WO2018003526A1 - タイヤ用ゴム組成物 - Google Patents
タイヤ用ゴム組成物 Download PDFInfo
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- WO2018003526A1 WO2018003526A1 PCT/JP2017/022195 JP2017022195W WO2018003526A1 WO 2018003526 A1 WO2018003526 A1 WO 2018003526A1 JP 2017022195 W JP2017022195 W JP 2017022195W WO 2018003526 A1 WO2018003526 A1 WO 2018003526A1
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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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- 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
- B60C1/0025—Compositions of the sidewalls
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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
- B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
- B60C11/0008—Tyre tread bands; Tread patterns; Anti-skid inserts characterised by the tread rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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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
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/10—Copolymers of styrene with conjugated dienes
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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
- C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C08L57/02—Copolymers of mineral oil hydrocarbons
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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
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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
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
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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
- 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
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Definitions
- the present invention relates to a rubber composition for tires that improves the wet grip performance, on-snow performance, cut resistance, wear resistance, and processability of a pneumatic tire.
- Pneumatic tires for multi-purpose sports vehicles (SUVs) and light trucks are designed for off-road running and durability (cut resistance), on-road comfort and quietness, and all-season use. Excellent performance in a wide variety of areas, such as on-snow performance when driving on snowy road surfaces, wet grip performance, dry grip performance, and wear resistance when traveling on non-snow-covered road surfaces (wet road surfaces and dry road surfaces) Is required.
- Patent Document 1 discloses that wet grip performance and wear resistance are improved by using a rubber composition for a tire containing butadiene rubber, an emulsion-polymerized styrene butadiene rubber having an amount of bonded styrene of 35% by weight or more, and an aromatic modified terpene resin. is suggesting.
- this rubber composition for tires has insufficient performance on snow and cut resistance when running on a snowy road surface, and it has been necessary to improve the processability of the rubber composition.
- Patent Document 2 discloses that a rubber component containing 5 to 50% by mass of a modified conjugated diene copolymer and natural rubber and / or diene synthetic rubber is mixed with 50 to 95% by mass of silica and 50 to 5% by mass of carbon black. It is proposed to improve grip performance and wear resistance with a rubber composition for tire treads comprising 60 to 140 parts by mass of a reinforcing filler consisting of 5% and 5 to 60 parts by mass of a resin. However, this rubber composition for tire tread cannot sufficiently improve wet grip performance and on-snow performance, and may lack cut resistance, wear resistance and workability, and further improvement is required. It was done.
- An object of the present invention is to provide a rubber composition for a tire that improves on-snow performance, cut resistance, wear resistance, and workability to a level higher than conventional levels while ensuring excellent wet grip performance of a pneumatic tire. There is to do.
- the rubber composition for tires of the present invention that achieves the above-described object comprises 50 mass parts or more of emulsion-polymerized styrene butadiene rubber having a bound styrene content of 30 mass% or less, 20 to 40 mass parts of butadiene rubber, and WN mass of natural rubber.
- a diene system comprising 50 parts by mass or more of emulsion-polymerized styrene butadiene rubber having a bound styrene content of 30% by mass or less, 20 to 40 parts by mass of butadiene rubber and WN parts by mass of natural rubber.
- the tire rubber composition of the present invention 50 to 120 parts by mass of a filler is blended with 100 parts by mass of the diene rubber, and the silica accounts for 10% by mass or more in the filler.
- the CTAB specific surface area is preferably 120 to 180 m 2 / g.
- the pneumatic tire comprising the rubber composition for tires of the present invention can improve performance on snow, cut resistance and wear resistance while improving wet grip performance. Moreover, since it is produced using a rubber composition for tires with good processability, the above-described high-quality tire can be stably obtained.
- FIG. 1 is a cross-sectional view in the tire meridian direction showing an example of an embodiment of a pneumatic tire using the rubber composition for a tire of the present invention.
- the pneumatic tire illustrated in FIG. 1 has a tread portion 1, a sidewall portion 2 and a bead portion 3, a carcass layer 4 is mounted between the left and right bead portions 3 and 3, and both end portions thereof are bead cores 5.
- the tire is folded from the inside to the outside.
- a belt layer 6 is disposed outside the carcass layer 4 in the tire tread portion 1 in the tire radial direction, and a tread rubber 7 is disposed outside the belt layer 6.
- the tire rubber composition of the present invention can be suitably used for the tread rubber 7 and the sidewall portion 2. Especially, it is good to use for the tread rubber 7.
- the rubber component is a diene rubber.
- the diene rubber necessarily includes emulsion-polymerized styrene butadiene rubber, butadiene rubber and natural rubber having a bound styrene content of 30% by mass or less, and the total of these diene rubbers is 100 parts by mass.
- butadiene rubber usually used in a rubber composition for tires can be used.
- the content of butadiene rubber is 20 to 40 parts by mass, preferably 24 to 38 parts by mass, more preferably 28 to 36 parts by mass, per 100 parts by mass of the diene rubber. If the content of butadiene rubber is less than 20 parts by mass, the performance on snow is deteriorated. When the content of butadiene rubber exceeds 40 parts by mass, the wet grip performance decreases.
- the performance on snow can be improved by containing an emulsion-polymerized styrene butadiene rubber having a bound styrene content of 30% by mass or less. Moreover, workability can be made favorable.
- the amount of bound styrene in the emulsion-polymerized styrene-butadiene rubber is 30% by mass or less, preferably 20 to 28% by mass.
- the amount of bound styrene in the emulsion-polymerized styrene-butadiene rubber exceeds 30% by mass, the performance on snow deteriorates. Moreover, there exists a tendency for workability to fall.
- the amount of bound styrene is measured by infrared spectroscopic analysis (Hampton method).
- the content of the emulsion-polymerized styrene butadiene rubber is 50 parts by mass or more, preferably 52 to 64 parts by mass, more preferably 54 to 62 parts by mass in 100 parts by mass of the diene rubber. If the content of the emulsion-polymerized styrene butadiene rubber is less than 50 parts by mass, the effect of improving the performance on snow cannot be obtained sufficiently.
- wet grip performance can be improved by containing natural rubber.
- the content of natural rubber in 100 parts by mass of diene rubber is defined as WN parts by mass.
- the content WN of the natural rubber is the balance of the emulsion-polymerized styrene butadiene rubber and butadiene rubber in 100 parts by mass of the diene rubber.
- the upper limit of the natural rubber content WN is 30 parts by mass, preferably 28 parts by mass, and more preferably 26 parts by mass.
- the lower limit of the natural rubber content WN is preferably 6 parts by mass, more preferably 8 parts by mass, and even more preferably 10 parts by mass.
- the rubber composition for tires of the present invention can improve the behavior of dynamic viscoelasticity, which is an index of exothermic property and wet grip performance, by blending silica.
- silica usually used for a rubber composition for tires, for example, wet method silica, dry method silica, or surface-treated silica can be used. Such silica can be used by appropriately selecting from commercially available silica.
- Silica preferably has a CTAB specific surface area of preferably 120 to 180 m 2 / g, more preferably 140 to 170 m 2 / g.
- CTAB specific surface area of silica is less than 120 m 2 / g, wet performance deteriorates.
- the CTAB specific surface area of silica exceeds 180 m 2 / g, the effect of reducing the heat generation cannot be sufficiently obtained.
- the CTAB specific surface area of silica is measured according to JIS K6217-3.
- the blending amount WS of silica has a specific relationship with the blending amount WN of natural rubber. That is, the ratio (WN / WS) of the blending amount WN of the natural rubber to the blending amount WS of the silica blending amount is set to 0.4 to 1.0, preferably 0.5 to 0.8.
- the ratio (WN / WS) of the blend amount of natural rubber and silica is less than 0.4, the viscosity increases and the processability deteriorates. Also, wet grip performance and wear resistance tend to decrease.
- the blending ratio (WN / WS) exceeds 1.0, the wet grip performance decreases.
- the blending amount WS of silica has a specific relationship with the blending amount WT of the aromatic-modified terpene resin, as will be described later.
- Silica can be blended with fillers other than silica.
- fillers other than silica include carbon black, clay, calcium carbonate, aluminum hydroxide, talc, and mica. Of these, carbon black is preferred. By compounding carbon black, the strength of the rubber composition can be improved, and the wear resistance and cut resistance can be improved. These other fillers can be used alone or in combination.
- the amount of the filler containing silica is preferably 50 to 120 parts by mass, more preferably 55 to 110 parts by mass, and further preferably 60 to 90 parts by mass with respect to 100 parts by mass of the diene rubber. If the blending amount of the filler is less than 50 parts by mass, the wet grip performance may be deteriorated. Moreover, when the compounding quantity of a filler exceeds 120 mass parts, there exists a possibility that exothermic property may become large.
- the blending amount of silica is preferably 10% by mass or more, more preferably 10 to 40% by mass in the total filler. If the amount of silica is less than 10% by mass, the effect of improving wet grip performance and reducing heat generation cannot be obtained sufficiently.
- a silane coupling agent together with silica to improve the dispersibility of the silica with respect to the diene rubber.
- the compounding amount of the silane coupling agent is preferably 3 to 15% by mass, more preferably 4 to 10% by mass with respect to the compounding amount of silica.
- the amount of the silane coupling agent is less than 3% by mass, the dispersibility of silica cannot be sufficiently improved.
- the compounding quantity of a silane coupling agent exceeds 15 mass%, silane coupling agents will aggregate and condense and it will become impossible to acquire a desired effect.
- the type of the silane coupling agent is not particularly limited, but a sulfur-containing silane coupling agent is preferable.
- the sulfur-containing silane coupling agent include bis- (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) disulfide, 3-trimethoxysilylpropylbenzothiazole tetrasulfide, and ⁇ -mercaptopropyl. Examples thereof include triethoxysilane and 3-octanoylthiopropyltriethoxysilane.
- the tire rubber composition of the present invention improves wet grip performance by blending an aromatic modified terpene resin.
- aromatic-modified terpene resin improves the dispersibility of fillers such as silica and carbon black and further improves the compatibility between the filler and the diene rubber.
- other resin components such as C5-C9 petroleum resin, unmodified terpene resin, rosin resin, terpene phenol resin, hydrogenated terpene resin, phenol resin, xylene resin, etc.
- blends When it mix
- an aromatic-modified terpene resin having a softening point of preferably 100 ° C. or higher, more preferably 120 to 170 ° C. may be blended. If the softening point of the aromatic modified terpene resin is less than 100 ° C., the effect of improving the wet performance may not be sufficiently obtained. In this specification, the softening point of the aromatic modified terpene resin is measured based on JIS K6220-1 (ring and ball method).
- the compounding amount of the aromatic modified terpene resin is such that when the compounding amount of silica is WS parts by mass and the compounding amount of the aromatic modified terpene resin is WT parts by mass, the ratio (WS / WT) between the two is 2.0 to 5. 0, preferably 3.0 to 4.0.
- the ratio of the blending amount of silica and aromatic modified terpene resin (WS / WT) is less than 2.0, on-snow performance decreases and wear resistance decreases. Moreover, exothermicity becomes large.
- the ratio of the blending amount (WS / WT) exceeds 5.0, the wear resistance decreases.
- the aromatic modified terpene resin is obtained by polymerizing a terpene such as ⁇ -pinene, ⁇ -pinene, dipentene, limonene and at least one aromatic compound of styrene, ⁇ -methylstyrene, and vinyltoluene.
- Aromatically modified terpene resin is preferably used.
- the tire rubber composition of the present invention contains an appropriate amount of oil.
- the oil include oils usually added to tire rubber compositions such as aroma oil and process oil, and oil-extended components added to emulsion-polymerized styrene butadiene rubber.
- the amount of oil refers to the sum of oil-extended oil and post-added oil components contained in diene rubbers such as emulsion-polymerized styrene butadiene rubber.
- the total amount of oil and aromatic modified terpene resin is preferably less than 50 parts by mass, more preferably less than 45 parts by mass, and even more preferably less than 40 parts by mass with respect to 100 parts by mass of the diene rubber. To be decided.
- the total of the oil and the aromatic-modified terpene resin is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and further preferably 25 parts by mass or more with respect to the lower limit.
- the glass transition temperature (hereinafter referred to as “polymer Tg”) of a diene rubber comprising emulsion-polymerized styrene butadiene rubber, butadiene rubber and natural rubber is preferably ⁇ 85 to ⁇ 55 ° C. More preferably, it is -75 to -65 ° C. If the polymer Tg is higher than -55 ° C, the performance on snow and the wear resistance may be lowered. If the polymer Tg is lower than -85 ° C, the wet grip performance may be deteriorated.
- the polymer Tg is the sum of values obtained by multiplying the glass transition temperature (Tg) of emulsion-polymerized styrene-butadiene rubber, butadiene rubber and natural rubber by the mass fraction of the emulsion-polymerized styrene-butadiene rubber, butadiene rubber and natural rubber.
- the glass transition temperature (hereinafter referred to as “compound Tg”) of the rubber composition for tires is preferably ⁇ 80 to ⁇ 50 ° C., more preferably ⁇ 70 to ⁇ 60 ° C. If the compound Tg is higher than -50 ° C, the performance on snow and the wear resistance may be lowered. Further, if the compound Tg is lower than ⁇ 80 ° C., the wet grip performance may be deteriorated.
- the compound Tg is an emulsion-polymerized styrene-butadiene rubber, butadiene rubber, natural rubber, aromatic, and a glass transition temperature (Tg) of emulsion-polymerized styrene-butadiene rubber, butadiene rubber, natural rubber, aromatic modified terpene resin and oil.
- Tg glass transition temperature
- various additives generally used in rubber compositions such as a vulcanization or crosslinking agent, an anti-aging agent, and a plasticizer can be blended.
- the rubber composition can be kneaded by a conventional method and used for vulcanization or crosslinking. As long as the amount of these additives is not contrary to the object of the present invention, a conventional general amount can be used.
- the rubber composition for tires can be produced by mixing the above components using a normal rubber kneading machine such as a Banbury mixer, a kneader, or a roll.
- the tire rubber composition of the present invention can constitute a tread portion and a sidewall portion of a pneumatic tire.
- the tire rubber composition may be used in at least one selected from these parts. Among these, it is preferable to constitute the tread portion.
- the pneumatic tire using the tire rubber composition of the present invention in these parts can improve wet grip performance, and improve performance on snow, cut resistance and wear resistance to the conventional level or more. I can do it.
- the rubber composition for tires having good processability is produced, a high-quality tire excellent in wet grip performance, performance on snow, cut resistance and wear resistance can be stably obtained.
- the pneumatic tire using the tire rubber composition described above for the tread portion or the sidewall portion is a pneumatic tire for a multipurpose sports vehicle (SUV) or a light truck or a pneumatic tire for all seasons.
- the pneumatic tire of the present invention can reduce heat generation and improve wet grip performance and on-snow performance to the conventional level or more.
- Examples 1 to 10 26 types of rubber compositions (Examples 1 to 10, Standard Examples and Comparative Examples 1 to 15) having the compositions shown in Tables 1 to 3 having the compounding agents shown in Table 4 as common recipes, were respectively sulfur and vulcanized.
- the ingredients other than the accelerator were weighed and kneaded for 5 minutes with a 16 L Banbury mixer, which was discharged and cooled to room temperature. This was supplied to an open roll, and sulfur and a vulcanization accelerator were added and mixed to prepare a tire rubber composition.
- the Mooney viscosity of the 26 types of rubber compositions obtained was measured by the following method.
- vulcanized rubber sheets were prepared by vulcanization at 160 ° C. for 20 minutes in respective molds, and dynamic viscoelasticity was obtained by the following method. Measured and used as an index of wet grip performance and on-snow performance.
- the cut resistance and wear resistance were evaluated by the following methods.
- Mooney viscosity The Mooney viscosity of the obtained rubber composition was compliant with JIS K6300-1: 2001, using a Mooney viscometer with an L-shaped rotor, preheating time of 1 minute, rotor rotation time of 4 minutes, and 100 ° C. Measured under conditions. The obtained results were expressed as an index with the reciprocal of the value of the standard example being 100, and are shown in the column of “workability” in Tables 1 to 3. A larger index means a lower Mooney viscosity and better workability.
- Dynamic viscoelasticity 0 ° C tan ⁇ and -10 ° C E '
- the dynamic viscoelasticity of the obtained vulcanized rubber sheet was measured with a viscoelasticity spectrometer manufactured by Toyo Seiki Seisakusho Co., Ltd. at an initial strain of 10%, an amplitude of ⁇ 2%, and a frequency of 20 Hz. E ′ of ⁇ 10 ° C. was determined.
- the obtained result of tan ⁇ (0 ° C.) is shown in the column of “Wet grip performance” in Tables 1 to 3 as an index with the value of the standard example as 100.
- the results of E ′ ( ⁇ 10 ° C.) obtained are listed in the “Snow Performance” column of Tables 1 to 3 as an index with the reciprocal of the value of the standard example as 100.
- Cut resistance Using the obtained vulcanized rubber sheet, in accordance with JIS K6251, a dumbbell JIS No. 3 type test piece was prepared, and a tensile test was performed at a pulling speed of 500 mm / min at room temperature (20 ° C.). The tensile strength at break was measured. The obtained results are listed in the column of “Cut resistance” in Tables 1 to 3 as an index for setting the value of the standard example to 100. A larger index means stronger tensile break strength and better cut resistance.
- Abrasion resistance The obtained vulcanized rubber sheet was conditioned in accordance with JIS K6264 using a Lambone abrasion tester (Iwamoto Seisakusho Co., Ltd.) at a temperature of 20 ° C., a load of 49 N, a slip rate of 25%, and a time of 4 minutes. The amount of wear was measured. The obtained results are shown in Tables 1 to 3 as “wear resistance” with an index where the reciprocal of the value of the standard example is 100. Higher index means higher wear resistance and better tire durability.
- BR Butadiene rubber
- Nippon Zeon BR1220 E-SBR-1 emulsion-polymerized styrene butadiene rubber, Nipol 1723 manufactured by Nippon Zeon Co., Ltd., 23.4% by mass of bound styrene, and 37.5 parts by mass of an oil-extended component with respect to 100 parts by mass of styrene butadiene rubber.
- E-SBR-2 emulsion polymerization styrene butadiene rubber, Nipol 1739 manufactured by Nippon Zeon Co., Ltd., 38.9% by mass of bound styrene, and 37.5 parts by mass of oil-extended component with respect to 100 parts by mass of styrene butadiene rubber.
- ⁇ NR Natural rubber
- TSR20 S-SBR solution polymerized styrene butadiene rubber
- Nipol NS460 manufactured by Nippon Zeon Co., Ltd., 26.1% by mass of bound styrene
- Carbon black Show black 339 manufactured by Cabot Japan
- Silica-1 Zeosil 1165MP (CTAB specific surface area 155 m 2 / g) manufactured by Rhodia ⁇
- Silica-2 Rhodia Zeosil 115GR (CTAB specific surface area 110 m 2 / g)
- Coupling agent Sulfur-containing silane coupling agent, Si69 manufactured by Evonik Degussa
- Aromatically modified terpene resin-1 YS resin TO-125 manufactured by Yasuhara Chemical Co., Ltd., softening point 125 ° C.
- Aromatically modified terpene resin-2 YS resin TO-85 manufactured by Yasuhara Chemical Co., softening point 85 ° C ⁇ C5-C9 petroleum resin: PetroTac 120V manufactured by Tosoh Corporation
- Unmodified terpene resin YS resin PX1000 manufactured by Yasuhara Chemical Terpene phenol resin: YS Polystar N125 manufactured by Yasuhara Chemical Process oil: Extract No. 4 S manufactured by Showa Shell Sekiyu KK
- ⁇ Stearic acid Beads stearic acid manufactured by NOF Corporation
- Zinc flower Zinc oxide 3 types manufactured by Shodo Chemical Co., Ltd.
- Anti-aging agent 6PPD manufactured by Flexis
- Vulcanization accelerator-1 Noxeller CZ-G manufactured by Ouchi Shinsei Chemical Co., Ltd.
- Vulcanization accelerator-2 Soxinol DG manufactured by Sumitomo Chemical Co., Ltd.
- Sulfur Fine powder sulfur with Jinhua seal oil manufactured by Tsurumi Chemical Co., Ltd.
- the rubber compositions for tires of Examples 1 to 10 are all on the snow and have cut resistance while maintaining wet grip performance as compared with the rubber compositions for tires of the standard examples. And maintenance and improvement of wear resistance.
- the rubber composition for tires has a small Mooney viscosity and good processability.
- the tire rubber composition of Comparative Example 1 is an emulsion-polymerized styrene butadiene rubber having a butadiene rubber content of more than 40 parts by mass and a bound styrene content of 30% by mass or less. Since the content of is less than 50 parts by mass, the wet grip performance is inferior. Since the rubber composition for tires of Comparative Example 2 has a butadiene rubber content exceeding 40 parts by mass, the wet grip performance is inferior. Since the rubber composition for tires of Comparative Example 3 has a butadiene rubber content of less than 20 parts by mass, the performance on snow is inferior and the wear resistance is inferior.
- the rubber composition for tires of Comparative Example 5 is an emulsion-polymerized styrene-butadiene rubber E- in which the amount of bonded styrene exceeds 30% by mass instead of the emulsion-polymerized styrene-butadiene rubber E-SBR-1 in which the amount of bonded styrene is 30% by mass or less. Since SBR-2 is blended, processability and performance on snow are inferior.
- the rubber composition for tires of Comparative Example 7 has a content of emulsion-polymerized styrene butadiene rubber E-SBR-1 having a bound styrene content of 30% by mass or less and less than 50 parts by mass. So wet grip performance is poor.
- the rubber composition for tires of Comparative Example 8 is inferior in workability and wet grip performance because the mass ratio of natural rubber to silica (WN / WS) exceeds 1.0.
- the rubber composition for tires of Comparative Example 9 is inferior in workability, wet grip performance, cut resistance and wear resistance because the mass ratio (WN / WS) of natural rubber to silica is less than 0.4.
- the rubber composition for tires of Comparative Example 10 is inferior in workability, wet grip performance, cut resistance and wear resistance because the mass ratio (WS / WT) of silica and aromatic modified terpene resin exceeds 5.0.
- the rubber composition for tires of Comparative Example 11 is inferior in snow performance, cut resistance and wear resistance because the mass ratio (WB / WT) of butadiene rubber and aromatic modified terpene resin is less than 2.0.
- the rubber composition for tires of Comparative Example 12 is inferior in wet grip performance, on-snow performance, cut resistance, and wear resistance because a C5-C9 petroleum resin is blended in place of the aromatic modified terpene resin. Since the rubber composition for tires of Comparative Example 13 was blended with an unmodified terpene resin instead of the aromatic modified terpene resin, the wet grip performance was inferior. Since the rubber composition for tires of Comparative Example 14 was blended with a terpene phenol resin instead of the aromatic modified terpene resin, the wet grip performance and on-snow performance were poor.
- the tire rubber composition of Comparative Example 15 is inferior in processability, wet grip performance, and cut resistance because the mass ratio (WN / WS) of natural rubber to silica is less than 0.4.
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Abstract
Description
得られたゴム組成物のムーニー粘度をJIS K6300-1:2001に準拠して、ムーニー粘度計にてL形ロータを使用し、予熱時間1分、ロータの回転時間4分、100℃の条件で測定した。得られた結果は、標準例の値の逆数を100とする指数で表わし表1~3の「加工性」の欄に示した。この指数が大きいほどムーニー粘度が低く、加工性が良好であることを意味する。
得られた加硫ゴムシートの動的粘弾性を、東洋精機製作所社製粘弾性スペクトロメーターを用いて、初期歪み10%、振幅±2%、周波数20Hzで測定し、温度0℃のtanδ、および-10℃のE'を求めた。得られたtanδ(0℃)の結果は、標準例の値を100とする指数にしてとして表1~3の「ウェットグリップ性能」の欄に記載した。「ウェットグリップ性能」の指数が大きいほどtanδ(0℃)が大きく、タイヤにしたときにウェットグリップ性能が優れることを意味し、ウェットグリップ性能の指数が98以上を合格レベルとする。また得られたE'(-10℃)の結果は、標準例の値の逆数を100とする指数にしてとして表1~3の「雪上性能」の欄に記載した。「雪上性能」の指数が大きいほどE'(-10℃)が小さく、タイヤにしたときに雪上性能が優れることを意味する。
得られた加硫ゴムシートを使用し、JIS K6251に準拠して、ダンベルJIS3号形試験片を作製し、室温(20℃)で500mm/分の引張り速度で引張り試験を行い、破断したときの引張り破断強度を測定した。得られた結果は、標準例の値を100にする指数として表1~3の「耐カット性能」の欄に記載した。この指数が大きいほど引張破断強度が強く耐カット性が優れることを意味する。
得られた加硫ゴムシートをJIS K6264に準拠して、ランボーン摩耗試験機(岩本製作所社製)を使用して、温度20℃、荷重49N、スリップ率25%、時間4分の条件で摩耗量を測定した。得られた結果は、標準例の値の逆数を100とする指数にし、「耐摩耗性能」として表1~3に示した。この指数が大きいほど耐摩耗性が高く、タイヤ耐久性に優れることを意味する。
・BR:ブタジエンゴム、日本ゼオン社製Nipol BR1220
・E-SBR-1:乳化重合スチレンブタジエンゴム、日本ゼオン社製Nipol 1723、結合スチレン量が23.4質量%、油展成分をスチレンブタジエンゴム100質量部に対し37.5質量部含む。
・E-SBR-2:乳化重合スチレンブタジエンゴム、日本ゼオン社製Nipol 1739、結合スチレン量が38.9質量%、油展成分をスチレンブタジエンゴム100質量部に対し37.5質量部含む。
・NR:天然ゴム、TSR20
・S-SBR:溶液重合スチレンブタジエンゴム、日本ゼオン社製Nipol NS460、結合スチレン量が26.1質量%、油展成分をスチレンブタジエンゴム100質量部に対し37.5質量部含む。
・カーボンブラック:キャボットジャパン社製ショウブラック339
・シリカ-1:ローディア社製Zeosil 1165MP(CTAB比表面積155m2/g)
・シリカ-2:ローディア社製Zeosil 115GR(CTAB比表面積110m2/g)
・カップリング剤:硫黄含有シランカップリング剤、エボニック デグッサ社製Si69
・芳香族変性テルペン樹脂-1:ヤスハラケミカル社製YSレジンTO-125、軟化点125℃
・芳香族変性テルペン樹脂-2:ヤスハラケミカル社製YSレジンTO-85、軟化点85℃
・C5-C9系石油樹脂:東ソー社製ペトロタック120V
・未変性テルペン樹脂:ヤスハラケミカル社製YSレジンPX1000
・テルペンフェノール樹脂:ヤスハラケミカル社製YSポリスターN125
・プロセスオイル:昭和シェル石油社製エキストラクト4号S
・ステアリン酸:日油社製ビーズステアリン酸
・亜鉛華:正同化学工業社製酸化亜鉛3種
・老化防止剤:フレキシス社製6PPD
・加硫促進剤-1:大内新興化学社製ノクセラーCZ-G
・加硫促進剤-2:住友化学社製ソクシノールD-G
・硫黄:鶴見化学工業社製金華印油入微粉硫黄
比較例2のタイヤ用ゴム組成物は、ブタジエンゴムの含有量が40質量部を超えるので、ウェットグリップ性能が劣る。
比較例3のタイヤ用ゴム組成物は、ブタジエンゴムの含有量が20質量部未満であるので、雪上性能が劣り、耐摩耗性が劣る。
比較例4のタイヤ用ゴム組成物は、天然ゴムを配合しなかったので、雪上性能、耐カット性および耐摩耗性が劣る。
比較例5のタイヤ用ゴム組成物は、結合スチレン量が30質量%以下の乳化重合スチレンブタジエンゴムE-SBR-1の代わりに、結合スチレン量が30質量%を超える乳化重合スチレンブタジエンゴムE-SBR-2を配合したので、加工性および雪上性能が劣る。
比較例6のタイヤ用ゴム組成物は、結合スチレン量が30質量%以下の乳化重合スチレンブタジエンゴムE-SBR-1の代わりに、結合スチレン量が30質量%以下の溶液重合スチレンブタジエンゴムS-SBRを配合したので、加工性が劣る。
比較例8のタイヤ用ゴム組成物は、天然ゴムとシリカのの質量比(WN/WS)が1.0を超えるので、加工性およびウェットグリップ性能が劣る。
比較例9のタイヤ用ゴム組成物は、天然ゴムとシリカのの質量比(WN/WS)が0.4未満であるので、加工性、ウェットグリップ性能、耐カット性能および耐摩耗性が劣る。
比較例10のタイヤ用ゴム組成物は、シリカと芳香族変性テルペン樹脂の質量比(WS/WT)が5.0を超えるので、加工性、ウェットグリップ性能、耐カット性および耐摩耗性が劣る。
比較例11のタイヤ用ゴム組成物は、ブタジエンゴムと芳香族変性テルペン樹脂の質量比(WB/WT)が2.0未満であるので、雪上性能、耐カット性および耐摩耗性が劣る。
比較例13のタイヤ用ゴム組成物は、芳香族変性テルペン樹脂の代わりに未変性テルペン樹脂を配合したので、ウェットグリップ性能が劣る。
比較例14のタイヤ用ゴム組成物は、芳香族変性テルペン樹脂の代わりにテルペンフェノール樹脂を配合したので、ウェットグリップ性能および雪上性能が劣る。
比較例15のタイヤ用ゴム組成物は、天然ゴムとシリカのの質量比(WN/WS)が0.4未満であるので、加工性、ウェットグリップ性能および耐カット性能が劣る。
2 サイドウォール部
Claims (3)
- 結合スチレン量が30質量%以下である乳化重合スチレンブタジエンゴムを50質量部以上、ブタジエンゴムを20~40質量部および天然ゴムをWN質量部からなるジエン系ゴム100質量部に、芳香族変性テルペン樹脂をWT質量部およびシリカをWS質量部配合してなり、前記天然ゴムの配合量(WN)と前記シリカの配合量(WS)の比(WN/WS)が0.4~1.0、前記シリカの配合量(WS)と前記芳香族変性テルペン樹脂の配合量(WT)の比(WS/WT)が2.0~5.0であることを特徴とするタイヤ用ゴム組成物。
- 前記ジエン系ゴム100質量部に対し、充填剤を50~120質量部配合すると共に、該充填剤中、前記シリカが10質量%以上を占め、かつ該シリカのCTAB比表面積が120~180m2/gであることを特徴とする請求項1に記載のタイヤ用ゴム組成物。
- 請求項1又は2に記載のタイヤ用ゴム組成物からなることを特徴とする空気入りタイヤ。
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WO2020256082A1 (ja) * | 2019-06-20 | 2020-12-24 | 株式会社ブリヂストン | タイヤ |
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RU2805484C2 (ru) * | 2021-03-05 | 2023-10-17 | Дзе Йокогама Раббер Ко., Лтд. | Каучуковая композиция для шины и шина, содержащая такую композицию |
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JP6838599B2 (ja) * | 2018-12-17 | 2021-03-03 | 横浜ゴム株式会社 | 空気入りタイヤ |
KR102212887B1 (ko) * | 2019-09-25 | 2021-02-08 | 금호타이어 주식회사 | 스노우 제동력이 유지되면서 젖은 노면에서의 제동력이 향상된 타이어용 트레드 고무 조성물 |
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