WO2015186755A1 - タイヤトレッド用ゴム組成物 - Google Patents
タイヤトレッド用ゴム組成物 Download PDFInfo
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- WO2015186755A1 WO2015186755A1 PCT/JP2015/066091 JP2015066091W WO2015186755A1 WO 2015186755 A1 WO2015186755 A1 WO 2015186755A1 JP 2015066091 W JP2015066091 W JP 2015066091W WO 2015186755 A1 WO2015186755 A1 WO 2015186755A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Definitions
- the present invention relates to a rubber composition for a tire tread in which the balance between wet performance and wear resistance and performance on snow is further improved.
- All-season pneumatic tires for passenger cars are required to have excellent on-snow performance when running on snowy road surfaces, as well as wet performance and wear resistance when running on non-snowy road surfaces (wet and dry road surfaces).
- silica is blended into a tire rubber composition.
- silica has a problem that the wear resistance is lowered because the reinforcing performance is small when blended with diene rubber, compared with carbon black.
- the silica content is increased or the particle size is made finer, the dispersibility of the silica is lowered and the wear resistance is further lowered, or the flexibility of the rubber composition is lost and the snow composition is lost. There is a problem that the performance decreases.
- Patent Documents 1 and 2 propose to improve the dispersibility of silica by using a rubber composition in which silica is blended with a terminal-modified styrene-butadiene rubber whose terminal is modified with polyorganosiloxane or the like.
- a rubber composition in which silica is blended with a terminal-modified styrene-butadiene rubber whose terminal is modified with polyorganosiloxane or the like.
- the level of demand that consumers expect to improve wear resistance, wet performance and on-snow performance is higher, and there is a need to further improve these properties.
- An object of the present invention is to provide a rubber composition for a tire tread in which the balance between wet performance and wear resistance and performance on snow is improved to a level higher than conventional levels.
- the rubber composition for a tire tread of the present invention that achieves the above object is a diene rubber 100 wt% containing 40 wt% or more of a terminal-modified styrene butadiene rubber, 8 to 35 wt% of natural rubber, and 15 to 40 wt% of butadiene rubber.
- a rubber composition comprising 66 to 110 parts by weight of a filler containing 50% by weight or more of silica based on the part, wherein the terminal-modified styrene butadiene rubber is derived from a compound in which a functional group at the terminal thereof reacts with a silanol group
- the styrene unit content is 38 to 48% by weight
- the oil-extended oil content is less than 30% by weight
- the ratio of the blended amount of butadiene rubber (BR) to the natural rubber (NR) (BR / NR ) Is more than 1.0 and 2.5 or less
- the embrittlement temperature of the rubber composition is ⁇ 45 ° C. or less.
- the rubber composition for a tire tread of the present invention contains a functional group that reacts with a silanol group on a silica surface, has a styrene unit content of 38 to 48% by weight, and an oil extended amount of less than 30 parts by weight.
- a filler containing 50% by weight or more of silica to 100 parts by weight of diene rubber containing natural rubber and butadiene rubber, the affinity between the diene rubber and silica can be increased. Can improve the wet performance and wear resistance.
- the wet performance and wear resistance can be improved by setting the ratio (BR / NR) of butadiene rubber (BR) and natural rubber (NR) to more than 1 and not more than 2.5 and embrittlement temperature at -45 ° C or less. And the performance on snow can be improved over the conventional level.
- Silica preferably has a DBP absorption of 160 to 220 ml / 100 g, a nitrogen adsorption specific surface area of 145 to 193 m 2 / g, and a CTAB specific surface area of 140 to 184 m 2 / g.
- the total oil component is preferably 25 to 50% by weight in 100% by weight of the tire tread rubber composition.
- terminal-modified styrene butadiene rubber it is preferable that one or both terminal functional groups are derived from at least one compound selected from a polyorganosiloxane compound, an epoxy compound, and a hydrocarbyloxysilicon compound.
- the terminal-modified styrene butadiene rubber can have an isoprene segment at one end.
- the pneumatic tire using the rubber composition of the present invention in the tread portion can improve the balance between wet performance and wear resistance and performance on snow to a level higher than the conventional level.
- FIG. 1 is a partial cross-sectional view in the tire meridian direction showing an example of an embodiment of a pneumatic tire using the tire tread rubber composition of the present invention.
- FIG. 1 shows an example of an embodiment of a pneumatic tire using a rubber composition for a tire tread.
- the pneumatic tire includes a tread portion 1, a sidewall portion 2, and a bead portion 3.
- the pneumatic tire has two carcass layers 4 in which reinforcing cords extending in the tire radial direction are arranged between the left and right bead portions 3 at predetermined intervals in the tire circumferential direction and embedded in a rubber layer.
- the both ends are folded back from the inner side in the tire axial direction so as to sandwich the bead filler 6 around the bead core 5 embedded in the bead part 3.
- An inner liner layer 7 is disposed inside the carcass layer 4.
- a belt cover layer 9 is disposed on the outer peripheral side of the belt layer 8.
- a tread portion 1 is formed of a tread rubber layer 10 on the outer peripheral side of the belt cover layer 9.
- the tread rubber layer 10 is preferably composed of the rubber composition for tire tread of the present application.
- a side rubber layer 11 is disposed outside the carcass layer 4 of each sidewall portion 2, and a rim cushion rubber layer 12 is provided outside the folded portion of the carcass layer 4 of each bead portion 3.
- a studless tire is not limited to embodiment of the pneumatic tire illustrated in FIG.
- the rubber component is a diene rubber
- the diene rubber necessarily includes terminal-modified styrene butadiene rubber, natural rubber, and butadiene rubber.
- the terminal-modified styrene butadiene rubber is a styrene butadiene rubber produced by solution polymerization in which a molecular chain has a functional group at one or both ends.
- the skeleton of the modified styrene butadiene rubber preferably has an isoprene segment at one end thereof.
- the affinity with silica is improved, and the wet performance and wear resistance can be further improved.
- the functional group of the modified styrene butadiene rubber is a functional group derived from a compound that reacts with a silanol group on the silica surface.
- the compound that reacts with the silanol group is not particularly limited.
- polyorganosiloxanes, epoxy compounds, hydrocarbyloxysilicon compounds and compounds are preferred.
- the terminal-modified styrene butadiene rubber used in the present invention has a styrene unit content of 38 to 48% by weight, preferably 40 to 45% by weight.
- the rubber composition has high rigidity and strength, and the wear resistance and wet performance when a pneumatic tire is made higher. Can do.
- the terminal-modified styrene butadiene rubber forms a fine phase separation form with respect to other diene rubbers.
- the terminal-modified styrene-butadiene rubber comes to be localized near the silica particles, and the affinity of the terminal-modified group acts more efficiently on the silica, thereby further increasing the affinity and improving the dispersibility of the silica. Can be good. If the styrene unit content of the terminal-modified styrene-butadiene rubber is less than 38% by weight, the effect of forming a fine phase separation form with respect to other diene rubbers cannot be obtained sufficiently. Further, the effect of increasing the rigidity and strength of the rubber composition cannot be sufficiently obtained.
- the styrene unit content of the terminal-modified styrene butadiene rubber exceeds 48% by weight, the glass transition temperature (Tg) of the styrene butadiene rubber rubber is increased, and the balance of viscoelastic properties is deteriorated.
- Tg glass transition temperature
- the styrene unit content of the terminal-modified styrene butadiene rubber is measured by infrared spectroscopic analysis (Hampton method).
- the concentration of the terminal modified group in the terminal modified styrene butadiene rubber is determined by the relationship with the weight average molecular weight (Mw) of the terminal modified styrene butadiene rubber.
- Mw weight average molecular weight of the terminal-modified styrene butadiene rubber.
- the weight average molecular weight of the terminal-modified styrene butadiene rubber is preferably 600,000 to 1,000,000, more preferably 650,000 to 850,000.
- the weight average molecular weight of the terminal-modified styrene butadiene rubber is less than 600,000, the concentration of the modifying group at the terminal of the terminal-modified styrene butadiene rubber increases, and the properties of the rubber composition improve the dispersibility of the silica, but the polymer itself Because of the low molecular weight, there is a possibility that strength and rigidity may not be exhibited, and the improvement range of high-temperature viscoelastic properties is also reduced. In addition, the wear resistance of the rubber composition may be reduced.
- the weight average molecular weight of the terminal-modified styrene butadiene rubber exceeds 1,000,000, the concentration of the modifying group at the terminal of the terminal-modified styrene butadiene rubber becomes low, the affinity with silica is insufficient, and the dispersibility may be deteriorated.
- the weight average molecular weight (Mw) of terminal modified styrene butadiene rubber shall be measured by standard polystyrene conversion by gel permeation chromatography (GPC).
- the vinyl unit content of the terminal-modified styrene butadiene rubber is preferably 20 to 35% by weight, more preferably 26 to 34% by weight.
- the glass transition temperature (Tg) of the terminal-modified styrene butadiene rubber can be optimized.
- the fine phase separation form of the terminal-modified styrene butadiene rubber formed with respect to other diene rubbers can be stabilized.
- the vinyl unit content of the terminal-modified styrene butadiene rubber is less than 20% by weight, the Tg of the terminal-modified styrene butadiene rubber becomes low, and the wet grip performance may be deteriorated.
- the vinyl unit content of the terminal-modified styrene-butadiene rubber exceeds 35% by weight, the vulcanization rate may decrease, the strength and rigidity may decrease, and the loss tangent (tan ⁇ at 60 ° C.) may increase.
- the vinyl unit content of the terminal-modified styrene butadiene rubber is measured by infrared spectroscopic analysis (Hampton method).
- the terminal-modified styrene butadiene rubber can improve the molding processability of the rubber composition by adding an oil component (oil extension).
- the oil extended amount is less than 30% by weight, preferably 10% by weight or more and less than 30% by weight, in 100% by weight of the terminal-modified styrene butadiene rubber.
- the amount of the oil-extended amount of the terminal-modified styrene butadiene rubber exceeds 30 parts by weight, the degree of freedom in composition design when oil, softener, tackifier or the like is added to the rubber composition is reduced.
- the content of the terminal-modified styrene butadiene rubber is 40% by weight or more, preferably 40 to 78% by weight, more preferably 42 to 70% by weight, and further preferably 45 to 60% by weight in 100% by weight of the diene rubber. % By weight.
- the content of the terminal-modified styrene butadiene rubber is less than 40% by weight in the diene rubber, the affinity with silica is lowered, so that the dispersibility cannot be improved. Further, if the content of the terminal-modified styrene butadiene rubber exceeds 78% by weight in the diene rubber, the wear resistance may be lowered.
- the rubber composition for a tire tread of the present invention can improve wear resistance and wet grip performance while maintaining performance on snow at a high level by containing natural rubber.
- the blending amount of the natural rubber is 8 to 35% by weight, preferably 10 to 25% by weight, in 100% by weight of the diene rubber.
- the blending amount of the natural rubber is less than 8% by weight, the performance on snow, the wet grip performance and the wear resistance cannot be sufficiently improved.
- the blending amount of natural rubber exceeds 35% by weight, wet grip properties are lowered.
- natural rubber what is usually used for the rubber composition for tires is good.
- the rubber composition for tire tread of the present invention can improve wear resistance and performance on snow by containing butadiene rubber.
- the blending amount of butadiene rubber is 15 to 40% by weight, preferably 25 to 35% by weight, in 100% by weight of diene rubber.
- Abrasion resistance falls that the compounding quantity of a butadiene rubber is less than 8 weight%.
- the compounding quantity of butadiene rubber exceeds 40 weight%, there exists a concern about deterioration of chipping resistance.
- the butadiene rubber those usually used in rubber compositions for tires may be used.
- the ratio (BR / NR) of the blending amount (BR) of the butadiene rubber to the blending amount (NR) of the natural rubber exceeds 1.0 and is 2.5 or less, preferably 1.5-2. 3. If the ratio of butadiene rubber to natural rubber (BR / NR) is 1.0 or less, the balance between wet performance and wear resistance and performance on snow cannot be improved, and especially performance on snow is improved. Can not do it. On the other hand, when the ratio (BR / NR) of the blending amount exceeds 2.5, the wet grip property is deteriorated.
- diene rubbers other than the terminal-modified styrene butadiene rubber, natural rubber and butadiene rubber can be blended as the diene rubber as long as the object of the present invention is not impaired.
- examples of other diene rubbers include isoprene rubber, unmodified styrene butadiene rubber, butyl rubber, and halogenated butyl rubber. Such diene rubbers can be used alone or as a plurality of blends.
- a filler containing 50% by weight or more of silica is blended in an amount of 66 to 110 parts by weight with respect to 100 parts by weight of the diene rubber.
- the wet grip property and the wear resistance of the rubber composition can be balanced at a higher level.
- the blending amount of the filler is less than 66 parts by weight, a high level of wet grip property cannot be ensured.
- the wear resistance is deteriorated.
- the content of silica in 100% by weight of the filler is 50% by weight or more, preferably 70 to 100% by weight.
- the blending of the terminal-modified styrene butadiene rubber increases the affinity with silica and improves the dispersibility, so that the effect of blending silica can be further enhanced.
- silica usually used in rubber compositions for tire treads, for example, wet method silica, dry method silica, or surface-treated silica can be used.
- the particle property of silica is not particularly limited, but preferably it satisfies all the following three particle characteristics.
- DBP absorption is 160-220ml / 100g
- the DBP absorption amount of silica is preferably 160 to 220 ml / 100 g.
- the breaking strength is lowered.
- the DBP absorption exceeds 220 ml / 100 g, the viscosity becomes too high and the mixing processability deteriorates.
- the DBP absorption amount of silica is determined in accordance with JIS K6217-4 oil absorption amount A method.
- N 2 SA Nitrogen adsorption specific surface area of 145 to 193 m 2 / g
- the nitrogen adsorption specific surface area (N 2 SA) of silica is preferably 145 to 193 m 2 / g. If the N 2 SA of silica is less than 145 m 2 / g, wet grip properties deteriorate, which is not preferable. Further, when the N 2 SA of silica is more than 193m 2 / g, the dispersibility of the silica is deteriorated, the wear resistance is deteriorated. Moreover, since a rubber composition becomes hard and the performance on snow falls, it is not preferable.
- the N 2 SA of silica is determined according to JIS K6217-2.
- CTAB CTAB specific surface area
- the CTAB specific surface area (CTAB) of the silica is preferably 140 to 184 m 2 / g. If the CTAB of silica is less than 140 m 2 / g, the wet grip property is deteriorated, which is not preferable. On the other hand, when the CTAB of silica exceeds 184 m 2 / g, the dispersibility of silica deteriorates and the wear resistance deteriorates, which is not preferable.
- the CTAB for silica is determined in accordance with JIS K6217-3.
- Silica satisfying all of the particle properties (1) to (3) described above can improve the dispersibility of silica by blending with the above-mentioned terminal-modified styrene butadiene rubber. For this reason, the terminal-modified styrene butadiene rubber and the silica having the above-mentioned particle properties can modify the tan ⁇ of the rubber composition, and obtain a further synergistic effect. Further, by blending natural rubber and butadiene rubber together with the terminal-modified styrene butadiene rubber, it is possible to make the rubber composition excellent in wear resistance and on-snow performance.
- silica satisfying all the particle properties (1) to (3) can be used alone as silica.
- this silica and other silica that does not satisfy the particle properties (1) to (3) may be used together.
- Silica can be used by appropriately selecting from commercially available products. Moreover, the silica obtained by the normal manufacturing method can be used.
- the rubber composition of the present invention it is preferable to blend a silane coupling agent together with silica, so that the dispersibility of silica can be improved and the reinforcing property with the diene rubber can be further increased.
- the silane coupling agent is preferably added in an amount of 3 to 20% by weight, more preferably 5 to 15% by weight, based on the amount of silica.
- the compounding amount of the silane coupling agent is less than 3% by weight of the silica weight, the effect of improving the dispersibility of silica cannot be obtained sufficiently.
- the compounding quantity of a silane coupling agent exceeds 20 weight%, silane coupling agents will condense and it will become impossible to acquire a desired effect.
- the silane coupling agent is not particularly limited, but a sulfur-containing silane coupling agent is preferable.
- a sulfur-containing silane coupling agent is preferable.
- the rubber composition for a tire tread of the present invention can contain other fillers other than silica.
- fillers other than silica include carbon black, clay, mica, talc, calcium carbonate, aluminum hydroxide, aluminum oxide, and titanium oxide. Of these, carbon black is preferred.
- the rubber strength can be increased by blending other fillers containing carbon black.
- the content of the other filler is 50% by weight or less, preferably 0 to 30% by weight, out of 100% by weight of the filler. If the content of other fillers exceeds 50% by weight, the fuel efficiency is deteriorated.
- the embrittlement temperature of the rubber composition for a tire tread of the present invention is ⁇ 45 ° C. or less, preferably ⁇ 60 ° C. to ⁇ 50 ° C. When the embrittlement temperature of the rubber composition is higher than ⁇ 45 ° C., the performance on snow is deteriorated.
- the embrittlement temperature of the rubber composition for a tire tread is a 50% impact embrittlement temperature required in accordance with JIS K6261.
- the total oil component is preferably 25 to 50% by weight, more preferably 30 to 45% by weight in 100% by weight of the rubber composition. If the sum of the oil components is less than 25% by weight, the performance on snow may not be sufficiently improved. On the other hand, if the sum of the oil components exceeds 50% by weight, the wear resistance may not be sufficiently improved.
- the total of oil components is the sum of oil components contained in rubber compositions composed of oil components such as oil-extended oils in diene rubbers and natural oils, synthetic oils, plasticizers and the like added during preparation of the rubber composition. Say.
- Rubber composition for tire tread includes rubber composition for tire tread such as vulcanization or crosslinking agent, vulcanization accelerator, anti-aging agent, plasticizer, processing aid, liquid polymer, terpene resin, thermosetting resin, etc.
- Various compounding agents generally used can be blended.
- Such a compounding agent can be kneaded by a general method to form a rubber composition, which can be used for vulcanization or crosslinking.
- the compounding amounts of these compounding agents can be the conventional general compounding amounts as long as they do not contradict the purpose of the present invention.
- the rubber composition for a tire tread can be produced by mixing each of the above components using a known rubber kneading machine such as a Banbury mixer, a kneader, or a roll.
- the rubber composition for a tire tread of the present invention can be suitably used for a pneumatic tire.
- Pneumatic tires using this rubber composition in the tread part especially all-season pneumatic tires for passenger cars, are used for snow performance on snowy road surfaces and wet performance and wear resistance when running on non-snowy road surfaces.
- the balance with the property can be improved to a level higher than the conventional level.
- Examples 1 to 7 and Comparative Examples 1 to 8 having the compounding agents shown in Table 3 as the common compounding and the compositions shown in Tables 1 and 2, sulfur and The components excluding the vulcanization accelerator were weighed and kneaded for 5 minutes with a 1.8 L closed mixer, and then the master batch was discharged and cooled at room temperature. This master batch was subjected to a 1.8 L closed mixer, and sulfur and a vulcanization accelerator were added and mixed to obtain a rubber composition for a tire tread.
- Tables 1 and 2 since the modified S-SBRs 1 and 2 are oil-extended products, the net rubber amount is shown in parentheses.
- the compounding quantity of the common component of Table 3 was described as a weight part with respect to 100 weight part of diene rubber shown to Table 1,2.
- Abrasion resistance The obtained pneumatic tire is mounted on a wheel with a rim size of 18 x 7 JJ, filled with air pressure of 220 kPa and mounted on a domestic 2.5 liter class test vehicle. For 10 laps continuously at a speed of 80 km / h. Thereafter, the state of wear on the tread surface was visually observed, and Comparative Example 1 was scored as 100. The obtained results are shown in Tables 1 and 2. It shows that abrasion resistance is so favorable that the value of evaluation is large, especially an index
- On-snow performance A 2.6km test course with one pneumatic tyre mounted on a wheel with a rim size of 18 x 7 JJ, mounted on a domestic 2.5-liter class test vehicle, and snow-covered under an air pressure of 200 kPa. The vehicle was run, and the handling stability at that time was scored by a sensitive evaluation by three expert panelists. The obtained results are shown in Tables 1 and 2 as an index with Comparative Example 1 as 100. The larger the index, the better the performance on snow (steering stability) on a snowy road surface, especially when the index is 102 or more.
- the obtained pneumatic tire is assembled to a wheel with a rim size of 18 x 7 JJ, mounted on a domestic 2.5 liter class test vehicle, and a test course of 2.6 km per lap consisting of a wet road surface under the condition of an air pressure of 220 kPa.
- the vehicle was run, and the handling stability at that time was scored by a sensitive evaluation by three expert panelists.
- the obtained results are shown in Tables 1 and 2 as an index with Comparative Example 1 as 100. It means that the wet steering stability on a wet road surface is excellent when the index is larger, particularly when the index is 102 or more.
- Modified S-SBR1 terminal-modified solution polymerized styrene butadiene rubber, styrene unit content 42% by weight, vinyl unit content 32% by weight, weight average molecular weight (Mw) 750,000, Tg -25 ° C, oil extended
- Mw weight average molecular weight
- Modified S-SBR2 terminal-modified styrene butadiene rubber, styrene unit content is 21% by weight, vinyl unit content is 63% by weight, weight average molecular weight (Mw) is 440,000, Tg is ⁇ 27 ° C.
- BR Butadiene rubber
- Nippon Zeon BR1220 NR natural rubber
- SIR20 Silica 1 Zeosil 1165MP manufactured by Rhodia
- DBP absorption amount is 200 ml / 100 g
- nitrogen adsorption specific surface area (N 2 SA) is 160 m 2 / g
- CTAB specific surface area (CTAB) is 159 m 2 / g
- Silica 2 Rhodia Zeosil Premium 200MP, DBP absorption 203 ml / 100 g, nitrogen adsorption specific surface area (N 2 SA) 200 m 2 / g, CTAB specific surface area (CTAB) 197 m 2 / g.
- Carbon black Toast Carbon Co., Ltd.
- Seest KH Silane coupling agent Si69, bis (3-triethoxysilylpropyl) tetrasulfide oil manufactured by Evonik Degussa Oil: Extract No. 4 S manufactured by Showa Shell Sekiyu KK
- 1,6-bis (trichlorosilyl) hexane 0.08 mmol was then obtained.
- 0.027 mmol of polyorganosiloxane A represented by the above formula (1) was added in the form of a 20% by mass concentration of xylene solution and reacted for 30 minutes.
- an amount of methanol corresponding to 2 moles of n-butyllithium used was added to obtain a solution containing modified S-SBR2.
- Irganox 1520L (manufactured by Ciba Specialty Chemicals) was added to this solution as an anti-aging agent in an amount of 0.15 parts by mass with respect to 100 parts by mass of modified S-SBR2, and the oil-extended oil content was 27.
- Add FUCKOL ERAMIC 30 (manufactured by Shin Nippon Oil Co., Ltd.) to 27 wt%, remove the solvent by steam stripping, and vacuum dry at 60 ° C. for 24 hours to obtain solid rubber. It was collected. The obtained solid rubber was dehydrated with a roll and dried in a drier to obtain modified S-SBR2.
- Zinc oxide 3 types of zinc oxide manufactured by Shodo Chemical Industry Co., Ltd.
- Stearic acid Bead stearic acid manufactured by Chiba Fatty Acid Co.
- Anti-aging agent Antigen 6C manufactured by Sumitomo Chemical Co., Ltd.
- Wax Sunnock manufactured by Ouchi Shinsei Chemical Co., Ltd.
- Sulfur Fine powdered sulfur with Jinhua seal oil manufactured by Tsurumi Chemical Co., Ltd.
- Vulcanization accelerator 1 CBS vulcanization accelerator, Noxeller CZ-G manufactured by Ouchi New Chemical Co.
- Vulcanization accelerator 2 Vulcanization accelerator DPG, Noxeller D manufactured by Ouchi Shinsei Chemical Co., Ltd.
- the rubber compositions for tire treads of Examples 1 to 8 can improve the balance between wet performance and wear resistance and performance on snow compared to the conventional level.
- the rubber composition of Comparative Example 1 has a weight ratio (BR / NR) of 1 or less and is based on this.
- the embrittlement temperature is higher than ⁇ 45 ° C., so the performance on snow and the wear resistance are deteriorated.
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Abstract
Description
シリカのDBP吸収量は好ましくは160~220ml/100gにする。DBP吸収量が160ml/100g未満であると、破断強度が低下することになる。DBP吸収量が220ml/100gを超えると、粘度が高くなり過ぎて混合加工性が悪化する。シリカのDBP吸収量は、JIS K6217-4吸油量A法に準拠して求めるものとする。
シリカの窒素吸着比表面積(N2SA)は好ましくは145~193m2/gにする。シリカのN2SAが145m2/g未満であるとウェットグリップ性が悪化し好ましくない。またシリカのN2SAが193m2/gを超えると、シリカの分散性が悪化し、耐摩耗性が悪化する。またゴム組成物が硬くなり雪上性能が低下するため好ましくない。なおシリカのN2SAはJIS K6217-2に準拠して求めるものとする。
シリカのCTAB比表面積(CTAB)は好ましくは140~184m2/gにする。シリカのCTABが140m2/g未満であるとウェットグリップ性が悪化し好ましくない。またシリカのCTABが184m2/gを超えると、シリカの分散性が悪化し、耐摩耗性が悪化し好ましくない。なおシリカのCTABはJIS K6217-3に準拠して求めるものとする。
得られた空気入りタイヤをリムサイズ18×7JJのホイールに組付け、空気圧220kPaを充填し国産2.5リットルクラスの試験車両に装着し、テストコースの1周5kmの周回路の乾燥路面を速度80km/時で連続して10周走行した。その後トレッド面における摩耗の状態を目視により観察し、比較例1を100として点数付け評価した。得られた結果を表1,2に示した。評価の値が大きいほど、特に指数が102以上であると、耐摩耗性が良いことを示す。
得られた空気入りタイヤをリムサイズ18×7JJのホイールに組付け、国産2.5リットルクラスの試験車両に装着し、空気圧200kPaの条件で積雪状態にした1周2.6kmのテストコースを実車走行させ、そのときの操縦安定性を専門パネラー3名による感応評価により採点した。得られた結果は比較例1を100とする指数として、表1,2に示した。この指数が大きいほど、特に指数が102以上であると、積雪路面における雪上性能(操縦安定性)が優れていることを意味する。
得られた空気入りタイヤをリムサイズ18×7JJのホイールに組付け、国産2.5リットルクラスの試験車両に装着し、空気圧220kPaの条件で湿潤路面からなる1周2.6kmのテストコースを実車走行させ、そのときの操縦安定性を専門パネラー3名による感応評価により採点した。得られた結果は比較例1を100とする指数として、表1,2に示した。この指数が大きいほど、特に指数が102以上であると、湿潤路面におけるウェット操縦安定性が優れていることを意味する。
・変性S-SBR1:末端変性溶液重合スチレンブタジエンゴム、スチレン単位含有量が42重量%、ビニル単位含有量が32重量%、重量平均分子量(Mw)が75万、Tgが-25℃、油展オイルの含有量が27.27重量%、後述する製造方法により調製した末端変性溶液重合スチレンブタジエンゴム。
・変性S-SBR2:末端変性スチレンブタジエンゴム、スチレン単位含有量が21重量%、ビニル単位含有量が63重量%、重量平均分子量(Mw)が44万、Tgが-27℃、油展オイルの含有量が27.27重量%、後述する製造方法により調製した末端変性溶液重合スチレンブタジエンゴム。
・BR:ブタジエンゴム、日本ゼオン社製Nipol BR1220
・NR:天然ゴム、SIR20
・シリカ1:ローディア社製Zeosil 1165MP、DBP吸収量が200ml/100g、窒素吸着比表面積(N2SA)が160m2/g、CTAB比表面積(CTAB)が159m2/g。
・シリカ2:ローディア社製Zeosil Premium 200MP、DBP吸収量が203ml/100g、窒素吸着比表面積(N2SA)が200m2/g、CTAB比表面積(CTAB)が197m2/g。
・カーボンブラック:東海カーボン社製シーストKH
・シランカップリング剤:エボニックデグサ社製Si69、ビス(3-トリエトキシシリルプロピル)テトラスルフィド
・オイル:昭和シェル石油社製エキストラクト4号S
窒素置換された内容量10Lのオートクレーブ反応器に、シクロヘキサン4533g、スチレン338.9g(3.254mol)、ブタジエン468.0g(8.652mol)、イソプレン20.0g(0.294mol)およびN,N,N′,N′-テトラメチルエチレンジアミン0.189mL(1.271mmol)を仕込み、攪拌を開始した。反応容器内の内容物の温度を50℃にした後、n-ブチルリチウム5.061mL(7.945mmol)を添加した。重合転化率がほぼ100%に到達した後、さらにイソプレン12.0gを添加して5分間反応させた後、1,6-ビス(トリクロロシリル)ヘキサンの40wt%トルエン溶液0.281g(0.318mmol)を添加し、30分間反応させた。さらに、下記に示すポリオルガノシロキサンAの40wt%キシレン溶液18.3g(0.318mmol)を添加し、30分間反応させた。メタノール0.5mLを添加して30分間攪拌した。得られたポリマー溶液に老化防止剤(イルガノックス1520、BASF社製)を少量添加し、油展オイルの含有量が27.27重量%になるようにフッコールエラミック30(新日本石油(株)製)を添加した後、スチームストリッピング法により固体状のゴムを回収した。得られた固体ゴムをロールにより脱水し、乾燥機中で乾燥を行い、変性S-SBR1を得た。
窒素置換された100mlアンプル瓶に、シクロヘキサン28gおよびテトラメチルエチレンジアミン8.6mmolを添加し、さらに、n-ブチルリチウム6.1mmolを添加した。次いで、イソプレン8.0gをゆっくりと添加し、60℃のアンプル瓶内で120分反応させることにより、イソプレンブロック(開始剤1とする)を得た。この開始剤1の重量平均分子量(Mw)は2200、分子量分布(Mw/Mn)は1.08、およびイソプレン単位由来のビニル結合含有量は72.3wt%であった。
・酸化亜鉛:正同化学工業社製酸化亜鉛3種
・ステアリン酸:千葉脂肪酸社製ビーズステアリン酸
・老化防止剤:住友化学社製アンチゲン6C
・ワックス:大内新興化学工業社製サンノック
・硫黄:鶴見化学工業社製金華印油入微粉硫黄
・加硫促進剤1:加硫促進剤CBS、大内新興化学工業社製ノクセラーCZ-G
・加硫促進剤2:加硫促進剤DPG、大内新興化学工業社製ノクセラーD
2 サイドウォール部
3 ビード部
4 カーカス層
5 ビードコア
6 ビードフィラー
7 インナーライナー層
8 ベルト層
9 ベルトカバー層
10 トレッドゴム層
11 サイドゴム層
12 リムクッションゴム層
Claims (6)
- 末端変性スチレンブタジエンゴムを40重量%以上、天然ゴムを8~35重量%、ブタジエンゴムを15~40重量%含むジエン系ゴム100重量部に対し、シリカを50重量%以上含む充填剤を66~110重量部配合したゴム組成物であって、前記末端変性スチレンブタジエンゴムが、その末端の官能基がシラノール基と反応する化合物に由来し、そのスチレン単位含有量が38~48重量%、その油展オイルの含有量が30重量%未満であり、前記天然ゴム(NR)に対するブタジエンゴム(BR)の配合量の比(BR/NR)が1.0を超え2.5以下であると共に、前記ゴム組成物の脆化温度が-45℃以下であることを特徴とするタイヤトレッド用ゴム組成物。
- 前記シリカが、DBP吸収量が160~220ml/100g、窒素吸着比表面積が145~193m2/g、CTAB比表面積が140~184m2/gであることを特徴とすることを特徴とする請求項1に記載のタイヤトレッド用ゴム組成物。
- 前記タイヤトレッド用ゴム組成物100重量%中、オイル成分の合計が25~50重量%であることを特徴とする請求項1または2に記載のタイヤトレッド用ゴム組成物。
- 前記末端変性スチレンブタジエンゴムの少なくとも一つの末端の官能基が、ポリオルガノシロキサン化合物、エポキシ化合物、ヒドロカルビルオキシ珪素化合物から選ばれる少なくとも1種の化合物に由来することを特徴とする請求項1~3のいずれかに記載のタイヤトレッド用ゴム組成物。
- 前記末端変性スチレンブタジエンゴムの一つの末端にイソプレンセグメントを有する請求項4に記載のタイヤトレッド用ゴム組成物。
- 請求項1~5のいずれかに記載のタイヤトレッド用ゴム組成物を使用した空気入りタイヤ。
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WO2019244850A1 (ja) * | 2018-06-18 | 2019-12-26 | 株式会社ブリヂストン | ゴム組成物およびタイヤ |
JP2021066755A (ja) * | 2019-10-17 | 2021-04-30 | 住友ゴム工業株式会社 | ゴム組成物の製造方法およびタイヤの製造方法 |
WO2023190688A1 (ja) * | 2022-03-31 | 2023-10-05 | 横浜ゴム株式会社 | タイヤ用ゴム組成物 |
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JP6071980B2 (ja) * | 2014-11-14 | 2017-02-01 | 住友ゴム工業株式会社 | 加硫ゴム組成物の製造方法、加硫ゴム組成物およびそれを用いたスタッドレスタイヤ |
JP6071979B2 (ja) * | 2014-11-14 | 2017-02-01 | 住友ゴム工業株式会社 | 加硫ゴム組成物の製造方法、加硫ゴム組成物およびそれを用いたスタッドレスタイヤ |
JP6249034B2 (ja) | 2016-03-25 | 2017-12-20 | 横浜ゴム株式会社 | タイヤトレッド用ゴム組成物 |
KR101883341B1 (ko) | 2016-10-27 | 2018-07-31 | 금호타이어 주식회사 | 고 내마모성 타이어 트레드용 고무 조성물 |
JP2018172593A (ja) * | 2017-03-31 | 2018-11-08 | 日本ゼオン株式会社 | 油展変性共役ジエン系ゴムおよびその製造方法 |
JP6384568B1 (ja) * | 2017-05-16 | 2018-09-05 | 横浜ゴム株式会社 | 空気入りタイヤ |
JP6881583B2 (ja) * | 2017-07-21 | 2021-06-02 | 横浜ゴム株式会社 | 空気入りタイヤ |
WO2019116701A1 (ja) | 2017-12-15 | 2019-06-20 | 株式会社ブリヂストン | ゴム組成物、加硫ゴム及びタイヤ |
KR102084129B1 (ko) * | 2018-03-29 | 2020-03-03 | 한국타이어앤테크놀로지 주식회사 | 타이어 트레드용 고무 조성물 및 이를 포함하는 타이어 |
JP7434703B2 (ja) * | 2018-08-06 | 2024-02-21 | 住友ゴム工業株式会社 | トレッド用ゴム組成物及び空気入りタイヤ |
JP7127705B2 (ja) | 2021-01-08 | 2022-08-30 | 横浜ゴム株式会社 | 空気入りタイヤ |
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