JPH0643520B2 - Rubber composition for tires - Google Patents

Description

TECHNICAL FIELD The present invention relates to a rubber composition for tires suitable for tire treads and the like.

[Conventional technology]

2. Description of the Related Art In recent years, various attempts have been made to reduce rolling resistance of tire rubber members, particularly tire tread rubber members, in order to save energy for automobiles. In order to reduce the rolling resistance of this tire, it is sufficient to reduce the energy loss of the vulcanized rubber, and as the evaluation index of the vulcanized rubber, impact resilience of 50 to 80 ° C and t of 50 to 80 ° C are used.
an δ, Goodrich heat generation, etc. are used, and the raw rubber has a high impact resilience at 50 to 80 ° C.
A rubber having a small tan δ at -80 ° C or a small grid-rich heat generation is preferable.

In recent years, styrene-butadiene copolymers having various structures polymerized with an organolithium catalyst and styrene-butadiene copolymers having a polymer terminal modified with a functional group have been proposed as raw rubbers having high impact resilience.

For example, a styrene-butadiene copolymer obtained by modifying or coupling a polymer terminal with a tin compound, styrene-butadiene having a polymer terminal modified with a nitrogen-containing compound such as an isocyanate compound, an oxazolidinone compound, and a dialkylaminobenzophenone compound. Copolymers and the like have been proposed.

However, a styrene-butadiene copolymer obtained by using an organolithium catalyst as an initiator has a vinyl bond in the butadiene portion in the range of 10 to 90% and a trans bond in the range of 5 to 70% by the addition of a Lewis base or other additives. The vulcanizate has insufficient tensile strength and abrasion resistance as compared with a styrene-butadiene copolymer obtained by emulsion polymerization having 17% vinyl bond and 67% trans bond, for example. It was also inferior in terms of sex.

Further, the styrene-butadiene copolymer obtained by modifying the polymer terminal with a functional group as described above does not have extension crystallinity,
There is a problem that the high temperature tensile strength is low.

[Problems to be solved by the invention]

The present invention has been made against the background of the above-mentioned conventional technical problems, and an object of the present invention is to provide a rubber composition for tires which simultaneously satisfies impact resilience, abrasion resistance, mechanical properties, and low heat buildup.

[Means for solving problems]

That is, the present invention provides (a) an isocyanate compound and / or an isothiocyanate compound, (b) an isocyanuric acid derivative and / or a thiocarbonyl-containing compound corresponding to the derivative, (d) an amide compound and / or an imide compound, e) N-alkyl substituted oxazolidinone compound,
(f) pyridyl-substituted ketone compound and / or pyridyl-substituted vinyl compound, and (g) modified with at least one compound selected from the group of lactam compounds, wherein the trans bond content of the diene moiety is 70 to 90%, and Rubber raw material 10 containing 20% by weight or more of a diene (co) polymer having a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 20 to 150.
The present invention provides a rubber composition for a tire, wherein 20 to 100 parts by weight of carbon black and 0.1 to 5 parts by weight of a vulcanizing agent are blended with 0 part by weight.

The present invention, when obtaining a rubber composition for tires, by reacting a specific compound with a polymer immediately after being polymerized, various properties such as impact resilience, abrasion resistance, low heat buildup and mechanical properties are further improved. The improved diene (co) polymer is used as a raw material rubber.

The catalyst system used in producing the diene (co) polymer used in the present invention is preferably (h) an organomagnesium compound and / or an organic alkali metal compound (hereinafter referred to as “(h) component”) , (I) Organic alkaline earth metal compounds (however, excluding organomagnesium compounds, the following "(i)
Component)) as well as (j) organoaluminum compound (hereinafter referred to as “(j) component”).

First, as the organomagnesium compound which is one compound of the component (h), a dicycloalkylmagnesium compound and a diallylmagnesium compound can be mentioned.
Specifically, dimethyl magnesium, dipropyl magnesium, dibutyl magnesium, ethylbutyl magnesium, ethylhexyl magnesium, dihexyl magnesium, dioctyl magnesium, didecyl magnesium, didodecyl magnesium, dicyclohexyl magnesium, dicyclopentyl magnesium, diphenyl magnesium, ditolyl magnesium, ethyl. Magnesium bromide, ethyl magnesium chloride, allyl magnesium bromide, propyl magnesium bromide, n
-Butyl magnesium chloride, phenyl magnesium bromide, phenyl magnesium iodide and the like.

Further, the organic alkali metal compound which is the other compound of the component (h), ethyl lithium, propyl lithium,
Alkyllithium such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, 1,4-dilithiobutane, a reaction product of butyllithium and divinylbenzene, alkylenedilithium, phenyllithium, stilbendilithium, iso Examples thereof include propenylbenzenedilithium, sodium naphthalene, potassium naphthalene, lithium naphthalene and the like.

The organomagnesium compound or the organoalkali metal compound as the component (h) can be used alone or in a mixture.

The amount of the component (h) used varies depending on the molecular weight of the produced (co) polymer and the Mooney viscosity, but is usually 0.05 to 10 mmol, preferably 0.1 to 8 mmol per 100 g of the monomer.

The organic alkaline earth metal compound (excluding the magnesium compound) used as the component (i) is an organic metal compound of barium, calcium, or strontium, specifically, barium dimethoxide, barium diethoxide. , Barium diisopropoxide, barium di n-butoxide, barium di sec-butoxide, barium di t-butoxide, barium di (1,1-
Dimethylpropoxide), barium di (1,2-dimethylpropoxide), barium di (1,1-dimethylbutoxide), barium di (1,1-dimethylpentoxide), barium di (2-ethylhexanoxide), barium di (1 -Methyl hebutoxide), barium diphenoxide, barium di (p-methylphenoxide), barium di (p-butylphenoxide), barium di (o-
Methylphenoxide), barium di (p-octylphenoxide), barium di (p-nonylphenoxide),
Barium di (p-dodecyl phenoxide), barium di (α-naphthoxide), barium di (β-naphthoxide), barium (o-methoxyphenoxide), barium di (m-methoxyphenoxide), barium di (p-)
Examples thereof include barium compounds such as methoxyphenoxide), barium (o-ethoxyphenoxide), and barium di (4-methoxy-1-naphthoxide). (However, R ^{1 to} R ⁵ are hydrogen atoms or 1 to 20 carbon atoms.
Is an alkyl group or an alkoxyl group).

Further, a partial hydrolyzate in which 0.1 to 0.5 equivalent of an alkoxide group or a phenoxide group is substituted with a hydroxy group per atom of barium is also used.

Further, as the component (i), a calcium compound or a strontium compound corresponding to the barium compound can be mentioned.

The amount of component (i) used is 0.01 to 20 equivalents, preferably 0.1 to 10 equivalents, per gram atom of metal atom of the magnesium compound or organic alkali metal compound used as component (h). .

Furthermore, the organoaluminum compound which is the component (j) has the general formula AlR ⁶ R ⁷ R ⁸ (wherein R ⁶ , R ⁷ and R ⁸
Are the same or different and each is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms and not all hydrogen atoms), and specifically, trimethylaluminum, triethylaluminum, triisopropylaluminum, tributyl Aluminum, triisobutyl aluminum, trihexyl aluminum, tricyclohexyl aluminum, diisobutyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, ethyl aluminum dihydride, propyl aluminum dihydride, isobutyl aluminum dihydride, etc. may be mentioned.

The amount of the component (j) used is 0.02 to 2.0 equivalents, preferably 0.5 to 1.1 per 1 gram atom of the metal atom of the magnesium compound or the organic alkali metal compound used as the component (h). It is 0 equivalent.

As a catalyst component, in addition to the components (h), (i), and the above components, a conjugated diene may be optionally used in a proportion of 0.05 to 20 mol per mol of the component (h) during catalyst preparation. Good. As the conjugated diene used for preparing the catalyst, isoprene, 1,3-butadiene, 1,3-pentadiene and the like which are the same as the monomers for polymerization are used.

Conjugated dienes as catalyst components are not essential, but by using them together, the catalytic activity of the catalyst components is further improved.

The catalyst is prepared, for example, by reacting the components (h) to (j) dissolved in an inert organic solvent and, if necessary, a conjugated diene. In that case, the order of addition of each component may be arbitrary. These components are preferably mixed, reacted and aged in advance from the viewpoint of improving the polymerization activity and shortening the polymerization initiation induction period, but even if the catalyst components are added directly to the solvent and the monomer during the polymerization in sequence. Good.

The polymerization solvent is an inert organic solvent, for example, an aromatic hydrocarbon solvent such as benzene, toluene and xylene, an aliphatic hydrocarbon solvent such as n-pentane, n-hexane, n-butane and cyclohexane, and methylcyclo. Alicyclic hydrocarbon solvents such as pentane, cyclohexane and mixtures thereof can be used.

The polymerization temperature is generally -20 ° C to 150 ° C, preferably 30 to 120 ° C. The polymerization reaction may be a batch system or a continuous system.

The monomer concentration in the solvent is usually 5 to 50% by weight,
It is preferably 10 to 35% by weight.

Further, in order to prevent the catalyst system and the polymer of the present invention from being deactivated in order to produce a copolymer, it is possible to minimize the mixture of oxygen, water, carbon dioxide gas or other deactivating compounds into the polymerization system. Consideration is required.

Conjugated dienes that can be polymerized with the catalyst system of the present invention include:
3-butadiene, isoprene, 2,3-dimethyl-1,
There are 3-butadiene, 1,3-pentadiene, myrcene and the like, which may be used alone or in combination of two or more, and 1,3-butadiene is particularly preferable.

Further, the diene (co) polymer used in the present invention includes
In addition to the conjugated dienes, vinyl aromatic compounds such as styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, p-butylstyrene and vinylnaphthalene, as well as vinylpyridine, acrylonitrile, methacrylonitrile and methyl (meth ) It is possible to copolymerize acrylates, acrylates, etc., preferably vinyl aromatic compounds, especially styrene.

In the present invention, first, thus, the conjugated diene is homopolymerized or the aromatic vinyl compound such as styrene and the conjugated diene are copolymerized in an inert organic solvent using the catalyst system comprising the components (h) to (j). To produce a (co) polymer. The (co) polymer thus obtained has a trans bond of the diene moiety of 70 to 90%, preferably 75 to 90%.
87%, the content of bound aromatic vinyl compound is 5 to 45% by weight, more preferably 10 to 35% by weight, and the styrene chain is preferably random.
When the trans bond of the diene portion is less than 70%, the tensile strength is
Abrasion resistance is poor, and when it exceeds 90%, impact resilience is reduced. The content of the aromatic vinyl compound in the produced (co) polymer is 5 to 5 from the viewpoint of tensile strength and impact resilience of the vulcanized rubber.
45% by weight is preferred.

Further, the produced (co) polymer has a random styrene chain, for example, I.I. M. Oxidative decomposition method such as Kolthoff (J. Polymer Sci., 1 , 4
29 (1946)), the content of block polystyrene in the copolymer is 10% by weight or less, preferably 5% by weight or less, and the long-chain block polystyrene is 10% by weight.
If it exceeds, the impact resilience of the vulcanizate decreases.

The rubber composition for a tire of the present invention is obtained by modifying the polymer terminal of the thus obtained (co) polymer by reacting a specific compound with a novel (co) polymer having a functional group introduced. It is a mixture.

By this modification, the effects of improving impact resilience, abrasion resistance, heat generation characteristics, and mechanical characteristics can be obtained.

In the present invention, the specific compound to be reacted after the production of the (co) polymer includes (a) an isocyanate compound and / or
Or an isothiocyanate compound (hereinafter referred to as “(a) component”), (b) isocyanuric acid derivative and / or a thiocarbonyl content compound corresponding to the derivative (hereinafter referred to as “(b) component”), (d) amide compound and / Or imide compound (hereinafter referred to as "(d) component"), (e) N-alkyl-substituted oxazolidinone compound (hereinafter referred to as "(e) component"), (f) pyridyl-substituted ketone compound and / or pyridyl-substituted vinyl compound ( Hereinafter referred to as "(f) component"),
And (g) lactam compound (hereinafter referred to as “(g) component”)
At least one compound selected from the group can be mentioned.

Among these compounds, specific examples of the isocyanate compound or the isothiocyanate compound which is the component (a) include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, and polymeric. Types of diphenylmethane diisocyanate (C-MDI), phenyl isocyanate, isophorone diisocyanate, hexamethylene diisocyanate, butyl isocyanate, 1,3,5-benzenetriisocyanate, phenyl isothiocyanate, phenyl-1 , 4-diisothiocyanate and the like.

Specific examples of the isocyanuric acid derivative as the component (b) and the thiocarbonyl-containing compound corresponding to the derivative include carbamic acid derivatives such as methyl carbamate and methyl N, N-diethylcarbamate, isocyanuric acid, N, N ′,
Mention may be made of isocyanuric acid derivatives such as N'-trimethylisocyanuric acid and the thiocarbonyl-containing compounds corresponding to these derivatives.

Specific examples of the amide compound or imide compound as the component (d) include N, N-dimethylformamide, acetamide, N, N-diethylacetamide, aminoacetamide, N, N-dimethyl-N ', N'-dimethylamino. Acetamide, N, N-dimethylaminoacetamide, N, N-ethylaminoacetamide, N, N-dimethyl-N'-ethylaminoacetamide, acrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, nicotinamide , Isonicotinamide, picolinic acid amide, N, N-dimethylisonicotinamide, succinic acid amide, phthalic acid amide, N, N,
N ', N'-tetramethylphthalamide, oxamide, N, N, N', N'-tetramethyloxamide, 2
-Amide compounds such as furancarboxylic acid amide, N, N-dimethyl-2-furancarboxylic acid amide, quinoline-2-carboxylic acid amide, N-ethyl-N-methyl-quinolinecarboxylic acid amide, succinimide, N- Examples thereof include imide compounds such as methylsuccinimide, maleimide, N-methylmaleimide, phthalimide and N-methylphthalimide.

Specific examples of the N-alkyl-substituted oxazolidinone compound which is the component (e) include 1,3-diethyl-2-imidazolidinone, 1,3-dimethyl-2-imidazolidinone,
1,1-dipropyl-2-imidazolidinone, 1-methyl-3-ethyl-2-imidazolidinone, 1-methyl-
3-propyl-2-imidazolidinone, 1-methyl-3
-Butyl-2-imidazolidinone, 1-methyl-3-
(2-Methoxyethyl) -2-imidazolidinone, 1-
Methyl-3- (2-ethoxyethyl) -2-imidazolidinone, 1,3-di- (2-ethoxyethyl) -2-imidazolidinone and the like can be mentioned.

Specific examples of the pyridine-substituted ketone compound or pyridyl-substituted vinyl compound as the component (f) include methyl-2-
Pyridyl ketone, methyl-4-pyridyl ketone, propyl-2-pyridyl ketone, di-4-pyridyl ketone, propyl-3-pyridyl ketone, 2-benzoylpyridine, 2-vinylpyridine, 4-vinylpyridine and the like can be mentioned. it can.

Specific examples of the lactam compound as the component (g) include N-
Methyl-2-pyrrolidone, 2-piperidone, N-methyl-2-piperidone, 2-quinolone, N-methyl-quinolone and the like.

The compounds comprising the components (a) to (b) and the components (d) to (g) may be used alone or in combination of two or more.

The amount of these compounds used is based on a functional group such as an isocyanate group, an isothiocyanate group, a carbonyl group, a vinyl group or an aldehyde group per 1 g atom equivalent of a magnesium atom or an alkali metal atom in the component (h). , Usually 0.2 to 10 equivalents, preferably 0.5 to 5.
If it is less than 0.2 equivalents, the vulcanized rubber is inferior in the impact resilience and low exothermicity, while if it exceeds 10 equivalents, unreacted substances increase and odor is generated, or the vulcanization speed is increased. However, the effects of the impact resilience and low heat buildup of the vulcanizate are reduced, which is not preferable.

In addition to the compounds of the components (a) to (b) and the components (d) to (g) to (g), the molecular weight distribution of the resulting diene-based polymer is broadened, and the cold flow of raw rubber is reduced. In order to achieve this, a (k) metal halide compound (hereinafter referred to as “(k) component”) such as a bifunctional or higher functional tin halide compound or a silicon halide compound is used as the magnesium atom or alkali It can also be added in the range of 0.05 to 5 equivalents, preferably 0.1 to 1.5 equivalents, based on the halogen atom, per 1 g of the metal atom.

Examples of the component (k) include dibutyldichlorotin, diphenyldichlorotin, methyltrichlorotin, butyltrichlorotin, phenyltrichlorotin, tetrachlorotin, bis (trichlorostannyl) ethane, dibutyldichlorosilicon, methyltrichlorosilicon, tetrachloro. Examples thereof include silicon and tin carboxylate compounds, and these compounds can be used alone or in combination.

The reaction temperature of the (co) polymer and the compound is usually room temperature to 120 ° C., preferably 50 to 100 ° C., or the reaction time is usually several seconds to several hours.

After the reaction is completed, steam is blown into the polymer solution to remove the solvent, or a poor solvent such as methanol is added to solidify the modified (co) coalescence, followed by drying on a hot roll or under reduced pressure (co) weight. You can get coalesced. In addition, the solvent was removed from the polymer solution directly under reduced pressure (co).
It is also possible to obtain a polymer.

Further, the molecular weight of the (co) polymer obtained in the present invention can be varied over a wide range, but its polystyrene-equivalent weight average molecular weight is usually 5 × 10 ⁴ to 1
00 × 10 ⁴ , preferably 10 × 10 ⁴ to 80 × 10 ^4.
If it is less than 5 × 10 ⁴ , the vulcanized rubber is inferior in tensile strength, abrasion resistance, impact resilience, and heat generation, while if it exceeds 100 × 10 ⁴ , it is inferior in workability and the torque during kneading with a roll or Banbury is low. Is unfavorable because it causes an excessively large amount, the compound is heated to a high temperature and deteriorates, and the dispersion of the carbon black is poor and the vulcanized rubber production process is inferior.

The diene-based (co) polymer obtained in the present invention has a Mooney viscosity (ML) particularly when used as an industrial rubber product.
_{1 + 4} , 100 ° C.) is usually in the range of 20 to 150, preferably 30 to 80, and for the same reason as the above-mentioned weight average molecular weight, when it is less than 20, the physical properties of the vulcanized rubber are inferior.
If it exceeds 50, the workability becomes poor.

The tire rubber composition of the present invention, the diene-based (co) polymer, alone or blended with other synthetic rubber or natural rubber is blended as a raw rubber, if necessary oil extended with process oil, Next, carbon black as a filler,
It is prepared by adding usual vulcanized rubber compounding agents such as a vulcanizing agent and a vulcanization accelerator.

In this case, in order to exhibit the excellent characteristics of the diene (co) polymer compounded in the present invention, the diene (co) polymer of the present invention is contained in the raw rubber in an amount of 20% by weight or more, preferably Is required to be contained in an amount of 30% by weight or more.

Other synthetic rubbers to be blended and used include cis-1,4-polyisoprene, emulsion-polymerized styrene-butadiene copolymer, solution-polymerized styrene-butadiene copolymer, low cis-1,4-polybutadiene, High cis-1,4-polybutadiene, ethylene-propylene-diene copolymer, chloroprene, halogenated butyl rubber,
Examples thereof include acrylonitrile-butadiene rubber (NBR).

As the process oil used for oil extension, for example, paraffin-based, naphthene-based, aromatic-based, etc. can be mentioned. However, for applications where tensile strength and abrasion resistance are important, the aromatic-based one has impact resilience. A naphthene-based or paraffin-based material is used for applications where importance is attached to low-temperature characteristics, and the amount used is 5 to 100 parts by weight with respect to 100 parts by weight of raw material om. If the amount of carbon black exceeds 100 parts by weight, the tensile strength and impact resilience of the vulcanized rubber are significantly reduced.

Furthermore, as the carbon black used, HA
Carbon black such as F, ISAF, SAF,
Preferably, the iodine adsorption amount (IA) is 60 mg / g or more, and the dibutyl phthalate oil absorption amount (DBP) is 80 ml / 10.
0 g or more of carbon black is used. The amount of the carbon black used is 20 to 100 parts by weight, preferably 30 to 80 parts by weight, based on 100 parts by weight of the raw rubber, and if the amount is less than 20 parts by weight, the vulcanizate has sufficient tensile strength and abrasion resistance. On the other hand, if it exceeds 100 parts by weight, impact resilience, heat generation and the like are deteriorated.

Furthermore, sulfur is usually used as the vulcanizing agent,
The amount used is 0.1 to 100 parts by weight of raw rubber.
It is 5 parts by weight, preferably 1 to 2 parts by weight. If it is less than 0.1 parts by weight, the tensile strength, abrasion resistance and impact resilience of the vulcanized rubber will decrease, while if it exceeds 5 parts by weight, it will become hard and the rubber elasticity will increase. Lost.

Furthermore, the vulcanization accelerator is not particularly limited, but is preferably M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ.
Examples thereof include thiazole-based vulcanization accelerators such as (N-cyclohexyl-2-benzothiazylsulfenamide), and the amount thereof is 0.1 to 5 parts by weight, preferably 100 parts by weight of the raw rubber. Is 0.2 to 3 parts by weight.

The tire rubber product of the present invention, if necessary, silica other than carbon black, calcium carbonate, filler such as titanium oxide, zinc oxide, stearic acid, antioxidant,
Additives such as antiozonants may also be added.

The rubber composition for a tire of the present invention is obtained by kneading using a kneader such as a roll or an internal mixer, and after the molding process, vulcanization is performed, a tire tread,
It can be used not only for tire applications such as undertread, car curls, sidewalls, and beat parts, but also for applications such as hoses, belts, shoe soles, window frames, seal materials, anti-vibration rubber, and other industrial products. It is preferably used as rubber for tire treads.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

In the examples, parts and% mean parts by weight and% by weight, unless otherwise specified.

Further, various measurements in the examples were based on the following methods.

The reaction between the polymer immediately after being polymerized by the catalyst system and the specific modifying compound is the change in Mooney viscosity before and after the reaction, or the model reaction with the number average molecular weight of several thousand, and confirmed by GPC analysis and infrared analysis. It was

The Mooney viscosity was measured by preheating for 1 minute, measurement for 4 minutes, and temperature of 100 ° C. (according to JIS K6300).

The microstructure of the (co) polymer was determined by the infrared absorption spectrum method (Morero method).

A vulcanizate obtained by kneading and blending the (co) polymer of the present invention or a commercially available rubber with a 230 cc Brabender and a 6-inch roll according to the following formulation, and then vulcanizing at 145 ° C. for a predetermined time. Various measurements were performed using.

Formulation (part) Polymer 100 Carbon black (HAF) 50 Aromatic oil 10 Stearic acid 2 Zinc white 3 Anti-aging agent (810NA) ^{* 1} 1 Vulcanization accelerator (CZ) ^{* 2} 0.6〃 (M) ^{* 3} 0.6 〃 (D) ^{* 4} 0.4 〃 (NOBS) ^{* 5} 0.5 Sulfur 1.5 * 1) N-phenyl-N'-isopropyl-p-phenylenediamine * 2) N-cyclohexyl-2- Benzothiazoline sulfenamide * 3) 2-mercaptobenzothiazole * 4) 1,3-diphenylguanidine * 5) N-oxydiethylene-2-benzothiazolesulfenamide Tensile properties and impact resilience were measured according to JIS K6301.

Abrasion resistance was in accordance with ASTM D2228 (Pico method). The Pico abrasion index was determined by using the abrasion amount of a vulcanized product of a styrene-butadiene copolymer (manufactured by Japan Synthetic Rubber Co., Ltd., # 1500) by the Pico method as a reference index 100 (see Comparative Test Example 1). The larger the index, the better the abrasion resistance.

Reference Example 1 A dry autoclave having an inner volume of 5 with a stirrer and a jacket was purged with nitrogen and charged with 2,500 g of cyclohexane and 500 g of 1,3-butadiene which had been purified and dried in advance, and the autoclave was heated to 70 ° C. The catalyst shown in 1 was added to initiate the polymerization. The polymerization reaction is
It was performed under isothermal conditions.

Polymerization-type diphenylmethane diisocyanate was added as a coupling agent at the stage when the addition rate of polymerization reached about 95% to terminate the polymerization.

Next, 0.7 g of di-t-butyl-p-cresol as an anti-aging agent was added to 100 g of rubber (as solid content), followed by desolvation and drying according to a conventional method to obtain a polymer A.

The microstructure of poly-1,3-butadiene obtained by this reaction has a cis-1,4 bond content of 10% and a vinyl bond content of 4%.
%, And trans-1,4 binding was 86%. The results are shown in Table 1.

The GPC chart of this polymer is shown in FIG.
As is clear from FIG. 1, the molecular weight distribution obtained by a differential refractometer and the molecular weight distribution obtained by ultraviolet rays (UV, 254 nm) appear in correspondence with the GPC count, and the UV absorption spectrum is closer to the lower molecular weight side. It can be seen that the absorption intensity is high and corresponds to the number of terminals of the polymer.

Thus, it can be seen that even when 1,3-butadiene is polymerized alone using the specific catalyst system used in the present invention, a coupling reaction occurs with the specific compound as in the present invention.

Reference Examples 2 to 10 Using the catalyst system shown in Table 1 in the same manner as in Reference Example 1,
Copolymerization of 3-butadiene (400 g) and styrene (100 g) and a coupling reaction using the compounds shown in Table 1 were performed to obtain polymers B to J.

Examples 1 to 11 In Polymers B to J obtained in Reference Examples 2 to 10, natural rubber (NR) and commercially available styrene-butadiene copolymer (# 1) were used.
500, manufactured by Japan Synthetic Rubber Co., Ltd., trans-1,4 bond = 68%, bonded styrene content = 23.5%, Mooney viscosity = 52), polybutadiene (JSR BR01, manufactured by Japan Synthetic Rubber Co., Ltd., cis-). 1,4 bond = 96%, Mooney viscosity 44, hereinafter referred to as "BR"), or unmodified styrene-butadiene copolymer (HT-SBR, trans-) obtained by the catalyst system shown in Reference Example 1 of Table 1. 1,4 bond = 83%, bonded styrene content = 15%, Mooney viscosity =
45) was blended, kneaded and blended with a 230 cc Brabender and a 6 inch roll according to the above formulation, and then various measurements were performed using a vulcanized product that was vulcanized at 145 ° C. for a predetermined time. Shown in the table.

Comparative Examples 1 to 5 Polymer B, natural rubber (NR), commercially available styrene-
Butadiene rubber (# 1500) or unmodified styrene-butadiene copolymer (HT-SBR) was singly or blended and kneaded with a 230 cc Brabender and a 6 inch roll according to the above compounding recipe, and then 1
Table 2 shows the results of various measurements performed on the vulcanized product which was vulcanized at 45 ° C. for a predetermined time.

Comparative Example 6 Using the isocyanate group-modified styrene-butadiene copolymer described in Reference Example 10 in Table 1 and Polymer J, 50 parts each of Polymer J and NR (natural rubber) were blended according to the blending recipe, and added. The physical properties of the vulcanized rubber are shown in Table 2 (continued). As a result of this experiment, it is found that when Polymer J having a low trans content of 51% is used, the tensile strength and the wear resistance are inferior.

EFFECTS OF THE INVENTION The present invention is a rubber composition containing a novel diene (co) polymer having a specific functional group obtained by reacting a specific compound, and when used as an industrial rubber product. ,
A vulcanizate having good impact resilience, mechanical properties (in particular, modulus and tensile strength) and heat generation properties, and having greatly improved abrasion resistance as compared with known conjugated diene (co) polymers can be obtained.

[Brief description of drawings]

FIG. 1 is a GPC chart of the polymer A obtained in Reference Example 1.

 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Mitsuhiko Sakakibara 2-11-24 Tsukiji, Chuo-ku, Tokyo Within Nippon Synthetic Rubber Co., Ltd. (72) Inventor Noboru Oshima 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (72) Inventor Hiroshi Mohri 3-4-8-205 Ogawahigashi-cho, Kodaira-shi, Tokyo (72) Inventor Tatsuo Fujimaki 3-2-3 Fujimi-cho, Higashimurayama-shi, Tokyo Shinbu Musashino Sky Heights No. 613

Claims (3)

[Claims] 1. (a) Isocyanate compound and / or isothiocyanate compound, (b) Isocyanuric acid derivative and / or thiocarbonyl-containing compound corresponding to the derivative, (d) Amide compound and / or imide compound, (e) )
Modified with at least one compound selected from the group consisting of N-alkyl-substituted oxazolidinone compounds, (f) pyridyl-substituted ketone compounds and / or pyridyl-substituted vinyl compounds, and (g) lactam compounds, and the trans bond content of the diene moiety is 70-90% and Mooney viscosity (M
(L _{1 + 4} , 100 ° C.) 20 to 100 parts by weight of a rubber raw material containing 20% by weight or more of a diene (co) polymer having a temperature of 20 to 150, and 20 to 100 parts by weight of carbon black and a vulcanizing agent. A rubber composition for a tire, characterized by containing 0.1 to 5 parts by weight. 2. The tire rubber composition according to claim 1, wherein the diene (co) polymer is a butadiene polymer or a styrene-butadiene copolymer. 3. The rubber composition for a tire according to claim 1, wherein the diene (co) polymer is a styrene-butadiene copolymer having a bound styrene content of 5 to 45% by weight.