JPH11246711A - Rubber composition, tire, and outsole - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a tire material excellent in gripping property and not slippery for a road covered with snow or ice, or wet, etc. SOLUTION: A norbornene polymer (e.g. a polymer prepd. by ring-opening polymerization of 5-norbornene) which contains a natural rubber and/or a diene synthetic rubber, and a softening agent (e.g. a naphthenic oil having a pour point of not lower than -30 deg.C), or a powder made by vulcanizing the polymer and pulverized (e.g. to 10-50 mesh) is compounded with a resinous or a liquid rubber tackifier (e.g. terpene resin) and used as a tire tread material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a slip-resistant rubber composition, a tire, and an outsole excellent in performance on wet roads, performance on snow, and performance on ice.

[0002]

2. Description of the Related Art Conventionally, it has been proposed to use a norbornene-based polymer for a tread of a studless tire. For example, the peak position of tan δ is −5 ° C. to + 35 ° C.
Using a rubber composition containing a powdered rubber of a norbornene-based copolymer and an aromatic oil in the range of
No. 133248), and the glass transition temperature is -40 ° C.
A rubber composition containing the above styrene-butadiene copolymer rubber, norbornene polymer, carbon black having a nitrogen gas adsorption specific surface area of 350 m ² or more, and 80 to 280 parts by weight of extending oil with respect to 100 parts by weight of rubber. A rubber composition in which 2 to 30 parts by weight of a softener and 2 to 15 parts by weight of a norbornene-based polymer having a molecular weight of 3,000,000 or more are mixed with 100 parts by weight of rubber. (For example, JP-A-6-212030). However, there is no known example in which a tackifier is added thereto, and an improvement in grip force on a road surface at a low temperature has been demanded, but a sufficient one has not been known.

[0003] Recently, rubber compositions for tire treads containing natural rubber or polyisoprene rubber, solution-polymerized styrene-butadiene copolymer rubber, modified rosin as a tackifier, and reinforcing filler have been proposed. (JP-A-9-328579). However, this composition is known for wet braking, but not for ice braking.

[0004] A similar problem has also been encountered with the outsole of shoes.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a rubber composition for tire treads or outsole, which has excellent grip on the road surface on snow and ice, on wet road surfaces, etc., and which does not slip easily. It is an object of the present invention to provide a tire having a modified tire tread, and a molded cross-linked outsole.

[0006]

Means for Solving the Problems As a result of diligent research, the present inventors have found that by blending a rubber containing a softener-containing norbornene-based polymer and a tackifier, it is possible to form a rubber composition on a snowy or ice-covered or wet road surface after crosslinking by molding. It has been found that a molded product having excellent slip resistance can be obtained, and the present invention has been completed.

Thus, according to the present invention, a rubber composition for a tire tread containing a natural rubber and / or a diene-based synthetic rubber, a norbornene-based polymer containing a softener, and a tackifier, and the rubber composition are provided. A tire having a tread is provided.

(Rubber) The rubber used in the rubber composition of the present invention is a natural rubber and / or a diene-based synthetic rubber. The diene-based synthetic rubber is not particularly limited, and isoprene rubber, emulsion-polymerized styrene-butadiene copolymer rubber, solution-polymerized styrene-butadiene copolymer rubber (for example, the amount of bound styrene is 5 to 50% by weight, , 2-vinyl bond amount of 10 to 80%), high trans-styrene-butadiene copolymer rubber (for example, a 1,4-trans bond amount of a butadiene bond unit portion of 70 to 9
5%), low cis-butadiene rubber, high cis-butadiene rubber, high trans-butadiene rubber (for example, when the amount of 1,4-trans bond in the butadiene bond unit portion is 70%).
~ 95%), styrene-isoprene copolymer rubber, ethylene-propylene-diene terpolymer rubber, butadiene-isoprene copolymer rubber, solution-polymerized random styrene-butadiene-isoprene copolymer rubber, emulsion-polymerized random styrene- Butadiene-isoprene copolymer rubber, high vinyl-styrene-butadiene-low vinyl-styrene-butadiene-block copolymer rubber, polystyrene-polybutadiene-polystyrene-block copolymer rubber and the like are exemplified, preferably natural rubber, butadiene rubber, isoprene Rubber, styrene-butadiene copolymer rubber, and styrene-butadiene-isoprene copolymer rubber are preferred.

The glass transition temperature of the natural rubber and / or the diene-based synthetic rubber used in the present invention is not particularly limited, but is usually 20 ° C. or lower, preferably 0 ° C. or lower, more preferably -20 ° C. or lower. The lower the glass transition temperature, the better the cold resistance and the better the low-temperature properties such as hardness and skid resistance.

The Mooney viscosity of the natural rubber and / or the diene-based synthetic rubber used in the present invention is not particularly limited, either.
Usually, it is 10 to 150, preferably 20 to 100, more preferably 30 to 60. If the Mooney viscosity is too low, it tends to deform after molding in extrusion molding, etc.
In the case of a tire tread or the like, a problem may occur in post-processing. If the Mooney viscosity is too high, molding becomes difficult and workability tends to be a problem. In addition, when laminating with a cloth in post-processing such as a tire tread, the tackiness may be insufficient and a problem may occur.

In the present invention, rubber may be used alone or in combination of two or more.

(Norbornene Polymer Containing Softener) The norbornene polymer containing a softener used in the present invention is obtained by vulcanizing a norbornene polymer to which a softener is added, or a vulcanized product obtained by adding a softener. It is a thing.

The norbornene polymer used in the present invention is:
If a polymer obtained by ring-opening polymerization of a norbornene-based monomer,
There is no particular limitation.

In the norbornene-based monomer, the carbon at the 2- and / or 3-position of the norbornene ring is a hydrogen atom and the carbon number is 1
Having a structure bonded to an alkyl group having 1 to 4 carbon atoms, an alkylene group having 1 to 4 carbon atoms, an alkylidene group having 1 to 4 carbon atoms, or an aromatic hydrocarbon residue having 6 to 20 carbon atoms. Is 5-norbornene, 2-methyl-5-norbornene, 2-ethyl-5-norbornene, 2-butyl-5-
Norbornene, 2,3-dimethyl-5-norbornene,
2-vinyl-5-norbornene and the like are exemplified.

The method for producing the norbornene-based polymer is also not particularly limited. For example, the method may be carried out in the presence of a catalyst such as ruthenium chloride and a reducing agent such as methanol or an alcohol.
At 140 ° C., a norbornene-based polymer can be obtained by bulk polymerization of a norbornene-based monomer or solution polymerization in an organic solvent such as toluene (Japanese Patent Publication No. 47-3).
No. 5800).

The glass transition temperature of the norbornene-based polymer is not particularly limited either, but is preferably -50 to + 200 ° C, more preferably 0 to 150 ° C, and particularly preferably 10 to 50 ° C. When the glass transition temperature is in the preferred range, a tire tread excellent in abrasion resistance and excellent in balance between ice skid resistance and wet skid resistance can be obtained.

The molecular weight of the norbornene-based polymer is not particularly limited, either. The weight-average molecular weight (Mw) is 100,000 to 1 in terms of polystyrene measured by high performance liquid chromatography using tetrahydrofuran as a developing solvent.
0,000,000 is preferable, and 500,000
~ 7,000,000 are more preferred, and 700,
000-5,000,000 are particularly preferred. If the weight average molecular weight is in the preferred range, a tire tread excellent in abrasion resistance and excellent in ice skid resistance and wet skid resistance can be obtained.

In the present invention, the norbornene-based polymer may be used alone or in combination of two or more.

The softener used in the present invention imparts softness to rubber to increase plasticity, and is used for kneading work, dispensing work,
A compounding agent that facilitates extrusion work, molding work, etc., and also reduces the hardness of vulcanized rubber. In the present invention, in order to clarify the distinction from the tackifier described below, not a softener in a broad sense but a softener in a narrow sense, that is, only those containing oils as a main component is used as a softener. The softener used in the present invention is not particularly limited, and specifically, an aromatic oil,
Extending oils such as naphthenic oils and paraffinic oils or plasticizers are exemplified. Among these, aromatic oils and naphthenic oils are preferred, and aromatic oils are particularly preferred, from the viewpoint of good compatibility with rubber, excellent hysteresis loss (tan δ), and excellent skid resistance.

The softener has a pour point of -30.degree. C. because of its excellent balance among abrasion resistance, rubber elasticity and skid resistance.
Those described above are preferable, those having -15 to + 15 ° C are more preferable, and those having -10 to + 10 ° C are particularly preferable. Further, in order to effectively grip the road surface, the pour point is preferably −40 ° C. or less, and more preferably −50 ° C. or less.

These softeners may be used alone or in combination of two or more.

The amount of the softening agent is selected from the viewpoints of grip performance and easiness of kneading work.
1 to 1000 parts by weight, preferably 1 to 1000 parts by weight,
The amount is more preferably 0 to 600 parts by weight, particularly preferably 30 to 500 parts by weight.

The kneading of the norbornene-based polymer and the softening agent may be carried out using a roller, a pressure kneader, a Banbury mixer or the like. After kneading, it is wound around a roll heated to 70 to 90 ° C., and the sheet is taken out to obtain a softener-containing norbornene-based polymer excellent in workability such as molding.

In the present invention, in addition to the case where the norbornene-based polymer containing a softener is used as it is (hereinafter, the norbornene-based polymer containing a softener in that case is referred to as an oil-extended product), a crosslinked powder (hereinafter, referred to as a crosslinked powder) is used. It can also be used as. When used as a crosslinked powder, examples of the crosslinking agent include sulfur, sulfur donating compounds such as tetramethylthiuram disulfide, and peroxides such as dicumyl peroxide, and are not particularly limited.

The method for crosslinking the softener-containing norbornene-based polymer is not particularly limited, and may be a method suitable for the crosslinking agent used. From the viewpoint of production efficiency and the like, the crosslinking speed is adjusted by the amount and type of the crosslinking agent and the crosslinking accelerator so that the crosslinking can be performed by heating at 140 to 170 ° C. for about 10 to 15 minutes in a closed container. It is preferable to keep it.

The method of pulverizing the crosslinked softener-containing norbornene-based polymer is not particularly limited. For example, it may be pulverized using a water-cooled roll, a pulverizer, or the like, or may be frozen and pulverized. The particle size is preferably from 10 to 100 mesh, more preferably from 15 to 60 mesh. If the particle size is too large, the rubber composition of the present invention tends to fall off after being molded and crosslinked, and if too small, it may cause difficulty in gripping. In order to obtain a preferable particle size, for example, classification may be performed using a classifier.

(Tackifier) The tackifier is a compound that increases the tackiness of the surface of the unvulcanized rubber compound. In a broad definition, the softener may be included in the tackifier, but in the present invention, a narrower tackifier, that is, a tackifier that is a resin or a liquid rubber is used. In the present invention, there is no particular limitation as long as it is such a tackifier.

Specific examples of the tackifier which is a resin include a coumarone-indene resin, a petroleum hydrocarbon resin, a formaldehyde resin, a polyterpene resin, a rosin ester resin and the like, and include natural rubber and / or diene synthetic rubber. Compatibility with hysteresis loss (tan
δ), petroleum hydrocarbon resins and polyterpene resins are preferred because of their preferred skid resistance. Further, from the viewpoint of dispersibility in natural rubber and / or diene-based synthetic rubber by kneading, the melting point is preferably 120 ° C or lower, more preferably 110 ° C or lower, particularly preferably 100 ° C or lower,
It is preferably at least 10 ° C, more preferably at least 70 ° C.

Specific examples of the tackifier which is a liquid rubber are not particularly limited, but the weight average molecular weight is 20.
Those having 0 to 40000 are preferable, and those having 800 to 6000 are more preferable. If the molecular weight is too small, the effect is small, and if the molecular weight is too large, it is difficult to disperse well when the compatibility with natural rubber and / or diene-based synthetic rubber is poor. From the viewpoint of compatibility with natural rubber and / or diene synthetic rubber, liquid butadiene rubber,
Liquid isobutylene rubber, liquid nitrile / butadiene rubber, and those obtained by introducing a polar group such as a carboxyl group or a hydroxyl group into a conjugated diene-based synthetic rubber such as butadiene rubber are preferable.

(Rubber Composition) The rubber composition of the present invention is a rubber composition containing a natural rubber and / or a diene-based synthetic rubber, a softener-containing norbornene-based polymer, and a tackifier. If necessary, other compounding agents, for example, a vulcanizing agent, a vulcanization accelerator, a vulcanization aid, a coloring agent, a bulking agent, an antioxidant, as long as the object and effects of the present invention are not impaired. A compounding agent generally added to a rubber composition such as a filler may be added.

The compounding amount of the softening agent is preferably 10 parts by weight with respect to 100 parts by weight of natural rubber and / or diene-based synthetic rubber from the viewpoint of good skid resistance balance and good abrasion resistance.
To 100 parts by weight, more preferably 15 to 90 parts by weight, particularly preferably 20 to 50 parts by weight.

The compounding amount of the softener-containing norbornene-based polymer is preferably 1 to 100 parts by weight of natural rubber and / or diene-based synthetic rubber from the viewpoint of the balance between road grip and abrasion resistance. It is 1000 parts by weight, preferably 2 to 500 parts by weight, more preferably 5 to 400 parts by weight.

The amount of the tackifier is determined by the balance with the amount of the norbornene-based polymer containing a softener. The amount of the tackifier is preferably 1 to 500 parts by weight per 100 parts by weight of natural rubber and / or diene-based synthetic rubber.
Parts by weight, more preferably 2 to 100 parts by weight, particularly preferably 5 to 50 parts by weight. When the blending amount of the softener-containing norbornene-based polymer with respect to 100 parts by weight of natural rubber and / or diene-based synthetic rubber is 50 parts by weight or less, the blending amount of the softener-containing norbornene-based polymer is set to 1. The amount of the tackifier is preferably 1/2 to 2, more preferably 3/4 to 3/2, and more preferably 1, that is, the same amount as the softener-containing norbornene-based polymer. It is particularly preferred that there is.

In order to obtain the rubber composition of the present invention, there is no particular limitation on the method of blending each component of the natural rubber and / or the diene-based synthetic rubber, the softener-containing norbornene-based polymer, and the tackifier. For example, kneading using a roll or a closed kneader may be used. Even if the natural rubber and / or the diene-based synthetic rubber, the softener-containing norbornene-based polymer, and the tackifier are simultaneously kneaded, the natural rubber and / or the diene-based synthetic rubber and the softener-containing norbornene-based polymer are kneaded. The tackifier may be added and kneaded, or the natural rubber and / or the diene-based synthetic rubber and the tackifier may be kneaded, and then the softener-containing norbornene-based polymer may be added and kneaded. When a tackifier is added, dispersion becomes easier as the kneading temperature approaches the melting point of the tackifier.

The rubber composition of the present invention can be suitably used as a material for an outsole of a tire or a shoe, and is particularly suitable for a material of a tread of a tire, and is most suitable for a material of a tread of a passenger tire or a studless tire. It is.

[0036]

EXAMPLES Reference Examples, Examples and Comparative Examples will be given below.
The present invention will be described in detail.

The tensile strength is measured according to JIS K-6251.
It measured according to. Wet skid resistance at 23 ° C as standard waterproof sandpaper (JIS-CC)
-60-Cw) and measured on a wet road surface by water injection. The skid resistance of the ice was measured using a smooth ice plate of -5 ° C as the road surface, and both were DSIR Road Research.
The value was measured using a portable skid resistance tester manufactured by rc Laboratory and expressed as an index with the value of Comparative Example 1 being 100. Hysteresis loss is JIS
According to K-7198, frequency 10Hz, heating rate 2 ° C
/ Min, using a viscoelasticity measuring device RSA-II manufactured by Rheometrics Co., Ltd. under the measurement conditions of dynamic strain 0.1%, -20 to +
It was measured at 100 ° C.

REFERENCE EXAMPLE 1 A norbornene-based polymer (NOSOREX, manufactured by Nippon Zeon, weight average molecular weight 1,500,00) was placed in an internal mixer (kneader, 75 liters, jacket temperature 45 ° C.).
0, glass transition temperature 39 ° C.) 100 parts by weight, 200 parts by weight of an aromatic oil having a pour point of −50 ° C. (manufactured by Hansen & Rosendahl Co., Ltd., Pioneer SRW 8), 5 parts by weight of zinc oxide, 1 part by weight of stearic acid Part, 2, 4
-Bis (n-octylthiomethyl) -6-methylphenol (Irganox 1520, manufactured by Ciba-Geigy),
Titanium oxide (manufactured by Ishihara Sangyo, R-780, primary particle average particle size about 0.21 μm), sulfur 2 parts by weight, N-cyclohexyl-2-benzothiazolesulfenamide 15 parts by weight, and N-oxydiethylene-2- 1 part by weight of benzothiazyl sulfenamide was added and heated at 145 ° C. to obtain a crosslinked product of a norbornene-based polymer containing a softener. This crosslinked product was pulverized with a pulverizer, passed through a 20 mesh,
A pulverized product that does not pass through the mesh was selected to obtain a softener-containing norbornene-based polymer a (crosslinked powder a).

Reference Example 2 The procedure of Reference Example 1 was repeated, except that the amount of the softener was changed to 400 parts by weight, to obtain a softener-containing norbornene-based polymer b (crosslinked powder b).

Reference Example 3 A softening agent was used as an aromatic oil having a pour point of 5 ° C. (Fle Co., Ltd., Fle
xM) Except for changing to 50 parts by weight, the same treatment as in Reference Example 1 was performed to obtain a softener-containing norbornene-based polymer c (crosslinked powder c).

Reference Example 4 A softening agent was used as an aromatic oil having a pour point of 5 ° C. (Flekosan, Fle
xM) Except for changing to 100 parts by weight, the same treatment as in Reference Example 1 was carried out to obtain a softener-containing norbornene-based polymer d (crosslinked powder d).

Reference Example 5 Naphthenic oil having a pour point of -50 ° C. (Pionie, manufactured by Hansen & Rosendahl Co.) as a softening agent shown in an internal mixer (kneader, 75 liters, jacket temperature 45 ° C.)
r SEW 8) 400 parts by weight were added, and 100 parts by weight of a norbornene-based polymer (Norsolex, manufactured by Zeon Corporation, weight average molecular weight 1,500,000, glass transition temperature 39 ° C) was added while stirring with a rotor. After mixing for 12 minutes and confirming that the kneading temperature reached 145 ° C, the mixture was taken out, wound around an 18-inch roll, and dispensed.
Upon cooling, a softener-containing norbornene-based polymer e (oil extended product e) was obtained.

Reference Example 6 A softening agent was used as an aromatic oil having a pour point of 5 ° C. (Fle
xM) Except for changing to 100 parts by weight, the same treatment as in Reference Example 5 was carried out to obtain a softener-containing norbornene-based polymer f (oil extended product f).

Reference Example 7 The procedure of Reference Example 5 was repeated except that the softening agent was replaced by 100 parts by weight of a naphthenic oil having a pour point of −22.5 ° C. (manufactured by Nippon San Petroleum, Sansen 450). Thus, a polymer g (oil extended product g) was obtained.

Example 1 50 kg of natural rubber (SMR-5L) was masticated for 8 minutes in an internal mixer (kneader, 75 liters, jacket temperature 50 ° C.). After confirming that the kneading temperature reached 160 ° C., the mixture was taken out and aged overnight. 60 parts by weight of natural rubber kneaded in an internal mixer (kneader, 75 liters, jacket temperature 50 ° C.), oil-extended butadiene rubber (Nipol BR-1441 manufactured by Zeon Corporation, aromatic oil 37 per 100 parts by weight of butadiene rubber 37) 55 parts by weight (containing 40 parts by weight of butadiene rubber and 15 parts by weight of an aromatic oil), and kneaded for 2 minutes.
-H carbon black (Tokai Carbon, Seast K
H) 50 parts by weight, aromatic oil (Flex M) 15 parts by weight, zinc oxide 3 parts by weight, stearic acid 2 parts by weight,
Kneading was continued for another 10 minutes. After adding 2 parts by weight of sulfur (325 mesh) and N-oxydiethylene-2-benzothiazodylsulfenamide (manufactured by Ouchi Shinko Co., Ltd., Noxeller MSA), the mixture was kneaded for 1 minute, discharged, and discharged with a 22-inch roll.
The sheet was repeatedly cut and the sheet was taken out to obtain a blended rubber.

After winding this blended rubber for 1 minute on a 6-inch roll preheated to 80 ° C., the crosslinked powder a10
Parts by weight and 10 parts by weight of a tackifier (terpene resin, manufactured by Yasuhara Chemical, YS-TO-85) are added little by little,
The mixture was kneaded with a roll for 9 minutes, dispensed, and air-cooled to 25 ° C. to obtain a rubber composition A.

The rubber composition A was press-crosslinked in a mold at 160 ° C. for 15 minutes using a 150-ton press to obtain a vulcanized molded product. Tensile strength, wet and ice skid resistance, hysteresis loss (ta)
nδ) was determined. Table 1 shows the results.

Examples 2 to 7 The same procedures as in Example 1 were carried out except that one of the crosslinked powders b to d and one of the oil extended products e to g was used instead of the crosslinked powder a to obtain rubber compositions B to G. To obtain a vulcanized molded product, tensile strength, wet and ice skid resistance, hysteresis loss (t
anδ) was determined. Table 1 shows the results.

Example 8 A rubber composition H was obtained in the same manner as in Example 1 except that 30 parts by weight of the vulcanized powder b was used instead of 10 parts by weight of the crosslinked powder a to obtain a vulcanized molded product and a tensile molding. Strength, wet and ice skid resistance, hysteresis loss (tanδ)
Was examined. Table 1 shows the results.

Comparative Example 1 A rubber composition I was obtained in the same manner as in Example 1 except that the crosslinked powder a and the tackifier were not used.
The tensile strength, wet and ice skid resistance, and hysteresis loss (tan δ) were examined. Table 2 shows the results.

Comparative Example 2 A rubber composition J was obtained in the same manner as in Example 1 except that vulcanized powder b was used instead of vulcanized powder a, and no tackifier was used. Obtain, tensile strength, wet and ice skid resistance, hysteresis loss (tan δ)
Was examined. Table 2 shows the results.

Comparative Example 3 A rubber composition K was obtained in the same manner as in Example 1 except that 20 parts by weight of the oil extender e was used instead of the vulcanized powder a, and no tackifier was used. To obtain the product, tensile strength, wet and ice skid resistance, hysteresis loss (t
anδ) was determined. Table 2 shows the results.

Comparative Example 4 A rubber composition L was obtained in the same manner as in Example 1 except that the vulcanized powder a was not used, and a vulcanized molded product was obtained.
Wet and ice skid resistance and hysteresis loss (tan δ) were examined. Table 2 shows the results.

Comparative Example 5 A pour point of 5 ° C. was used instead of the tackifier without using the vulcanized powder a.
A rubber composition M was treated in the same manner as in Example 1 except that 10 parts by weight of an aromatic oil (Flex M, manufactured by Fujikosan Co., Ltd.) was used.
And vulcanized molded articles were obtained, and the tensile strength, wet and ice skid resistance, and hysteresis loss (tan δ) were examined. Table 2 shows the results.

[0055]

[Table 1]

[0056]

[Table 2]

From the comparison between Examples 1 to 8 and Comparative Example 1, it was found that the combination of the softener-containing norbornene resin and the tackifier improved the balance between wet and ice skid resistance, especially the ice skid resistance. It can also be seen that the hysteresis loss is greatly improved.

From the comparison between Examples 1 to 8 and Comparative Examples 2 and 3, it was found that when only the softener-containing norbornene-based resin was blended,
It can be seen that it is not sufficiently improved, and a comparison between Examples 1 to 8 and Comparative Example 4 reveals that even if the tackifier alone is not added, it is not sufficiently improved.

[0059]

The rubber composition of the present invention has excellent skid resistance on wet road surfaces, snow and ice, and also has excellent hysteresis loss and excellent balance.
Therefore, it is suitable as a material for rubber parts that need to have slip resistance with a road surface such as a tread portion of a studless tire and an outsole of a shoe.

(Aspect) As an aspect of the present invention, (1)
Rubber composition containing natural rubber and / or diene-based synthetic rubber, softener-containing norbornene-based polymer, and tackifier, (2) natural rubber and / or diene-based synthetic rubber are composed of natural rubber, butadiene rubber, isoprene A rubber selected from rubber, styrene-butadiene copolymer rubber, styrene-butadiene-isoprene copolymer rubber, or a rubber obtained by mixing a plurality of rubbers selected from these rubbers; (4) The rubber composition according to (1) or (2), wherein the natural rubber and / or the diene-based synthetic rubber has a glass transition temperature of 20 ° C. or lower, preferably 0 ° C. or lower, more preferably −20 ° C. or lower.
The rubber composition according to any one of (1) to (3), wherein the natural rubber and / or the diene-based synthetic rubber has a Mooney viscosity of 10 to 150, preferably 20 to 100, more preferably 30 to 60. Is exemplified.

According to an embodiment of the present invention, (5) the softening agent-containing norbornene-based polymer is a composition obtained by adding a softening agent to a norbornene-based polymer, or vulcanized by adding a softening agent to a powder. The rubber composition according to any one of (1) to (4), wherein the norbornene-based polymer is obtained by ring-opening polymerization of a norbornene-based monomer. (7) a norbornene-based monomer, wherein the carbon at the 2- and / or 3-position of the norbornene ring is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms,
(6) The rubber composition according to (6), which has a structure bonded to an alkylene group of 4, an alkylidene group of 1 to 4 carbon atoms, or an aromatic hydrogen sensitized residue of 6 to 20 carbon atoms.
(8) The norbornene-based monomer is 5-norbornene,
It is selected from 2-methyl-5-norbornene, 2-ethyl-5-norbornene, 2-butyl-5-norbornene, 2,3-dimethyl-5-norbornene and 2-vinyl-5-norbornene (6 ) Or (7), wherein the norbornene-based polymer has a glass transition temperature of -50 to + 200 ° C, preferably 0 to 150 ° C.
C, more preferably 10 to 50 C (5) to
The rubber composition according to any one of (8) and (10), wherein the norbornene-based polymer has a weight average molecular weight (Mw) of 100,000 in terms of polystyrene measured by high performance liquid chromatography using tetrahydrofuran as a developing solvent.
~ 10,000,000, preferably 500,000 ~
7,000,000, more preferably 700,000-
(5) The rubber composition according to any one of (5) to (9), wherein the softening agent is mainly composed of oils. The rubber composition according to any one of (12), wherein the softener is selected from aromatic oil, naphthenic oil, and paraffin oil (5).
(13) The rubber composition according to any of (11) to (11).
A softener having a pour point of -30 ° C or higher, preferably -1
5 to + 15 ° C, more preferably -10 to + 10 ° C
(14) The rubber composition according to any one of (5) to (12), wherein the softening agent has a pour point of -40 ° C or lower, preferably -50 ° C or lower (5). ~ (1
2) The rubber composition according to any one of (1) and (15), wherein the softener-containing norbornene-based polymer has a softener content of 1 to 1000 parts by weight, preferably 10 to 600 parts by weight, per 100 parts by weight of the norbornene-based polymer. Parts by weight, more preferably 1
The rubber composition according to any one of (5) to (14), wherein the rubber composition has a particle size of 10 to 100 mesh, wherein the softening agent-containing norbornene-based polymer is vulcanized and powdered. Is a rubber composition according to any one of (5) to (16), which has a mesh size of 15 to 40 mesh.

As an embodiment of the present invention, (17)
The tackifier is a resin or a liquid rubber (1) to
(16) The rubber composition according to any one of (16) and (18) the tackifier is selected from a coumarone-indene resin, a petroleum hydrocarbon resin, a formaldehyde resin, a polyterpene resin, and a rosin ester resin (17). The rubber composition according to (19), wherein the tackifier has a melting point of 120 ° C. or lower, preferably 110 ° C. or lower, more preferably 100 ° C.
Hereinafter, the rubber composition according to (18), which is preferably at least 10 ° C, more preferably at least 70 ° C, (20)
(17) The rubber composition according to (17), wherein the tackifier is a liquid rubber having a weight average molecular weight of 200 to 10,000, preferably 800 to 6,000, (21) the tackifier is liquid butadiene rubber, liquid isobutylene rubber, liquid nitrile. The rubber composition according to (17) or (20), which is selected from butadiene rubber and a liquid rubber having a polar group introduced into a conjugated diene-based synthetic rubber such as butadiene rubber, is exemplified.

Further, as an embodiment of the present invention, (2
2) Natural rubber and / or diene-based synthetic rubber 100
10 to 100 parts by weight, preferably 35 to 90 parts by weight, more preferably 30 to 50 parts by weight, based on parts by weight, (22) 100 parts by weight of natural rubber and / or diene-based synthetic rubber 1 to 1000 parts by weight, preferably 2 to 500 parts by weight, more preferably 5 to 400 parts by weight of a softener-containing norbornene-based polymer (1) to
(21) The rubber composition according to any of (21), (23) 1 to 500 parts by weight of a tackifier, preferably 2 to 100 parts by weight of natural rubber and / or diene-based synthetic rubber.
100 parts by weight, more preferably 5 to 50 parts by weight,
And natural rubber and / or diene-based synthetic rubber 100
When the amount of the softener-containing norbornene-based polymer is 50 parts by weight or less based on the weight of the softener-containing norbornene-based polymer, the amount of the tackifier is 1 based on the amount of the softener-containing norbornene-based polymer.
/ 2 to 2, preferably 3/4 to 3/2 (1) to
(22) The rubber composition according to any one of (22) and (24).
(1) Outsole of a shoe obtained by molding and crosslinking the rubber composition according to any one of (1) to (23), (25) (1) to (2)
Treads obtained by molding and cross-linking the rubber composition described in any of 3), (26) Tires having the treads described in (25), and the like.

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Claims (3)

[Claims] 1. A rubber composition comprising a natural rubber and / or a diene-based synthetic rubber, a softener-containing norbornene-based polymer, and a tackifier. 2. A tire having a tread obtained by crosslinking the rubber composition according to claim 1. 3. A shoe outsole formed by crosslinking the rubber composition according to claim 1.