is poor.

The composition comprising the above (A) and (B) comprises the following composition (C), (D), (E),
By blending (F), a more practical composition can be obtained.

Examples of the softener of the component (C) used in the present invention include the following.

Aromatic, naphthenic, paraffinic process oils, petroleum asphalts such as straight asphalt and bron asphalt, lubricating oils, petroleum softeners such as paraffin, liquid paraffin, petrolatum; coal tar;
Coal tar softeners such as coal tar pitch, and fatty oil softeners such as castor oil, linseed oil, rapeseed oil, and coconut oil; waxes such as beeswax, carnauba wax, and lanolin:
There are tall oil and sub.

These can be used alone or in combination of two or more. Preferred emollients are process oils.

The amount of the component (C) to be softened is determined by the component [(A) +
(B)] 1 to 100 parts by weight, preferably 3 to 100 parts by weight
-80 parts by weight, more preferably 5-50 parts by weight. 1
If the amount is less than 100 parts by weight, the kneading processability is inferior, and if it exceeds 100 parts by weight, abrasion resistance, mechanical strength and weather resistance are inferior.

The inorganic filler of the component (D) used in the present invention includes, for example, light calcium carbonate, heavy calcium carbonate, various surface-treated calcium carbonates, talc, magnesium hydroxide, mica, clay, barium sulfate, natural silica, and the like. ,
Synthetic silicic acid (white carbon), titanium oxide and various carbon blacks can be used. Of these inorganic fillers, heavy calcium carbonate is economically advantageous and preferred.

The compounding amount of the inorganic filler is 100% for the component [(A) + (B)].
The amount is 1 to 500 parts by weight, preferably 5 to 200 parts by weight, more preferably 10 to 100 parts by weight with respect to parts by weight. If the amount is less than 1 part by weight, the kneading property is inferior, and if it exceeds 500 parts by weight, impact resistance, abrasion resistance and mechanical strength are inferior.

The crosslinking agent of the component (E) used in the present invention includes sulfur and various organic peroxides. Specific examples of organic peroxides include digyl 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 simultaneously added for crosslinking. Specific examples of the vulcanization accelerator include dibenzothiazyl disulfide (MBTS), 2-methylcaptobenzothiazole (MBT), N-cyclohexyl-2-pentazothiazyl sulfenamide (CBS), and N-oxyzoethylene-2. -Benzothiazylsulfenamide (DB
S), tetramethylthiuram disulfide (TMTD), tetramethylthiuram monosulfide (TMTM) and the like.

The compounding amount of the crosslinking agent is 1 to 50 parts by weight, preferably 2 to 30 parts by weight based on 100 parts by weight of the component [((A) + (B)].
More preferably, it is 2 to 20 parts by weight. If the amount is less than 1 part by weight, mechanical strength and abrasion resistance are inferior.

As the foaming agent of the component (E) used in the present invention, a known inorganic or organic foaming agent can be used. It is also possible to use them together. Specific examples of the foaming agent include sodium bicarbonate, ammonium bicarbonate, sodium carbonate, ammonium carbonate, azodicarbonamide (ADCA), dinitrosopentamethylenetetramine (DNPT), dinitrosoterephthalamide, azobisisobutyronitrile, Barium azodicarboxylate, sulfonyl human azide, toluene sulfonyl hydrazide and the like can be mentioned. These foaming agents may be used in combination with known foaming aids such as urea and urea derivatives.

The amount of the foaming agent to be used is 1 to 50 parts by weight, preferably 5 to 40 parts by weight, per 100 parts by weight of the component [(A) + (B)]. If the amount of the foaming agent is less than 1 part by weight, only a foam having a low expansion ratio can be obtained. If the amount exceeds 50 parts by weight, the amount of gas generated by decomposition of the foaming agent increases, and a foam having a good appearance cannot be obtained.

If necessary, in addition to the above additives, a crosslinking aid, an inhibitor, a processing aid, a plasticizer, an adhesive, and the like may be appropriately added.

Although the following (1) and (8) have been shown as methods of using this patent, for example, the following (2), (3), (4),
(5), (6), and (7) can also be used.

(1) Method of (A) + (B) (2) (A) + (B) + (C) (3) (A) + (B) + (D) (4) (A) + (B) + (E) (5) (A) + (B) + (C) + (D) (6) (A) + (B) + (C) + (E) (7) (A) + (B) + (D) + (E) (8) (A) + (B) + (C) + (D) + (E) In addition to (1) to (8) above, The mixing method is not particularly limited, and can be a mixing method used for general rubber compounds such as a Banbury mixer, a pressure kneader, and an open roll.

The uncrosslinked composition thus obtained is, if necessary, molded into a sheet or the like, and then subjected to crosslinking and foaming in a heat medium.

In the non-crosslinked field, the rubber composition of the present invention can be formed by a thermoplastic resin molding method such as extrusion molding, film molding, blow molding, vacuum molding, injection molding, and the like. And sheet modifiers, profile extruded products, molded products, and foams of these products, including daily necessities, industrial products, automotive parts, footwear, cushioning materials, packaging materials, etc. Cross-linking material molding methods such as injection molding, press molding, hot air molding, etc. are all possible, and solid molded products and foam molded products can be obtained.
For example, daily necessities, audio components, electrical goods, industrial goods,
It is suitably used for automobile parts, covering materials, cushioning materials, packaging materials and the like.

e. Working Examples Next, the present invention will be described specifically with reference to working examples and comparative examples, but the present invention is not limited thereto unless it exceeds the gist of the present invention.

In Examples and Comparative Examples, the tensile strength at break (Tb), tensile strength at break and (Eb) conform to JIS K6301, the amount of Williams wear conforms to British st'd 903, and the weather resistance is the sunshine weather test (black panel 63 ° C rain cycle) Is 18 minutes
(E / B) at 60% or more after 20 hours was evaluated as (）), and less than 60% was evaluated as (X). Impact resistance (Izod impact) conforms to ASTM D-256 notch, 50kg ・ cm / cm or more is judged as (○), 50kg ・ cm / cm
Less than was judged as (x).

The kneading processability was determined based on the cohesiveness, winding property or extrusion kneading dispersibility in a three-pressure kneader and a 10-inch open roll. When the cohesiveness is within 5 minutes, the spreadability is good or the extrusion kneading dispersibility is good (（),
When the cohesiveness exceeded 5 minutes and the sticking property was poor or the extrusion kneading dispersibility was poor (x), it was judged as (x).

The method of mixing the resin composition of the present invention is not particularly limited. For example, modified hydrogenated diene copolymers (A) and (B)
(C), (D), (E), and (F) are mixed using a mixer such as a roll, a Banbury mixer, or an intermixer, or the modified hydrogenated diene copolymer (A)
Into pellets, crumbs or powder, (B)
After dry blending (C), (D), (E) and (F) with a mixer such as a Henschel mixer or a tumbler,
A method of melt-mixing with a mixer such as an extruder is used, but in any case, a condition apparatus that can sufficiently disperse and mix each component may be selected.

Sample 1: (1) After 500 g of degassed and dehydrated cyclohexane, 150 g of styrene and 350 g of 1,3-butadiene were charged into a 5-autoclave, 2.5 g of tetrahydrofuran and 0.34 g of n-butyllithium were added, and the polymerization temperature was raised to 30 to 80. The polymerization was performed at an elevated temperature. After the conversion reaches almost 100%, the SiO ₄
0.14 g was added. Thereafter, 2,6-di-tert-butylcatechol was added, the solvent was removed by a steam stripping method, and the polymer 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 tri- or more branched polymer of 56% by weight. The number average molecular weight by GPC analysis was 200,000, and Mw / Mn was 1.5.

(2) The conjugated diene-based copolymer polymerized in (1)
The solution was charged into an autoclave to obtain a 15% cyclohexane solution. After substituting the system with nitrogen, a solvent solution of nickel naphthenate: n-butyllithium: tetrahydrofuran = 1: 8: 20 (molar ratio) previously prepared in a separate container was added in an amount of 1 mol as nickel to 2000 mol of the olefin portion. It was charged to become. Thereafter, hydrogen was introduced into the reaction system, and a hydrogenation reaction was performed at 70 ° C. After controlling the hydrogenation rate from the amount of hydrogen absorbed and consumed, the hydrogen in the system was replaced with nitrogen, and the antioxidant 2,6-di-tert-butylparacresol 1 was added.
PHR was added. After repeated decolorization and coagulation, roll drying was carried out by a conventional method to obtain a hydrogenated diene copolymer having a hydrogenation rate of 95%.

Sample 2: Sample 1 (1) except that no coupling reaction was performed
30% by weight of vinyl bond and 30% of styrene
By weight, a styrene-butadiene copolymer was obtained. This was treated in the same manner as in Sample 1 (2) to obtain a hydrogenated diene copolymer having a hydrogenation ratio of 98%.

Samples 3 to 4: The hydrogenated diene copolymer shown in Table 1 was obtained in the same manner as described below.

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

-The bound styrene content was determined from a calibration curve by an infrared method based on the absorption of a phenyl group at 679 cm- ¹ .

-The vinyl bond content was determined by an infrared method (Morello method).

・ The molecular weight, molecular weight distribution, and coupling efficiency (C / E)
It was determined from gel permeation chromatography (GPC).

The hydrogenation rate was calculated from the decrease in the unsaturated bond portion of the ¹ H-NMR spectrum at 100 MHz measured at a concentration of 15% using ethylene tetrachloride as a solvent.

Examples 1, 2, 4, and 9 The components (A) of Examples 1 and 2 use the sample 3 of Table 1 above, and the components (A) of Examples 4 and 9 use the sample 4 of Table 1 above. And manufactured according to the following procedure.

That is, the partially hydrogenated diene copolymer shown in Table 1 above
Mixer (HAAKE BUCHLER, H
AAKE RHEOCORD SYSTEM40RHEOMIX MIXER 600), 2 minutes later, 2.5 parts of maleic anhydride was added, and after melting and mixing, an organic peroxide [2,5-dimethyl-2,5-di (t-butylperoxy)) was added. Hexane; Nippon Oil & Fats Co., Ltd., Perhexa 25B] (0.15 parts) was added, and the mixture was further kneaded for 5 minutes to obtain component (A). Otherwise, as shown in Table 2, these were kneaded in a 3 pressure kneader under a 70 ° C atmosphere, then sheeted with an open roll, and crosslinked at 160 ° C for 20 minutes, and evaluated. Table 2 shows the evaluation results.

Examples 3, 5, 6, 7, and 8 The components (A) in Examples 3, 5, and 6 use the sample 1 in Table 1 above, and the components (A) in Examples 7 and 8 use the sample 1 in Table 1 above. Was used. Others knead the components shown in Table 2 with an extruder,
The extrudate was cut and molded by the molding methods shown in Table-2. Table 2 shows the evaluation results.

Comparative Examples 1, 3, and 6 The component (A) of Comparative Examples 1, 3, and 6 was the same as that of the sample 1 in Table 1 above.
And a composition outside the scope of the present invention obtained by the same processing method as in Example 1. Table 2 shows the evaluation results.

Comparative Examples 2, 4, and 5 The components (A) in Comparative Rows 2, 4, and 5 are the same as those in Table 1 above.
This is a composition outside the scope of the present invention, obtained by the same processing method as in Example 3 using Table 2 shows the evaluation results.

Comparative Examples 7 and 8 A composition was obtained in the same manner as in Example 1 except that emulsion polymerization SBR1502 and hydrogenated block copolymer Clayton G1650 (manufactured by Shell Chemical) were used as components (A). Table 2 shows the evaluation results.

From Table 2, it is clear that the examples of the present invention have excellent performance satisfying all the evaluation items as compared with the comparative examples which are not included in the present invention.

f. Effects of the Invention The composition of the present invention has a high balance of mechanical strength, abrasion resistance, weather resistance, impact resistance, and kneading processability, and can be arbitrarily selected from crosslinked, noncrosslinked, foamed, and nonfoamed. It is an excellent composition that can be extruded, film-formed, blow-molded, vacuum-formed, and press-formed, and is used for rubber goods, daily parts, acoustic parts, industrial goods, transportation parts,
It is provided over a wide range of applications such as automobile parts, footwear, cushioning materials, packaging materials, and has a very large industrial utility value.

Claims (4)

(57) [Claims] 1. A hydrogenated diene comprising at least one conjugated diene polymer or a copolymer of at least one conjugated diene and 50% by weight or less of a vinyl aromatic compound, wherein the (co) polymer is modified with a functional group. A composite composition comprising 5 to 95% by weight of a polymer (A) and 95 to 5% by weight of a soft elastomer (B). 2. A 1,2 having a soft elastomer (B) having a vinyl bond content of 70% or more, a crystallinity of 5% or more and an intrinsic viscosity [η] (measured in toluene at 30 ° C.) of 0.5 dl / g or more. -At least one selected from the group consisting of a butadiene polymer, a block copolymer of a vinyl aromatic compound and a conjugated diolefin, a natural rubber, a diene-based synthetic rubber, a non-diene-based synthetic rubber, and an ethylene-vinyl acetate copolymer. The composite composition according to claim (1). 3. The modified hydrogenated diene polymer (A) has a number average molecular weight of 5,000 to 1,000,000 and a molecular weight distribution Mw / Mn <10.
And a diene (co) polymer having a vinyl bond content of 10% or more in the diene portion was hydrogenated, so that at least 70% of the olefinically unsaturated bonds of the (co) polymer were hydrogenated. Carboxyl group, acid anhydride group, amino group, hydroxyl group and an unsaturated compound having at least one functional group selected from the group of epoxy group as a functional group in the hydrogenated diene polymer are added to the hydrogenated diene polymer in an amount of 100% by weight. 2. The composite composition according to claim 1, wherein 0.01 to 30 parts by weight is added to 1 part by weight. 4. The polymer (A) according to claim 1, wherein the content is 5 to 95% by weight.
100 parts by weight of the total [(A) + (B)] of the polymer (B) and 95 to 5% by weight of claim (1), 1 to 100 parts by weight of the softening agent (C) and inorganic filler ( D) 1 to 500 parts by weight of a bridging agent (E) 1 to 50 parts by weight and a foaming agent (F) 1 to 50 parts by weight.