JPH03188138A - Rubber composition for tire slip preventing apparatus and tire slip preventing apparatus - Google Patents

Abstract

PURPOSE:To improve the strengths, elasticity, durability, high load bearing capacity, colorability, etc., by compounding a specific copolymer rubber, zinc methacrylate, and an org. peroxide. CONSTITUTION:By hydrogenating conjugated diene units of a copolymer rubber prepd. from an ethylenically unsatd. nitrile and a conjugated diene, a copolymer rubber contg. 20-60wt.% nitrile units and 30wt.% or less diene units is obtd. Separately, by reacting one mol of methacrylic acid with 0.5-3.2mol of a zinc compd. and removing coarse particles from the reaction product, zinc methacrylate contg. 5wt.% or lower coarse particles with particle diameters of 20mum or higher is prepd. 100 pts.wt. resulting rubber is compounded with 10-100 pts.wt. zinc methacrylate 0.2-10 pts.wt. org. peroxide, and, if necessary, a reinforcement such as silica, a colorant, a crosslinking aid, a plasticizer, a stabilizer, etc., giving the title compsn. which, when vulcanized, exhibits a modulus at 100% elongation of 50kg/cm<2> or higher.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a rubber tire slip prevention device and a tire that have high strength, high modulus of elasticity, and are excellent in durability, high load resistance, colorability, etc. The present invention relates to a rubber composition for anti-slip devices.

C. Prior Art] In order to prevent automobile tires from slipping on snowy, frozen, muddy, or other road surfaces, anti-slip devices such as metal chains are used.

In recent years, anti-slip devices have been developed that use polymer materials such as rubber and plastic instead of metal chains to prevent noise and damage to road surfaces.

Hitherto, such non-metallic tire slip prevention devices have been known to have various structures such as ladder type and net type.Also, as polymer materials, natural rubber (NR) has been known.
), styrene-butadiene copolymer rubber (SBR), polybutadiene rubber (BR), or polyurethane.

By the way, tire anti-slip devices have excellent running performance, maneuverability, ride comfort, ease of attachment and removal, and in order to be used under harsh conditions, they must have durability and strength characteristics (especially strength characteristics at low temperatures). , it is required to have excellent physical properties such as abrasion resistance, elastic modulus, and heat generation property. Furthermore, it is required that the molding process is easy and that the colorability is good.

However, conventionally used rubbers generally have poor strength characteristics and durability, and have the drawback of not being able to withstand high loads. Additionally, tire anti-slip devices must have a high modulus of elasticity in order to avoid deformation, detachment, or destruction due to the centrifugal force that accompanies tire rotation; however, high modulus of rubber makes it difficult to mold. , and the strength decreases significantly.

Therefore, in order to obtain rubber tire slip prevention devices with excellent strength and functionality, it is generally not necessary to mold and vulcanize only the rubber (in the rubber, steel cord, nylon net,
It is molded with a core material such as polyester fiber embedded in it. However, since tire anti-slip devices usually have a complex strip-like structure in the form of a ladder or net, it is extremely difficult to embed these core materials in the center of the rubber and then mold and vulcanize it. , and time-consuming.

In the past, various proposals have been made regarding methods for efficiently manufacturing rubber tire anti-slip devices using core materials (for example, JP-A-57-11040, JP-A-62-1).
No. 48250, JP-A-62-231714, JP-A-6
No. 3-3940, JP-A No. 63-37906, etc.) are still time-consuming and do not provide sufficient improvement in molding processability.

In addition, in order to obtain a rubber tire slip prevention device with a high elastic modulus without using a core material, a rubber composition in which short fibers are mixed and dispersed in natural rubber or styrene-butadiene copolymer rubber and oriented is used. A method of molding and vulcanizing the mesh rubber band has been proposed (Japanese Unexamined Patent Publication No. 62-205807), but this method cannot prevent a decrease in strength.

On the other hand, tire slip prevention devices using polyurethane are
Although a core material is not necessary, it has the problem of becoming soft and damaged due to heat generated during running.

[Problems to be Solved by the Invention] The object of the present invention is to provide a rubber tire anti-slip device and a tire anti-slip device that have high strength, high elastic modulus, and are excellent in durability, high load resistance, colorability, etc. An object of the present invention is to provide a rubber composition for use in rubber compositions.

Another object of the present invention is to provide a tire slip prevention device made of rubber that has excellent strength characteristics, elastic modulus, durability, etc., and is easy to mold and process without using a core material.

As a result of intensive research to overcome the problems of the prior art, the present inventors have discovered that an ethylenically unsaturated nitrile-conjugated diene polymer having a content of conjugated diene units in the polymer chain of 30% by weight or less A tire slip prevention device was created by vulcanization molding using a vulcanizable rubber composition containing polymerized rubber, zinc salt of methacrylic acid, and organic peroxide.
It has been found that it has high strength and high modulus of elasticity, excellent durability, high load resistance, etc., and has various properties such as being able to be colored freely without causing a decrease in physical properties.

When this tire slip prevention device was attached to an automobile tire and a running test was conducted, it showed excellent durability without breaking even after running for 500 km. Moreover, since the rubber composition exhibits the above-mentioned properties without using a core material, it has good moldability.

On the other hand, even when a metal salt of an ethylenically unsaturated carboxylic acid other than a zinc salt of methacrylic acid is blended, a satisfactory tire slip prevention device could not be obtained.

The present invention has been completed based on these findings.

[Means to solve the problem]

(Thus, according to the present invention, 100 parts by weight of a copolymer rubber in which the content of conjugated diene units in the polymer chain derived from at least ethylenically unsaturated nitrile and conjugated diene is 30% by weight or less, methacrylic Zinc salt of acid 10-10
A rubber composition for a tire anti-slip device is provided, which contains 0 parts by weight and 0.2 to 10 parts by weight of an organic peroxide.

Further, according to the present invention, there is provided a tire slip prevention device formed by vulcanization molding the rubber composition.

The present invention will be explained in detail below.

(Copolymer rubber) In the present invention, as a polymer material, a copolymer rubber (hereinafter referred to as (abbreviated as "ethylenically unsaturated nitrile-conjugated diene-based highly saturated copolymer rubber") is used.

The ethylenically unsaturated nitrile-conjugated diene-based highly saturated copolymer rubber used in the present invention is composed of an ethylenically unsaturated nitrile such as acrylonitrile and methacrylonitrile;
A copolymer rubber obtained by hydrogenating the conjugated diene unit of a copolymer rubber with a conjugated diene such as 3-butadiene, isoprene, or 1,3-pentadiene, a monomer copolymerizable with the above two types of monomers, e.g. , a vinyl aromatic compound, an unsaturated carboxylic acid ester, an unsaturated carboxylic acid alkyl ester, an unsaturated carboxylic acid alkoxyalkyl ester, an unsaturated carboxylic acid fluoroalkyl ester, etc., and a copolymerization thereof. This is a copolymer rubber in which the conjugated diene units in the rubber are hydrogenated.

Specific examples include acrylonitrile-butadiene copolymer rubber, acrylonitrile-butadiene-isoprene copolymer rubber, acrylonitrile-isoprene copolymer rubber, acrylonitrile-butadiene-acrylate copolymer rubber, acrylonitrile-butadiene-acrylic acid copolymer rubber, and acrylonitrile-butadiene copolymer rubber. Examples include -acrylate-methacrylic acid copolymer rubber and hydrogenated copolymer rubbers thereof. These copolymer rubbers can be used alone or in combination of two or more.

These copolymer rubbers contain 20 to 60% by weight of ethylenically unsaturated nitrile units in the polymer chain, and the content of conjugated diene units is reduced to 30% by weight or less by means such as partial hydrogenation.

If the amount of ethylenically unsaturated nitrile units is less than 20% by weight, the resulting copolymer rubber will have poor oil resistance. If it exceeds 60% by weight, the resulting copolymer rubber will have reduced flexibility. If the conjugated diene units exceed 30% by weight, no improvement in tensile strength can be achieved. Preferably, the conjugated diene units are 0 to 20% by weight.

(Zinc salt of methacrylic acid) The zinc salt of methacrylic acid used in the present invention can be obtained by reacting a zinc compound such as zinc oxide, zinc carbonate, or zinc hydroxide with methacrylic acid according to a conventional method. can. This zinc salt of methacrylic acid contains methacrylic acid and a zinc compound in a molar ratio of 1:0.5 to 1:3.2.
Preferably, those obtained by reaction within the range of 1:0.5 to 1:2.5 are desirable. Here, the molar ratio of methacrylic acid and zinc compound is a value calculated based on the molecular weight of methacrylic acid and the substitution of the zinc compound.

The blending ratio of zinc salt of methacrylic acid is 100% of the copolymer rubber.
The amount is 10 to 100 parts by weight. If this blending ratio is less than 10 parts by weight or more than 100 parts by weight, the effect of improving tensile strength will be reduced. The blending ratio of the zinc salt of methacrylic acid is preferably 20 to 90 parts by weight, particularly preferably 30 to 80 parts by weight.

In addition, zinc salt of methacrylic acid is a reaction product of methacrylic acid and a zinc compound in a molar ratio of 1:0.5 to 1:3.2, and the amount of methacrylic acid (i.e., the amount of methacrylic acid in the product) The amount of bound methacrylic acid is preferably 15 to 50 parts by weight, more preferably 20 to 40 parts by weight, based on 100 parts by weight of the copolymer rubber. If the amount of methacrylic acid is too small, 10
0% tensile stress is insufficient, and when used as a tire slip prevention device, it becomes easily deformed and damaged by centrifugal force.

The zinc salt of methacrylic acid is highly dispersed in the copolymer rubber, and in order to improve the tensile strength, the coarse particles are removed, that is, the coarse particles with a particle size of 20 μm or more are classified by wind classification or the like. It is desirable that the content is 5% by weight or less, more preferably 0% by weight.

In addition, the zinc salt of methacrylic acid can be prepared by adding methacrylic acid and a zinc compound to a copolymer rubber, and then in the copolymer rubber.
5 itu). In this case, it is preferable to use a zinc compound in which coarse particles with a particle size of 20 μm or more are substantially removed by classification so that the content is 5% by weight or less. The zinc compounds used are zinc oxide, zinc carbonate, zinc hydroxide, etc.
The blending ratio thereof is usually 5 to 80 parts by weight, preferably 10 to 60 parts by weight, per 100 parts by weight of the copolymer rubber. The blending ratio of methacrylic acid is usually 10 to 50 parts by weight, preferably 15 to 5 parts by weight, per 100 parts by weight of rubber.
0 parts by weight, more preferably 20 to 40 parts by weight. If the amount of methacrylic acid added is too small, 100% of the vulcanizate
This is not preferred because the tensile stress decreases. The molar ratio of methacrylic acid to zinc compound ranges from 1:05 to 1:3.2, preferably from 1:0.5 to 1:2.5.

(Organic Peroxide) The organic peroxide used in the present invention is not particularly limited as long as it is used for normal peroxide vulcanization of rubber.

Specific examples of such peroxides include dicumyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, benzoyl peroxide, 2,5-dimethyl-2,5- (t-butylperoxy)hexane 3.2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 2,5-dimethyl-2,5-mono(t-butylperoxy)hexane, α
, α゛-bis(t-butylperoxy-m-isopropyl)benzene, and the like.

These organic peroxides are used alone or in combination of two or more, and are usually used in an amount of 0.0% per 100 parts by weight of rubber. 2 to 10 parts by weight, preferably 0.5 to 8 parts by weight, particularly preferably 1 to 6 parts by weight
Used in parts by weight range.

It is desirable to appropriately determine the optimum amount depending on the required physical property values.

(Rubber composition) The rubber composition of the present invention contains an organic peroxide,
It is a vulcanizable rubber composition.

The rubber composition may be produced by any method as long as it provides good dispersion of the zinc salt of methacrylic acid or the methacrylic acid and zinc compound. Generally, rolls, banburys, kneaders normally used in the rubber industry
etc. are mixed.

In addition, the order of mixing each component is to mix the copolymer rubber and zinc salt of methacrylic acid in advance to obtain sufficient dispersion, and then add the organic peroxide, or add the zinc compound to the copolymer rubber in advance. A preferred method is to add and mix to obtain sufficient dispersion, then mix or absorb methacrylic acid, then add organic peroxide and mix uniformly.

The vulcanizable rubber composition of the present invention also contains reinforcing materials such as carbon black and silica, fillers such as calcium carbonate and talc, triallyl isocyanurate, trimethylolpropane triacrylate, and m-phenylene bismaleimide. Various additives commonly used in the rubber industry, such as crosslinking aids, plasticizers, stabilizers, vulcanization aids, and colorants, can be mixed and used as appropriate.

In the rubber composition of the present invention, it is preferable that the 100% tensile stress of the vulcanizate is 50 kg/crrr or more in terms of physical properties as a tire slip prevention device, but among these additives, silica is , is particularly preferred since it improves the 100% tensile stress of the vulcanizate. Further, even if various pigments are added as colorants, the physical properties such as tensile strength are hardly reduced, so it is possible to manufacture a tire slip prevention device with any color tone.

(Tire anti-slip device) The rubber composition of the present invention can be prepared by a conventional method,
For example, by making an unvulcanized rubber string by extrusion molding, placing it in a mold with grooves such as a ladder type or net type, and vulcanizing it by press molding, various structures of anti-slip tires can be manufactured. The device can be manufactured.

The tire slip prevention device of the present invention may use a core material, but it can also exhibit sufficient practical performance even when molded and vulcanized without using a core material.

The anti-slip device obtained using the rubber composition of the present invention was tested on a dry road by being attached to a tire.
Even after traveling 5,000 km, both strength and abrasion resistance remain at extremely good levels.

Due to these characteristics, it is suitable for fields that require high load resistance, such as anti-slip devices for TB tires.

〔Example〕

The present invention will be described in more detail below with reference to Reference Examples, Examples, and Comparative Examples. Incidentally, the blended parts in Examples and Comparative Examples are parts by weight.

In addition, in the Examples and Comparative Examples, the vulcanizable rubber composition was prepared by mixing the ingredients listed in each table in a kneader, excluding the organic peroxide, and then mixing the organic peroxide in a roll. Manufactured by.

The physical property measurement method and classification method are as follows.

<Tensile strength, elongation, hardness, 100% tensile stress> JIS
Measured according to K-6301.

<Dynamic exothermic property> Measured temperature 150% by Gutdrich flexmeter
Measured at °C.

<Pico Wear> Based on ASTM D-2228, the wear amount was measured using a Pico abrasion tester under the conditions of a load of 4.5 kg and 80 cycles, and was expressed in CC.

Classification> A zinc compound or a zinc salt of methacrylic acid was classified using a classifier manufactured by Albine (100MZR) under the following conditions.

Air amount 42 NITIl/hr Rotation speed 13,000 rpm <Particle size distribution> ■Centrifugal sedimentation type particle size distribution measuring device manufactured by Shimadzu Corporation (SA-
CF2 type) was used to measure the content (% by weight) of coarse particles with a particle size of 20 μm or more.

[Reference Example 1] (Synthesis of ethylenically unsaturated nitrile-conjugated diene-based highly saturated copolymer rubber) Acrylonitrile-butadiene copolymer rubber (rubber number A) having a bound acrylonitrile content of 37% was dissolved in methyl isobutyl ketone. , using a Pd-carbon catalyst to produce hydrogenated copolymer rubbers (rubber numbers B-G) having various conjugated diene unit contents listed in Table 1.

Similarly, acrylonitrile-butadiene copolymer rubber C with a bound acrylonitrile content of 45% or less, NBR
) is hydrogenated to obtain rubber number H- listed in Table 1.
A hydrogenated copolymer rubber of J was prepared.

(The following is a blank space) [Reference Example 2] (Synthesis of zinc salt of methacrylic acid) Zinc oxide was added to toluene, methacrylic acid was added dropwise with stirring, and the mixture was reacted for about 1 hour. After aging for 16 hours, the precipitate was filtered and dried under reduced pressure at 80°C. After drying, it was ground in a mortar and sifted through a 60-mesh wire mesh to obtain zinc salt of methacrylic acid (hereinafter sometimes abbreviated as Zn-MA).
I got it. The classified product is further classified using a wind classifier,
The content of coarse particles with a particle size of 20 μm or more was reduced to 5% by weight or less.

The results are shown in Table 2.

(Left below) [Example 1] N containing 37% of bound acrylonitrile listed in Table 1
Copolymer rubbers with different hydrogenation rates of BR (rubber numbers A to G)
A vulcanizable rubber composition was prepared according to the formulation shown in Table 3. The zinc salt of methacrylic acid was prepared by reacting methacrylic acid and zinc oxide in 5 situ in a copolymer rubber (molar ratio = 1:1.06).

Then, press vulcanization was performed under the vulcanization conditions listed in Table 3 to obtain 2
A vulcanized sheet with a thickness of mm was prepared, and the vulcanized physical properties were measured according to JISK-6301. The results obtained are shown in Table 3.

From the results in Table 3, it can be seen that when the content of conjugated diene units in the copolymer rubber is small (it is true that the tensile strength is improved), on the other hand, when the content of conjugated diene units in the copolymer rubber exceeds 30% by weight ( Experiment Nos. 6 to 7) or when SBR was used (Experiment No. 8), the tensile strength was low and the strength for use in a tire slip prevention device was insufficient.

[Example 2] N containing 45% of bound acrylonitrile listed in Table 1
Copolymer rubber with different hydrogenation rate of BR (rubber number H-J)
A vulcanizable rubber composition was prepared according to the formulation shown in Table 4. Similarly, press vulcanization was performed under the vulcanization conditions listed in Table 4, and the vulcanization physical properties were measured in the same manner as in Example 1.

The results are shown in Table 4.

From the results in Table 4, it can be seen that the rubber composition of the present invention has excellent strength and elongation properties, and that the lower the content of conjugated diene units in the copolymer rubber, the higher the tensile strength. I understand.

(Margin below) (*l) Same as footnote in Table 2, (*3) Same as footnote in Table 3.

[Example 3] Using hydrogenated NBR (rubber number E) listed in Table 1, vulcanizable rubber compositions were prepared by varying the amounts of zinc oxide and methacrylic acid added as listed in Table 5. . A vulcanized sheet was obtained by press vulcanization under the vulcanization conditions described in the same table, and the vulcanized physical properties were measured.

The results are shown in Table 5.

From Table 5, the molar ratio of methacrylic acid and zinc oxide is 1:0.
．． It can be seen that any ratio within the range of 5 to 1:3.2 exhibits high tensile strength and elongation.

(Left below) [Example 4] As zinc compounds, zinc compounds shown in Table 6 were classified with an air classifier to remove coarse particles with a particle size of 20 μm or more, and unclassified products were used, and As a copolymer rubber,
A compounded rubber composition was prepared using hydrogenated NBR (rubber number E) according to the compounding recipe shown in Table 6. A vulcanized product was obtained by press vulcanization under the vulcanization conditions described in the same table, and the vulcanized physical properties were measured.

The results are shown in Table 6.

As is clear from Table 6, the tensile strength can be further improved by classifying the zinc compound to remove coarse particles with a particle size of 20 μm or more.

(Left below) [Example 5] Using the hydrogenated NBR (rubber number E) listed in Table 1, the seventh
A compounded rubber composition was prepared according to the formulation shown in the table. A vulcanizate was obtained by press vulcanization under the vulcanization conditions described in the same table, and the results of measurement of the properties required for use in tire anti-slip devices are shown in Table 7.

As is clear from Table 7, the vulcanizate obtained from the rubber composition of the present invention has low dynamic exothermic property and shows very little change in hardness at high temperatures. Therefore, when this rubber composition is used in a tire slip prevention device, it does not easily soften and break due to heat generated during running.

(Margin below) ($1) Same as table 2 footnote, (Umbrella 3) Same as footnote in Table 3.

[Example 6] Hydrogenated NBR (manufactured by Nippon Zeon Co., Ltd., trade name: Z-Ball 2)
020, hydrogenation rate 90%, bound acrylonitrile amount 3
7%, conjugated diene unit content 6.3%), zinc salt of methacrylic acid (Zn-MA) listed in Table 2 and organic peroxide were blended according to the formulation listed in Table 8 to form a rubber composition. I prepared something.

Press vulcanization was performed under the vulcanization conditions described in the same table to obtain a 2 mm thick vulcanized sheet, and the vulcanized physical properties were measured.

The results are shown in Table 8.

As is clear from Table 8, when using zinc salt of methacrylic acid whose content of coarse particles with a particle size of 20 μm or more was 5% by weight or less by classification (Experiment No. 24 to 27), the content of coarse particles decreased. It can be seen that the tensile strength is even higher than when a large one is used (Experiment No. 28).

(The following is a blank space) [Example 7] A compounded rubber composition was prepared using the classified product of the zinc salt of methacrylic acid (No. 2) listed in Table 2 according to the formulation listed in Table 9. Press vulcanization under the vulcanization conditions listed in the same table, 2
A vulcanized sheet with a thickness of mm was obtained and the vulcanized physical properties were measured.

These results indicate that the vulcanizable rubber composition of the present invention has very high strength, especially at low temperatures, and also has excellent elongation, abrasion resistance, and 100% tensile stress. Therefore, it can be seen that the rubber composition is extremely excellent as a rubber composition for a tire slip prevention device.

On the other hand, when using SBR or BR (experiment numbers 32-33
) has low strength and elongation properties and insufficient abrasion resistance.

(The following is a blank space.) (Umbrella 7) Polybutadiene manufactured by Nippon Zeon Co., Ltd., product 2 two-ball BR1220 [Example 8] A rubber composition containing silica was prepared according to the formulation shown in Table 10. Press vulcanization was performed under the vulcanization conditions described in the same table, and the vulcanization physical properties were measured. The results are shown in the same table.

Usually when a filler such as carbon black is added, 10
Although the 0% tensile stress decreases, as is clear from Table 1O, when silica is blended into the rubber composition of the present invention, it is on the contrary improved. It also has improved wear resistance.

Table 10 (margins below) (*3) Same as footnotes in Table 3. (*6) Same as footnote in Table 8.

(8th grade) Manufactured by Nippon Aerosil Co., Ltd., product name Aerosil 200
[Example 9] As shown in Table 11, a compounded rubber composition was prepared by light color compounding. When only pigment was blended, a translucent vulcanizate was obtained. Furthermore, when titanium oxide was used in combination, an opaque vulcanizate with a vivid color was obtained.

As is clear from Table 11, it can be seen that the physical properties hardly change even when various pigments are added.

Table 11 (Margin below) (*3) Same as table 3 footnote. (*6) Same as footnote in Table 8.

[Example 10] The rubber composition of Experiment No. 5.11.15.19.24.30 was vulcanized and molded to produce a net-type belt-shaped tire slip prevention device (thickness 6 mm, no core material), and a tire We installed it on the vehicle and conducted an actual driving test on a dry road. Even after running for 5,000 km, there was no breakage, and both strength and abrasion resistance were at extremely good levels, demonstrating excellent performance.

[Example 11] Vulcanizable rubber compositions were prepared using the various rubbers shown in Table 12 and according to the formulations shown in Table 12. Same (, 1st
Press vulcanization was performed under the vulcanization conditions listed in Table 2, and the vulcanized physical properties were measured. However, the zinc oxide used was one in which the content of coarse particles with a particle size of 20 μm or more was 0% by weight by classification.

The results are shown in Table 12.

(Left below) Table 12 shows that the rubber compositions of the present invention (experiment numbers 40 to 4)
It can be seen that 1) has excellent strength and elongation properties, hardness, and 100% tensile stress. On the other hand, rubber compositions using natural rubber or NBR (experiment numbers 42 to 44)
Strength and elongation properties are insufficient. In addition, even if hydrogenated NBR is used as a copolymer rubber, when a metal salt of an ethylenically unsaturated carboxylic acid other than a zinc salt of methacrylic acid is blended (experiment numbers 45 to 47), the strength and elongation properties are insufficient. That's enough.

[Example 12] Using the rubber composition prepared in Example 11 (experiment numbers 40 to 47 in Table 12), the “non-metallic and cable-type A net-type tire slip prevention device with a structure similar to certification number 62-004A described in "Tire Anti-Slip Device Certified Product - Keno" was manufactured as a prototype. These tire anti-slip devices are
No core material was used in either case. Further, a tire slip prevention device with a core material was created using the rubber composition of Experiment No. 42 and a nylon net as the core material.

The thickness of these tire anti-slip devices is 6mm.
Met.

Dry road driving tests were conducted using the prototype tire slip prevention device.

Driving conditions: Speed 50 km/hr Vehicle type Toyota Corona (1800cc) Table 13 shows the driving test results.

From the results in Table 13, it can be seen that the tire anti-slip device obtained using the rubber composition of the present invention has very excellent properties.

(The following is a blank space) Table 13 [Effects of the Invention] According to the present invention, a non-slip tire with high strength and high modulus of elasticity, excellent durability, high load resistance, etc., and good colorability and moldability. A device and a rubber composition for the device can be provided.

Claims (11)

[Claims] (1) 100 parts by weight of a copolymer rubber in which the content of conjugated diene units in the polymer chain derived from at least ethylenically unsaturated nitrile and conjugated diene is 30% by weight or less;
A rubber composition for a tire anti-slip device containing 10 to 100 parts by weight of a zinc salt of methacrylic acid and 0.2 to 10 parts by weight of an organic peroxide. (2) The copolymer rubber is obtained by hydrogenating the conjugated diene units of a copolymer rubber containing 20 to 60% by weight of ethylenically unsaturated nitrile units derived from ethylenically unsaturated nitrile and conjugated diene. A composition according to claim 1. (3) The zinc salt of methacrylic acid is a product obtained by reacting methacrylic acid and a zinc compound at a molar ratio of 1:0.5 to 1:3.2. Composition of. (4) Claim 1, wherein the zinc salt of methacrylic acid contains 5% by weight or less of coarse particles with a particle size of 20 μm or more.
4. The composition according to any one of items 3 to 3. (5) The composition according to claim 1 or 2, wherein the zinc salt of methacrylic acid is produced by adding methacrylic acid and a zinc compound to a copolymer rubber and reacting them in the copolymer rubber. (6) Zinc salt of methacrylic acid is obtained by adding methacrylic acid and a zinc compound to a copolymer rubber in a molar ratio of 1:0.5 to 1:3.2 and reacting in the copolymer rubber. The composition according to claim 5, which is manufactured by: (7) The composition according to claim 5 or 6, wherein the zinc compound contains 5% by weight or less of coarse particles having a particle size of 20 μm or more. (8) The composition according to any one of claims 1 to 7, which contains silica and/or a colorant. (9) 100% tensile stress of vulcanizate is 50 kg/cm^2
The composition according to any one of claims 1 to 8, which is the above. (10) A tire slip prevention device obtained by vulcanizing and molding the composition according to any one of claims 1 to 9. (11) Claim 1 obtained by vulcanization molding without using a core material
The tire slip prevention device described in 0.