JP5912936B2 - Rubber composition for tire and studless tire - Google Patents

Description

The present invention relates to a rubber composition for a tire and a studless tire produced using the same.

In recent years, due to soaring fuel costs and the introduction of environmental regulations, the demand for lower fuel consumption of vehicles has become stronger, and even for studless tires used on icy and snowy roads, excellent fuel efficiency is required along with performance on snow and ice. ing. Conventionally, carbon black, which can easily interact with the rubber component and has an excellent reinforcing effect, has been used as a filler for tire rubber compositions. Is being considered for use.

However, silica has lower affinity with natural rubber, butadiene rubber, styrene butadiene rubber, etc., which are widely used for tires, and is inferior to carbon black in terms of mechanical strength (tensile strength and elongation at break). Many.

As a method for solving this problem, it has been proposed to use a silane coupling agent having reactivity with a rubber component or silica, but it is difficult to sufficiently advance the reaction with silica, and unreacted silica. May remain poorly dispersed and the desired performance may not be exhibited. Further, in order to prevent this, if a large amount of silane coupling agent is blended, due to the residual silane coupling agent, rubber burning during processing, degradation performance of vulcanized rubber, and the like may be caused.

Patent Document 1 discloses a tire rubber composition containing a basic aqueous solution having a pH of 8 to 12 and silica for the purpose of enhancing the compatibility between silica and rubber, but the interaction between rubber and silica is disclosed. Cannot be sufficiently obtained, and the improvement effect such as low fuel consumption is not satisfactory.

In addition, in the case of a studless tire, there is a tendency to add a large amount of plasticizer such as oil for the purpose of ensuring performance on snow and ice (low temperature performance), but this also tends to reduce wear resistance. Accordingly, it is desired to provide a silica-containing rubber that can improve fuel economy, snow and ice performance, wear resistance, and processability in a well-balanced manner.

JP 2000-219779 A

An object of the present invention is to solve the above-mentioned problems and provide a rubber composition for tires that improves fuel efficiency, performance on snow and ice, wear resistance, and processability in a well-balanced manner, and a studless tire using the same. .

The present invention comprises 5 to 200 parts by mass of silica and 0.1 to 40 parts by mass of cyclized rubber with respect to 100 parts by mass of the rubber component, and the content of butadiene rubber in 100% by mass of the rubber component is 10 to 10 parts by mass. It is related with the rubber composition for tires which is 80 mass%.

The cyclization rate of the cyclized rubber is preferably 0.1 to 40%.
The cyclized rubber is preferably at least one selected from the group consisting of cyclized natural rubber, cyclized isoprene rubber, and cyclized butadiene rubber.

It is preferable that 1-50 mass parts of carbon black is included with respect to 100 mass parts of the rubber component.
The present invention relates to a studless tire having a tread produced using the rubber composition.

According to the present invention, 5 to 200 parts by mass of silica and 0.1 to 40 parts by mass of cyclized rubber are included with respect to 100 parts by mass of the rubber component, and the content of butadiene rubber in 100% by mass of the rubber component is Since it is a 10-80 mass% rubber composition for tires, low fuel consumption, performance on snow and ice, wear resistance and processability can be improved in a well-balanced manner.

The rubber composition for tires of the present invention is obtained by blending a predetermined amount of silica and cyclized rubber with a rubber component containing a predetermined amount of butadiene rubber.

A compounded rubber in which silica is compounded with butadiene rubber generally has low dispersibility of silica and it is difficult to obtain desired performance. However, in the present invention, a rubber component such as silica and butadiene rubber can be obtained by compounding cyclized rubber. Interaction with is increased. Accordingly, the dispersibility of the silica is improved, the fuel efficiency, the performance on snow and ice, and the wear resistance can be improved, and good processability can be obtained, and the balance between these performances can be improved synergistically.

Further, by using a cyclized rubber having a predetermined cyclization rate, the dispersibility of silica is dramatically improved, and the performance balance can be remarkably improved.

The butadiene rubber (BR) is not particularly limited, and those that are common in the tire industry can be used. For the reason of sufficiently ensuring low temperature characteristics, the cis content of BR is preferably 70% by mass or more, more preferably 90% by mass or more, and further preferably 97% by mass or more.

The Mooney viscosity (ML _{1 + 4} (100 ° C.)) of BR is preferably 10 or more, more preferably 30 or more. If it is less than 10, the dispersibility of the filler tends to decrease. The Mooney viscosity is preferably 120 or less, more preferably 80 or less. If it exceeds 120, there is a concern about the occurrence of rubber burn (discoloration) during extrusion processing.

The molecular weight distribution (Mw / Mn) of BR is preferably 1.5 or more, more preferably 2.0 or more. If it is less than 1.5, workability may be deteriorated. The Mw / Mn of BR is preferably 5.0 or less, more preferably 4.0 or less. If it exceeds 5.0, the wear resistance tends to deteriorate. In the present invention, Mn and Mw are values converted from standard polystyrene using GPC.

The BR content in 100% by mass of the rubber component is 10% by mass or more, preferably 30% by mass or more, more preferably 40% by mass or more, and still more preferably 50% by mass or more, from the viewpoint of exerting necessary snow and ice performance. It is. The BR content is 80% by mass or less, preferably 70% by mass or less, and more preferably 65% by mass or less from the viewpoint of workability.

Other rubber components that can be used in the present invention include natural rubber (NR), epoxidized natural rubber (ENR), styrene butadiene rubber (SBR), diene rubber such as butadiene isoprene rubber, and butyl rubber such as chlorinated butyl rubber. Moreover, what condensed these rubber | gum, the modified thing, etc. can be used. Among them, it is preferable to use NR and / or ENR because it is environmentally friendly, can be prepared for a future decrease in oil supply, and can further improve wear resistance and improve the performance balance. More preferably, NR is used. These rubber components may be used alone or in combination of two or more.

The NR is not particularly limited. For example, SIR20, RSS # 3, TSR20, deproteinized natural rubber (DPNR), high-purity natural rubber (HPNR), etc., which are common in the tire industry can be used.

The content of NR in 100% by mass of the rubber component is preferably 10% by mass or more, more preferably 30% by mass or more, and further preferably 40% by mass or more. If it is less than 10% by mass, the fuel efficiency tends to decrease. The NR content is preferably 80% by mass or less, and more preferably 65% by mass. When it exceeds 80 mass%, workability will fall and the said performance balance tends to deteriorate.

In the present invention, from the viewpoint of the performance balance, the total content of BR and NR in 100% by mass of the rubber component is preferably 70% by mass or more, more preferably 90% by mass or more, and further preferably 100% by mass. .

The silica used in the present invention is not particularly limited, and examples thereof include dry process silica (anhydrous silicic acid), wet process silica (hydrous silicic acid) and the like, but because of the large number of silanol groups, wet process silica. Is preferred.

Nitrogen adsorption specific surface area of the silica _(N 2 SA) of preferably at least ^{40 m} 2 / g, more preferably at least ^{50m 2 / g, 100m 2 /} g or more, and particularly preferably equal to or greater than 150m ² / g. If it is less than 40 m < ² > / g, there exists a tendency for the fracture strength after vulcanization to fall. The _N 2 SA of the silica is preferably not more than 500 meters ² / g, more preferably at most 300m ² / g. When it exceeds 500 m ² / g, there is a tendency that low heat build-up and rubber processability are lowered.
The nitrogen adsorption specific surface area of silica is a value measured by the BET method according to ASTM D3037-81.

The content of silica is 5 parts by mass or more, preferably 10 parts by mass or more, more preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, and most preferably 30 parts by mass or more with respect to 100 parts by mass of the rubber component. It is. If it is less than 5 parts by mass, the low heat build-up may be insufficient. Moreover, this content is 200 mass parts or less, Preferably it is 120 mass parts or less, More preferably, it is 80 mass parts or less. When it exceeds 200 parts by mass, it becomes difficult to disperse the filler into the rubber, and the processability of the rubber tends to deteriorate.

The rubber composition of the present invention may contain a silane coupling agent.
The silane coupling agent is not particularly limited, and conventionally known silane coupling agents can be used. For example, bis (3-triethoxysilylpropyl) tetrasulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-tri Methoxysilylpropyl) sulfide type such as tetrasulfide; mercapto type such as 3-mercaptopropyltrimethoxysilane; vinyl type such as vinyltriethoxysilane; amino type such as 3-aminopropyltriethoxysilane; γ-glycidoxypropyl Examples thereof include glycidoxy type such as triethoxysilane; nitro type such as 3-nitropropyltrimethoxysilane; chloro type such as 3-chloropropyltrimethoxysilane.

The content of the silane coupling agent is preferably 0 to 20 parts by mass with respect to 100 parts by mass of the rubber component. If the amount exceeds 20 parts by mass, the effect of dispersing the filler cannot be obtained for an increase in cost, and further, the reinforcing property and wear resistance may be lowered, and unreacted silane coupling agent remains. Then, there is a possibility that the rubber may be burned during processing and the breaking strength of the rubber after vulcanization may be reduced. The lower limit is more preferably 0.5 parts by mass or more, still more preferably 3 parts by mass or more, and the upper limit is more preferably 15 parts by mass or less.

It is preferable that carbon black is blended in the rubber composition of the present invention. Thereby, reinforcing property, abrasion resistance, and performance on snow and ice can be improved, and the performance balance can be remarkably improved. Carbon black is not particularly limited, and examples thereof include SAF, ISAF, HAF, FF, and GPF.

Carbon black having an average particle size of 31 nm or less and / or a DBP oil absorption of 100 ml / 100 g or more is preferable. By blending such carbon black, necessary reinforcing properties are imparted, block rigidity, uneven wear resistance, and fracture strength are ensured, and the effects of the present invention are also remarkably obtained.

If the average particle size of the carbon black exceeds 31 nm, the wear resistance may be significantly deteriorated. The average particle diameter is more preferably 25 nm or less, and further preferably 23 nm or less. The average particle size is preferably 15 nm or more, and more preferably 19 nm or more. If it is less than 15 nm, the viscosity of the blended rubber is significantly increased, and the processability may be deteriorated. In the present invention, the average particle diameter is a number average particle diameter and is measured by a transmission electron microscope.

When the DBP oil absorption amount (dibutyl phthalate oil absorption amount) of carbon black is less than 100 ml / 100 g, the reinforcing property is low, and it may be difficult to ensure wear resistance. The DBP oil absorption is more preferably 105 ml / 100 g or more, and even more preferably 110 ml / 100 g or more. The DBP oil absorption is preferably 160 ml / 100 g or less, and more preferably 150 ml / 100 g or less. If it exceeds 160 ml / 100 g, it is difficult to produce carbon black itself. The DBP oil absorption of carbon black is measured according to JIS K6217-4: 2001.

The nitrogen adsorption specific surface area (N ₂ SA) of carbon black is preferably 80 m ² / g or more, and more preferably 110 m ² / g or more. If it is less than 80 m ² / g, the breaking strength may be deteriorated and it may be difficult to ensure wear resistance. Also, _N 2 SA of the carbon black is preferably not more than 200 meters ² / g, more preferably at most 150m ² / g. When it exceeds 200 m ² / g, the viscosity of the blended rubber is significantly increased, and the processability may be deteriorated. The N ₂ SA of carbon black is measured according to JIS K 6217-2: 2001.

The content of carbon black is preferably 1 part by mass or more and more preferably 3 parts by mass or more with respect to 100 parts by mass of the rubber component. If it is less than 1 part by mass, the reinforcing property may be inferior. The content is preferably 50 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 10 parts by mass or less. If it exceeds 50 parts by mass, the fuel efficiency tends to deteriorate.

50 mass% or more is preferable, as for the silica content (content rate) in a total of 100 mass% of a silica and carbon black, 60 mass% or more is more preferable, and 70 mass% or more is still more preferable. If it is less than 50% by mass, both the performance on snow and ice and the wear resistance cannot be achieved, and the effects of the present invention may not be exhibited. In addition, the content is preferably 95% by mass or less, and more preferably 93% by mass or less. If it exceeds 95% by mass, the weather resistance and ozone resistance may be significantly inferior.

The rubber composition of the present invention may contain other fillers, and examples include, but are not limited to, calcium carbonate, aluminum hydroxide, montmorillonite, cellulose, various short fibers, glass balloons and eggshells. It is not something.

As the cyclized rubber, compounds having various chemical structures have been proposed, but the cyclized rubber in the present invention is not limited to any of them, and any compound can be used. In the present invention, the cyclized rubber is not a rubber component but an additive (silica dispersion improver) having an action of improving the compatibility between silica and the rubber component and improving the silica dispersibility.

The cyclization rate of the cyclized rubber is preferably 0.1% or more, more preferably 1% or more, and further preferably 3% or more. If it is less than 0.1%, sufficient interaction with silica cannot be obtained, and the fuel efficiency may be deteriorated. The cyclization rate is preferably 40% or less, more preferably 35% or less, and still more preferably 30% or less. If it exceeds 40%, the cyclized rubber may gel or adhere to the kneader.

The cyclization rate is the ratio of double bonds reacted by the cyclization reaction to the number of double bonds of the raw rubber component (conjugated diene polymer) before the cyclization reaction. For example, by measuring the peak areas of protons derived from double bonds before and after the cyclization reaction of the conjugated diene polymer used as a raw material by ¹ H-NMR analysis, the cyclization reaction when the pre-cyclization reaction is 100 The ratio of the double bond remaining in the subsequent cyclized product can be obtained and measured as a value (%) represented by the formula: (100−the ratio of the double bond remaining in the cyclized product).

The number average molecular weight (Mn) of the cyclized rubber is preferably 1,000 to 1,000,000, more preferably 5,000 to 500,000, and 10,000 to 300,000. More preferably. If it is less than 1,000, the wear resistance and fuel efficiency may be deteriorated, and if it exceeds 1,000,000, the viscosity increases and the workability may be deteriorated.

The molecular weight distribution of the cyclized rubber, that is, the weight average molecular weight / number average molecular weight (Mw / Mn) is preferably 4 or less.
In addition, Mw / Mn is a standard polystyrene conversion value measured by GPC.

The glass transition temperature (Tg) of the cyclized rubber is not particularly limited and is usually −100 to 100 ° C., but preferably −90 to 80 ° C., more preferably −90 to 40 from the viewpoint of the effect of the present invention. ° C, particularly preferably -90 to 20 ° C, most preferably -90 to 5 ° C.

The gel amount of the cyclized rubber is preferably 10% by mass or less, more preferably 5% by mass or less from the viewpoint of the effect of the present invention, and a gel having substantially no gel is particularly preferable.

As the cyclized rubber, a conjugated diene polymer cyclized product can be preferably used. The conjugated diene polymer cyclized product is prepared by (co) polymerizing a conjugated diene monomer or a conjugated diene monomer and another monomer copolymerizable with the conjugated diene monomer by a known method. And the like obtained by cyclizing the conjugated diene polymer.

Examples of the conjugated diene monomer include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-pentadiene, 2-methyl- Examples include 1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, and the like. These monomers may be used alone or in combination of two or more.

Examples of other monomers copolymerizable with the conjugated diene monomer include styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, and p-tert. -Butylstyrene, α-methylstyrene, α-methyl-p-methylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, p-bromostyrene, 2-methyl-1,4-dichlorostyrene, Aromatic vinyl monomers such as 2,4-dibromostyrene and vinylnaphthalene; Chain olefin monomers such as ethylene, propylene and 1-butene; Cyclic olefin monomers such as cyclopentene and 2-norbornene; 1,5 -Hexadiene, 1,6-heptadiene, 1,7-octadiene, dicyclopentadiene, 5-ethylidene-2-no Non-conjugated diene monomers such as rubornene; (meth) acrylic acid esters such as methyl (meth) acrylate and ethyl (meth) acrylate; (meth) acrylonitrile, (meth) acrylamide and the like. These monomers may be used alone or in combination of two or more.

The content of the conjugated diene monomer unit in the conjugated diene polymer may be appropriately selected within a range not impairing the effects of the present invention, but is preferably 40 mol% or more, more preferably 60 mol% or more, and still more preferably. Is 80 mol% or more.

As the cyclized rubber, the conjugated diene polymer cyclized product described above can be used. Among them, cyclized natural rubber, cyclized isoprene rubber, cyclized butadiene rubber and the like are particularly preferable from the viewpoint of the effect of the present invention.

As described above, the conjugated diene polymer cyclized product can be prepared by cyclizing the conjugated diene polymer, but this cyclization reaction can be carried out by a known method, for example, after the (co) polymerization reaction, one-pot reaction as it is. And a method of cyclization by adding a cyclization catalyst in (3), (co) polymerization, a method of re-creating a solution from a dried conjugated diene polymer, and the like.

Here, in the cyclization reaction, for example, a known cyclization catalyst is allowed to act directly on raw rubber or on a rubber solution, and a part of chain molecules in the rubber molecule is cyclized to reduce double bonds. Thereby obtaining a cyclized rubber. Examples of the cyclization catalyst include organic sulfonic acids such as sulfuric acid and p-toluenesulfonic acid, and chlorosulfonic acid.

The content of the cyclized rubber is 0.1 parts by mass or more, preferably 2 parts by mass or more, more preferably 5 parts by mass or more with respect to 100 parts by mass of the rubber component. Moreover, this content is 40 mass parts or less, Preferably it is 30 mass parts or less. If the amount is less than 0.1 parts by mass, the effect of silica dispersion is not sufficient, and the effect of improving fuel economy tends to be difficult to obtain. If it exceeds 40 parts by mass, the rubber physical properties may be deteriorated.

In addition to the above components, the rubber composition of the present invention includes oils, waxes, anti-aging agents, additives such as stearic acid and zinc oxide, vulcanizing agents such as sulfur, vulcanization accelerators, vulcanization acceleration aids, etc. May be appropriately blended.

The oil content is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and still more preferably 20 parts by mass or more with respect to 100 parts by mass of the rubber component. If it is less than 10 parts by mass, the performance on snow and ice and the workability tend to decrease. The content is preferably 100 parts by mass or less, more preferably 80 parts by mass or less. When it exceeds 100 parts by mass, the wear resistance tends to decrease.

The rubber composition of the present invention is produced by a general method. That is, it can be produced by a method of kneading the above components with a kneader such as a Banbury mixer, a kneader, or an open roll and then vulcanizing. The rubber composition can be suitably used for a tread of a studless tire.

The studless tire of the present invention is manufactured by a usual method using the rubber composition. That is, the rubber composition containing the above components is extruded in accordance with the shape of the tread at an unvulcanized stage and molded together with other tire members by a normal method on a tire molding machine. Form a vulcanized tire. By heating and pressing the unvulcanized tire in a vulcanizer, the studless tire of the present invention can be manufactured.

The present invention will be specifically described based on examples, but the present invention is not limited to these examples.

(Production Example 1)
A pressure-resistant reactor equipped with a stirrer substituted with nitrogen was charged with 1400 g of dehydrated toluene and 18 mmol of n-butyllithium, and the internal temperature was maintained at 60 ° C. 487 g of isoprene was continuously added to the reactor over 15 minutes, and the internal temperature was controlled not to exceed 75 ° C. Thereafter, the mixture was reacted at 70 ° C. for 10.5 hours, and then 1.4 mmol of methanol was added as a polymerization terminator to terminate the polymerization reaction.
After stopping the polymerization reaction, the temperature was raised to 80 ° C., 4.24 g of p-toluenesulfonic acid was added, and the cyclization reaction was performed for 1 hour while maintaining the temperature at 80 ° C. Subsequently, an aqueous solution in which 1.70 g of sodium carbonate was dissolved in 5.1 g of water was added to stop the cyclization reaction, and the reaction solution was filtered to remove the catalyst residue. After adding 0.4 g of an anti-aging agent (Irganox 1010: manufactured by Ciba Specialty Chemicals) to this solution, toluene was distilled off and dried under reduced pressure to obtain a cyclized rubber 1.

(Production Example 2)
In a pressure vessel equipped with a stirrer purged with nitrogen, 300 g of liquid polyisoprene (Kuraray LIR-30: Mn = 28,000) and 700 g of toluene were charged. The mixture was heated to 80 ° C. to completely dissolve polyisoprene, and then 2 g of p-toluenesulfonic acid was added to carry out a cyclization reaction while maintaining the internal temperature at 80 ° C. After reacting for 1 hour, a 25% aqueous solution of sodium carbonate containing 0.8 g of sodium carbonate was added to stop the reaction, stirred at 80 ° C. for 30 minutes, and then filtered to remove the catalyst residue. After adding 0.3 g of an anti-aging agent (Irganox 1010: manufactured by Ciba Specialty Chemicals) to this solution, toluene was distilled off and dried under reduced pressure to obtain a cyclized rubber 2.

(Production Example 3)
A cyclized rubber 3 was obtained in the same manner as in Production Example 2, except that liquid polybutadiene (manufactured by Sartomer, Rycon 150, Mn = 5,200) was used instead of liquid polyisoprene.

(Production Example 4)
Instead of liquid polyisoprene, polybutadiene (Ube Industries, UBEPOL 150L, Mn = 250,000) was used, and the cyclized rubber 4 was prepared in the same manner as in Production Example 2 except that the cyclization reaction time was changed to 3 hours. Obtained.

The physical properties of the obtained cyclized rubber were measured by the following methods, and the results are shown in Table 1.

(Cyclization rate of cyclized rubber)
The cyclization rate of the cyclized rubber was determined from the peak area ratio of protons in the polymer before and after the cyclization reaction by ¹ H-NMR measurement using an NMR apparatus of AV400 manufactured by BRUKER, data analysis software TOP SPIN2.1. . In addition, the detailed cyclization rate calculation method is as having described in the following literature.
Y. Tanaka and H.M. Sato, J .; Polym. Sci: Poly. Chem. Ed. , 17, 3027 (1979)

(Number average molecular weight (Mn) and weight average molecular weight (Mw) of cyclized rubber)
The calibration curve obtained from the molecular weight distribution curve obtained by performing gel permeation (permeation) chromatography of cyclized rubber (GPC, manufactured by Tosoh Corporation) using polystyrene as a standard substance and tetrahydrofuran as a solvent at a temperature of 40 ° C. Mn and Mw were calculated.

(Glass transition temperature Tg of cyclized rubber)
The glass transition temperature of the cyclized rubber was measured using a differential scanning calorimeter (manufactured by Seiko Denshi Kogyo Co., Ltd .: SSC5200) under the conditions of a starting temperature of −100 ° C. and a heating rate of 10 ° C./min.

(Gel amount of cyclized rubber)
After 0.2 g of a sample cut to 2 mm square was immersed in 100 ml of toluene for 48 hours, the ratio of the dry weight of the gel remaining on the 80-mesh wire net was shown as a percentage.

The chemicals used in the examples and comparative examples are summarized below.
NR: RSS # 3
BR: UBEPOL BR150B manufactured by Ube Industries, Ltd. (cis 1,4 bond amount 97%, ML _{1 + 4} (100 ° C.) 40, Mw / Mn 3.3)
Cyclized rubber 1-4: Production Examples 1-4
Silica: Ultrasil VN3 (N ₂ SA: 175 m ² / g) manufactured by EVONIK-DEGUSSA
Carbon black: Dia Black I manufactured by Mitsubishi Chemical Corporation (ISAF carbon, average particle size 23 nm, DBP oil absorption 114 ml / 100 g)
Silane coupling agent: Si69 (bis (3-triethoxysilylpropyl) tetrasulfide) manufactured by EVONIK-DEGUSSA
Process oil: Process X-140 (aromatic process oil) manufactured by Japan Energy Co., Ltd.
Wax: Sunnock N manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
Stearic acid: Stearic acid “paulownia” manufactured by NOF Corporation
Zinc oxide: 2 types of anti-aging of zinc oxide manufactured by Mitsui Mining & Smelting Co., Ltd .: NOCRACK 6C (N- (1,3-dimethylbutyl) -N-phenyl-p-phenylene manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.) Diamine)
Sulfur: Powdered sulfur vulcanization accelerator manufactured by Tsurumi Chemical Industry Co., Ltd .: Noxeller NS (N-tert-butyl-2-benzothiazolylsulfenamide) manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.

<Examples and Comparative Examples>
In accordance with the formulation of Table 2, using a 1.7L Banbury mixer manufactured by Kobe Steel Co., Ltd., chemicals other than sulfur and a vulcanization accelerator were filled to a filling rate of 58%, and 140 rpm at 140 rpm. A kneaded product was obtained by kneading until reaching 0C. Next, using an open roll, sulfur and a vulcanization accelerator were added to the obtained kneaded product and kneaded to obtain an unvulcanized rubber composition.
Further, the obtained unvulcanized rubber composition was molded into a predetermined size, and a vulcanized rubber composition was obtained by press vulcanization at 150 ° C. for 20 minutes, and a vulcanization of about 2 mm × 130 mm × 130 mm was obtained. A rubber slab sheet was prepared.

Further, the obtained unvulcanized rubber composition is formed into a tread shape, bonded to another tire member, and vulcanized at 170 ° C. for 15 minutes, so that a test studless tire (tire size: 195 / 65R15) is obtained. Was made.

The following evaluation was performed about the obtained unvulcanized rubber composition, a vulcanized rubber slab sheet, and the studless tire for a test. The results are shown in Table 2.

(Processability)
Based on JIS K6300-1, Mooney viscosity (ML _{1 + 4} ) was measured at 130 ° C., and Comparative Example 1 was taken as 100, and the workability index was calculated from the following formula. The larger the index, the better the processability when unvulcanized.
(Processability index) = (Mooney viscosity of Comparative Example 1) / (Mooney viscosity of each formulation) × 100

(Viscoelasticity test)
Using a viscoelastic spectrometer VES manufactured by Iwamoto Seisakusho, the loss tangent (tan δ) of the vulcanized rubber slab sheet was measured under conditions of a temperature of 70 ° C., an initial strain of 10%, a dynamic strain of 2%, and a frequency of 10 Hz. The rolling resistance index of Comparative Example 1 was set to 100, and the index was displayed by the following formula. A larger index indicates that rolling resistance is reduced, which is preferable.
(Rolling resistance index) = (tan δ of Comparative Example 1) / (tan δ of each formulation) × 100

(Performance on snow and ice)
Using the test studless tire, the actual vehicle performance was evaluated on snow and ice under the following conditions. In addition, 195 / 65R15 size DS-2 pattern studless tires for passenger cars were manufactured as studless tires, and these tires were mounted on domestic 2000cc FR cars. The test place was the Hokkaido Nayoro Test Course of Sumitomo Rubber Industries, Ltd., the temperature on ice was -1 to -6 ° C, and the temperature on snow was -2 to -10 ° C.
Braking performance (on-ice braking stop distance): The stop distance on ice required to depress and stop the lock brake at a speed of 30 km / h was measured. Using Comparative Example 1 as a reference, the index was expressed by the following formula. The larger the index, the better the braking performance.
(Braking performance index) = (braking stop distance of comparative example 1) / (stop distance of each formulation) × 100

(Abrasion resistance)
The test studless tire was mounted on a domestic FF vehicle, and the groove search of the tire tread portion after a running distance of 8000 km was measured. The travel distance when the tire groove depth was reduced by 1 mm was calculated from the measured value, and indexed by the following formula. It shows that abrasion resistance is so favorable that an index | exponent is large.
(Abrasion resistance index) = (travel distance when 1 mm groove depth decreases) / (travel distance when tire groove of Comparative Example 1 decreases by 1 mm) × 100

In Comparative Example 2 in which the amount of oil was increased compared to Comparative Example 1, the workability and the performance on snow and ice were improved, but the wear resistance was greatly deteriorated, and a good improvement in performance balance was not observed. On the other hand, in Examples 1 to 4 in which 10 parts of cyclized rubber is added to silica compounded rubber, processability, fuel efficiency, performance on snow and ice, and wear resistance can be improved at the same time, and these performance balances can be synergistically improved. Became clear. Further, even in Examples 5 to 6 in which the addition amount of the cyclized rubber was increased, while maintaining the workability indexes “99” and “98” and the performance index on snow and ice “99” which are practically no problem, low fuel consumption, The wear resistance can be remarkably improved.

Claims (4)

5 to 200 parts by mass of silica, and 0.1 to 40 parts by mass of cyclized rubber (except when the cyclized rubber is an epoxidized diene rubber) with respect to 100 parts by mass of the rubber component,
The content of the butadiene rubber 100% by mass of the rubber component is Ri 10-80% by mass,
A tire rubber composition, wherein the cyclized rubber has a cyclization rate of 0.1 to 40% . The cyclized rubber, cyclized natural rubber, cyclized isoprene rubber and cyclizing at least one kind of claim 1 Symbol placement tire rubber composition is selected from the group consisting of butadiene rubber. The rubber composition for tires according to claim 1 or 2 containing 1-50 mass parts of carbon black with respect to 100 mass parts of said rubber components. The studless tire which has a tread produced using the rubber composition in any one of Claims 1-3 .