CN112272684A - Method for producing rubber composition for tire - Google Patents

Method for producing rubber composition for tire Download PDF

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Publication number
CN112272684A
CN112272684A CN201980038578.7A CN201980038578A CN112272684A CN 112272684 A CN112272684 A CN 112272684A CN 201980038578 A CN201980038578 A CN 201980038578A CN 112272684 A CN112272684 A CN 112272684A
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China
Prior art keywords
silica
group
mass
rubber
silane coupling
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CN201980038578.7A
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Chinese (zh)
Inventor
石井秀和
冈美幸
杉浦裕记
高木亮祐
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Yokohama Rubber Co Ltd
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Yokohama Rubber Co Ltd
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Priority claimed from JP2018074924A external-priority patent/JP6638756B2/en
Priority claimed from JP2018102370A external-priority patent/JP6809503B2/en
Application filed by Yokohama Rubber Co Ltd filed Critical Yokohama Rubber Co Ltd
Publication of CN112272684A publication Critical patent/CN112272684A/en
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • 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
    • C08K5/54—Silicon-containing compounds
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06—Waxes
    • C08L91/08—Mineral waxes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Provided is a method for producing a rubber composition for a tire, which has excellent hardness, low rolling resistance, and processability, in addition to wet grip performance. The rubber composition is produced by mixing 30 to 220 parts by mass of silica and 3 to 50 parts by mass of an aromatic oil per 100 parts by mass of a diene rubber, and mixing a silane coupling agent in an amount of 5 to 18% by mass relative to the amount of silica, wherein the silica, the silane coupling agent and the aromatic oil are put together into a mixer, mixed, and then the diene rubber is put into the mixer and kneaded.

Description

Method for producing rubber composition for tire
Technical Field
The present invention relates to a method for producing a rubber composition for a tire, which is excellent in hardness, low rolling resistance, and processability in addition to wet grip performance.
Background
Conventionally, a pneumatic tire is required to have excellent wet grip performance, excellent steering stability performance, and excellent fuel consumption performance (low rolling resistance) in order to improve safety. However, these characteristics are contradictory, and thus are difficult to satisfy at the same time. For example, it is known that a rubber composition for a tire is blended with silica to modify dynamic viscoelasticity characteristics in order to improve wet grip performance and low rolling resistance. However, when silica is blended, there is a problem that hardness is lower than when the same amount of carbon black is blended, and good driving stability cannot be obtained.
In order to further improve the wet grip performance and low rolling resistance of the rubber composition containing silica, it is known to blend a silane coupling agent or use silica having been subjected to surface treatment in advance in order to improve the dispersibility of silica in a diene rubber. However, when silica and a silane coupling agent are blended, the viscosity of the rubber composition may be increased and the processability may be lowered. Patent documents 1 and 2 propose to improve the dispersibility of silica by sequentially charging and/or separately kneading the constituent components of the rubber composition. However, the use of surface-treated silica or the successive charging and/or separate kneading has a problem of an increase in man-hours and an increase in production cost. Further, the problem of processability of the rubber composition is not necessarily sufficiently solved.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2016-151018
Patent document 2: japanese patent laid-open publication No. 2016-1699268
Disclosure of Invention
Problems to be solved by the invention
The purpose of the present invention is to provide a method for producing a rubber composition for a tire, which has excellent hardness, low rolling resistance, and processability in addition to wet grip performance.
Means for solving the problems
The method for producing a rubber composition for a tire according to the present invention for achieving the above object is a method for producing a rubber composition comprising 100 parts by mass of a diene rubber, 30 to 220 parts by mass of silica and 3 to 50 parts by mass of an aromatic oil, and a silane coupling agent in an amount of 5 to 18% by mass relative to the amount of silica, wherein the silica, the silane coupling agent, and the aromatic oil are charged into a mixer together, mixed, and then the diene rubber is charged and kneaded.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the production method of the present invention, since the total amount of silica, silane coupling agent, and aromatic oil is charged into the mixer and mixed, and then the diene rubber is charged and kneaded, the silica and silane coupling agent are easily brought into contact with each other, and the diene rubber is charged while the temperature of the mixer is lowered, and then a high shearing force is applied, so that the dispersibility of the silica can be further improved, and a rubber composition for a tire excellent in at least 1 selected from the group consisting of low rolling resistance, processability, and hardness in addition to wet grip performance can be obtained. Further, the pneumatic tire using the rubber composition for a tire can improve the wet performance and the steering stability by the excellent wet performance and the good hardness of the rubber composition for a tire.
In the production method of the present invention, carbon black may be put and mixed together with silica, a silane coupling agent, and an aromatic oil. The silica has a CTAB specific surface area of 150m2/g～300m2The ratio of the acid to the acid is preferably in terms of/g. The modified diene rubber may be contained in an amount of 40 mass% or more based on 100 mass% of the diene rubber.
In the production method of the present invention, a silane coupling agent represented by the general formula (1) can be used as the silane coupling agent. Further, zinc oxide may be added together with the diene rubber and mixed.
(CpH2p+1)t(CpH2p+1O)3-t-SiCqH2q-S-C(O)-CrH2r+1…(1)
(in the formula (1), p represents an integer of 1 to 3, q represents an integer of 1 to 3, r represents an integer of 1 to 15, and t represents an integer of 0 to 2.)
In the production method of the present invention, when the mixing step in the first stage of mixing silica, a silane coupling agent and a diene rubber and the mixing step in the final stage of mixing a vulcanization-based compounding agent thereafter are performed, the mixing completion temperature in the mixing step in the first stage is preferably 150 ℃ or higher.
Detailed Description
Generally, a method for producing a rubber composition for a tire includes at least 2 steps of: a kneading step (first-stage mixing step) of mixing and kneading a diene rubber, silica, a silane coupling agent, zinc oxide, carbon black, an aromatic oil, and a compounding agent other than a vulcanization-based compounding agent; and a step (final-stage mixing step) of cooling the mixture obtained in the kneading step and then mixing a vulcanization-based compounding agent. The method for producing a rubber composition for a tire of the present invention is characterized in that the kneading step (first-stage mixing step) is composed of at least 2 steps including: 1, putting all the silicon dioxide, the silane coupling agent and the aromatic oil into a mixer for mixing; and a 2 nd charging/mixing step of charging and kneading the diene rubber in a mixer containing silica and a silane coupling agent after the 1 st charging/mixing step. The zinc oxide may be added and kneaded at the same time as the diene rubber, or may be added and kneaded while maintaining the kneading after the diene rubber is added.
The manufacturing method of the present invention starts the first stage mixing process by performing a step of charging and mixing the entire amounts of silica, silane coupling agent, and aromatic oil in a mixer 1 st time. Thereby, the silica and the silane coupling agent are easily brought into contact with each other, and the silane coupling agent acts on the silica more effectively. This reduces the number of steps and production cost as compared with the case where the surface treatment of silica is performed in a separate step in the related art. Further, by mixing silica, a silane coupling agent and an aromatic oil first, the temperature of the mixer can be lowered, and the temperature at the time of subsequently kneading the diene rubber can be lowered, whereby the kneading strength in the mixer can be increased, and the dispersibility of silica can be improved. In the conventional first-stage mixing step in which a diene rubber is first put into a mixer and kneaded, and then various compounding agents are put into the mixer and kneaded, the temperature in the mixer increases and the viscosity of the diene rubber decreases due to the kneading of the diene rubber, and therefore, a high shearing force cannot be applied when silica is put into the mixer and kneaded later, and thus silica cannot be dispersed well.
The amount of the silica and the silane coupling agent charged into the mixer is 5 to 18 mass%, preferably 6 to 15 mass%, based on the amount of the silica. By setting the amount of the silane coupling agent to 5% by mass or more of the amount of silica, the dispersion of silica can be improved. Further, by setting the amount of the silane coupling agent to 18 mass% or less of the amount of silica, condensation of the silane coupling agents can be suppressed, and a rubber composition having desired hardness and strength can be obtained.
The silica, the silane coupling agent and the aromatic oil may be mixed by a mixer generally used for producing a rubber composition for a tire. The form of the rotor constituting the mixer may be either a mesh type or a non-mesh type. The rotation speed of the rotor may be set to a normal rotation speed in the production of the rubber composition for a tire.
In the present invention, the temperature at which the silica, the silane coupling agent and the aromatic oil are mixed is preferably 20 to 90 ℃, more preferably 30 to 70 ℃ by adjusting the set temperature of the mixer and the initial temperature of the silica. In particular, by setting the upper limit temperature at the time of mixing to 70 ℃, the step of charging and kneading the diene rubber after this step can be performed, whereby the shearing force can be increased and the dispersibility of silica can be improved.
The time for mixing the silica, the silane coupling agent, and the aromatic oil may be preferably 5 seconds to 2 minutes, and more preferably 20 seconds to 90 seconds. By setting the mixing time to 20 seconds or more, the silica, the silane coupling agent, and the aromatic oil can be mixed and sufficiently contacted. Further, by setting the mixing time to 90 seconds or less, the decrease in productivity can be suppressed.
In the production method of the present invention, carbon black may be charged and mixed together with silica, a silane coupling agent, and an aromatic oil, and rolling resistance and abrasion resistance may be made smaller. The carbon black is preferably put into the mixer together with the silica, the silane coupling agent and the aromatic oil. The mixing conditions for charging the carbon black may be the same as described above.
In the present invention, the diene rubber is put into a mixer after mixing of the silica, the silane coupling agent and the aromatic oil is completed, and the mixture is kneaded. The diene rubber may be charged into the mixer under the usual charging conditions. The conditions for kneading the silica, the silane coupling agent, and the aromatic oil with the diene rubber may be within the usual ranges.
The compounding agents other than the vulcanization-based compounding agent, which are compounded in the rubber composition for a tire, may be simultaneously charged with the diene-based rubber and kneaded, or may be charged and mixed after the completion of the kneading of the diene-based rubber. Examples of compounding agents other than the vulcanization-based compounding agent include various additives generally used in rubber compositions for tires, such as an antioxidant, a plasticizer, a processing aid, a liquid polymer, a terpene-based resin, and a thermosetting resin. These compounding agents may be used in conventional general amounts as long as the object of the present invention is not impaired. For example, a filler other than silica such as carbon black and the diene rubber may be simultaneously introduced and kneaded, or so-called rubber aids such as zinc oxide, stearic acid, and an antioxidant may be simultaneously introduced and kneaded with the diene rubber, or after the completion of the kneading of the diene rubber, aromatic oil may be introduced and mixed.
In the present invention, after the kneading step (the first mixing step) of mixing and kneading the diene rubber, silica, the silane coupling agent, carbon black, the aromatic oil, and the compounding agent other than the vulcanization-based compounding agent, the step (the final mixing step) of cooling the obtained mixture and mixing the vulcanization-based compounding agent is performed. The mixing completion temperature in the first mixing step is not particularly limited, but is preferably 150 ℃ or higher, more preferably 150 to 170 ℃, and still more preferably 150 to 165 ℃. By setting the mixing completion temperature in the first mixing step to 150 ℃ or higher, the viscosity of the rubber composition can be reduced, and the processability can be further improved.
Examples of the vulcanization-based compounding agent include a vulcanization or crosslinking agent, a vulcanization accelerator, and a vulcanization retarder. The method of mixing the vulcanization-based compounding agent can be performed in the same manner as in the production method of a general rubber composition for a tire. Further, the second-stage mixing step of further kneading the mixture obtained in the first-stage mixing step and the third-stage mixing step may be performed before the final-stage mixing step. The second mixing step is a step of taking out the kneaded product from the mixer in the first mixing step, cooling the kneaded product as necessary, and then feeding the cooled kneaded product into the same mixer or another mixer to mix the kneaded product. The third mixing step is a step of mixing the mixture obtained in the second mixing step in the same manner as described above. In the second-stage mixing step and/or the third-stage mixing step, the mixture obtained in each of the preceding-stage mixing steps may be charged and mixed as it is, or a compounding agent may be further additionally charged and mixed to the mixture.
The rubber composition for a tire produced in the present invention contains 30 to 220 parts by mass of silica and 3 to 50 parts by mass of aromatic oil per 100 parts by mass of diene rubber, and contains a silane coupling agent in an amount of 5 to 18% by mass of the amount of silica.
The diene rubber is not particularly limited as long as it is a diene rubber used in a usual rubber composition for a tire, and examples thereof include natural rubber, isoprene rubber, butadiene rubber, styrene-isoprene-butadiene rubber, nitrile rubber and the like. Among them, natural rubber, butadiene rubber and styrene-butadiene rubber are preferable.
These diene rubbers may be diene rubbers in which the terminal and/or side chain of the molecular chain is modified with a functional group having a hetero atom. Examples of the hetero atom include oxygen, nitrogen, silicon, and sulfur islands. Further, the modified diene rubber may be one modified with an epoxy group, a carboxyl group, an amino group, a hydroxyl group, an alkoxy group, a silyl group, an amide group, an oxysilyl group, a silanol group, an isocyanate group, an isothiocyanate group, a carbonyl group, an aldehyde group, or the like as a functional group.
Examples of the modified diene rubber include epoxy-modified natural rubber, epoxy-modified isoprene rubber, amino-modified styrene-butadiene rubber, hydroxy-modified styrene-butadiene rubber, silyl-modified styrene-butadiene rubber, oxysilyl-modified styrene-butadiene rubber, silanol-modified styrene-butadiene rubber, imino-modified styrene-butadiene rubber, carboxy-modified styrene-butadiene rubber, tin-modified styrene-butadiene rubber, and epoxy-modified styrene-butadiene rubber.
The modified diene rubber is preferably contained in an amount of 30% by mass or more, more preferably 35% by mass or more, based on 100% by mass of the diene rubber. The modified diene rubber is preferably contained in an amount of 100% by mass or less, more preferably 95% by mass or less, and still more preferably 90% by mass or less. By setting the content of the modified diene rubber to 40% by mass or more, the dispersibility of silica can be further improved, and the wet grip performance, low rolling resistance, processability and abrasion resistance can be further improved.
The zinc oxide may be blended with zinc oxide which is generally used for a rubber composition for a tire. The amount of zinc oxide blended is preferably 1.0 to 5.0 parts by mass, more preferably 1.5 to 4.5 parts by mass, per 100 parts by mass of the diene rubber. By setting the amount of zinc oxide to 1.5 parts by mass or more, deterioration of physical properties due to aging can be suppressed. Further, by making zinc oxide 4.5 parts by mass or less, the retardation of the vulcanization rate can be suppressed.
Examples of the silica include wet silica (hydrated silicic acid), dry silica (anhydrous silicic acid), calcium silicate, and aluminum silicate, and these can be used alone or in combination of 2 or more. Further, a surface-treated silica obtained by subjecting the surface of silica to surface treatment with a silane coupling agent can be used.
The CTAB adsorption specific surface area of the silica is not particularly limited, and is preferably 150m2/g～300m2G, more preferably 160m2/g～260m2The ratio of the acid to the acid is preferably in terms of/g. By making the CTAB adsorption specific surface area of the silica 150m2(ii) at least one of the rubber composition and the rubber composition has an abrasion resistance. Further, the CTAB adsorption specific surface area of the silica was set to 300m2Lower than g, the wet grip performance and the low rolling resistance can be improved. In the present specification, the CTAB specific surface area of the silica is a value determined by ISO 5794.
The silica is contained in an amount of 30 to 220 parts by mass per 100 parts by mass of the diene rubber. When importance is particularly attached to the abrasion resistance, it is preferable to add 30 to 180 parts by mass, and more preferably 70 to 140 parts by mass to 100 parts by mass of the diene rubber. When importance is attached to processability, the amount of the rubber is preferably 40 to 220 parts by mass, more preferably 50 to 200 parts by mass, based on 100 parts by mass of the diene rubber. By setting the amount of silica to 30 parts by mass or more, wet grip performance and low rolling resistance can be improved. Further, workability can be ensured by setting the amount of silica to 220 parts by mass or less, and abrasion resistance can be ensured by setting the amount of silica to 180 parts by mass or less.
The silane coupling agent is not particularly limited as long as it can be used for a rubber composition containing silica, and examples thereof include a silane coupling agent containing sulfur, a silane coupling agent containing an amino group, and the like. Further, a silane coupling agent represented by formula (1) and a polysiloxane represented by the average composition formula of formula (2) described later can be preferably used. Examples of the silane coupling agent include sulfur-containing silane coupling agents such as bis- (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) disulfide, 3-trimethoxysilylpropylbenzothiazole tetrasulfide, gamma-mercaptopropyltriethoxysilane, 3-octanoylthiopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethyl-butylidene) propylamine, Amino group-containing silane coupling agents such as N-phenyl-3-aminopropyltrimethoxysilane and hydrochloride of N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane. These silane coupling agents may be used alone or in combination.
In the production method of the present invention, a silane coupling agent represented by the following formula (1) can be preferably used.
(CpH2p+1)t(CpH2p+1O)3-t-SiCqH2q-S-C(O)-CrH2r+1…(1)
(in the formula (1), p represents an integer of 1 to 3, q represents an integer of 1 to 3, r represents an integer of 1 to 15, and t represents an integer of 0 to 2.)
In the formula (1), p is preferably 2 to 3, more preferably 2, from the viewpoints that the affinity with silica is high, the processability of the rubber composition for a tire is good, and the dispersibility of silica in the rubber composition for a tire is good. For the same reason, q is preferably 2 to 3, more preferably 3. In view of improving the scorch time during kneading of the rubber composition for a tire, r is preferably 5 to 10, more preferably 6 to 9, and still more preferably 7. t represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0. Such a silane coupling agent can be produced by a known method, and examples thereof include the method described in international publication No. 99/09036. Examples of commercially available products include NXT silane available from モメンティブ (Momentive Performance Material) and the like.
The sulfur-containing silane coupling agent is preferably a silane coupling agent having a mercapto group, and more preferably a polysiloxane represented by the average compositional formula of formula (2) below.
(A)a(B)b(C)c(D)d(R1)eSiO(4-2a-b-c-d-e)/2…(2)
(wherein A represents a 2-valent organic group represented by the following formula (3), B represents a 1-valent hydrocarbon group having 5 to 20 carbon atoms, C represents a hydrolyzable group, D represents a mercapto group-containing organic group, R1 represents a 1-valent hydrocarbon group having 1 to 4 carbon atoms, and a to e are real numbers satisfying relational expressions of 0. ltoreq. a < 1, 0. ltoreq. B < 1, 0. ltoreq. C < 3, 0. ltoreq. D < 1, 0. ltoreq. e < 2, 0. ltoreq. a + 2a + B + C + D + e < 4.
*-(CH2)n-Sx-(CH2)n-*…(3)
(in the formula (3), n represents an integer of 1 to 10, x represents an integer of 1 to 6, and represents a binding site.)
The polysiloxane (mercaptosilane compound) having the average composition formula represented by the above general formula (2) has a siloxane skeleton as its skeleton. The siloxane skeleton may have any one of a linear structure, a branched structure, and a 3-dimensional structure, or a combination thereof.
In the general formula (2), at least 1 of a and b is not 0. That is, at least 1 of a, b is greater than 0, and it may be that both a and b are greater than 0. Therefore, the polysiloxane necessarily contains at least one selected from a 2-valent organic group A containing a thioether group and a 1-valent hydrocarbon group B having 5 to 10 carbon atoms.
When the silane coupling agent containing the polysiloxane having the average composition formula represented by the general formula (2) has a 1-valent hydrocarbon group B having 5 to 10 carbon atoms, the mercapto group is protected, the Mooney scorch time is prolonged, and the affinity with rubber is excellent, so that the processability is further excellent. Therefore, the subscript B of the hydrocarbon group B in the formula (2) is preferably 0.10. ltoreq. b.ltoreq.0.89. Specific examples of the hydrocarbon group B are preferably a 1-valent hydrocarbon group having 6 to 10 carbon atoms, more preferably a 1-valent hydrocarbon group having 8 to 10 carbon atoms, and examples thereof include a hexyl group, an octyl group, and a decyl group. Thereby, the mercapto group can be protected, and the Mooney scorch time is long, the processability is more excellent, and the low heat generation property is more excellent.
When the silane coupling agent containing the polysiloxane having the average composition formula represented by the above general formula (2) has a sulfide group-containing 2-valent organic group a, the low heat generation property and the processability (particularly, the maintenance/prolongation of the mooney scorch time) are further improved. Thus, the subscript a of the 2-valent organic group A containing a sulfide group in the general formula (5) is preferably 0 < a.ltoreq.0.50.
In the above general formula (3), n represents an integer of 1 to 10, preferably an integer of 2 to 4. In addition, x represents an integer of 1 to 6, preferably an integer of 2 to 4. The organic group a may be, for example, a hydrocarbon group which may have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.
Specific examples of the group represented by the above general formula (3) include, for example, onium-CH2-S2-CH2-＊、＊-C2H4-S2-C2H4-＊、＊-C3H6-S2-C3H6-＊、＊-C4H8-S2-C4H8-＊、＊-CH2-S4-CH2-＊、＊-C2H4-S4-C2H4-＊、＊-C3H6-S4-C3H6-＊、＊-C4H8-S4-C4H8-, etc.
The silane coupling agent containing the polysiloxane having the average composition formula represented by the general formula (2) has a hydrolyzable group C, and thus has excellent affinity and/or reactivity with silica. From the reasons that the heat build-up is low, the processability is more excellent, and the dispersibility of silica is more excellent, it is preferable that the subscript C of the hydrolyzable group C in the general formula (2) is 1.2. ltoreq. c.ltoreq.2.0. Specific examples of the hydrolyzable group C include an alkoxy group, a phenoxy group, a carboxyl group, and an alkenyloxy group. The hydrolyzable group C is preferably a group represented by the following general formula (4) from the viewpoint of improving the dispersibility of silica and further improving the processability.
*-OR2…(4)
In the general formula (4), the symbol represents a binding site. R2 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group (arylalkyl) having 6 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and among them, an alkyl group having 1 to 5 carbon atoms is preferable.
Specific examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, octadecyl, and the like. Specific examples of the aryl group having 6 to 10 carbon atoms include phenyl group and tolyl group. Specific examples of the aralkyl group having 6 to 10 carbon atoms include, for example, benzyl group and phenylethyl group. Specific examples of the alkenyl group having 2 to 10 carbon atoms include a vinyl group, a propenyl group, a pentenyl group and the like.
The silane coupling agent containing the polysiloxane having the average composition formula represented by the general formula (2) has the mercapto group-containing organic group D, and thus can interact and/or react with the diene rubber, and is excellent in low heat generation properties. The subscript D of the mercapto group-containing organic group D is preferably 0.1. ltoreq. d.ltoreq.0.8. The mercapto group-containing organic group D is preferably a group represented by the following general formula (5) from the viewpoint of improving the dispersibility of silica and further improving the processability.
*-(CH2)m-SH…(5)
In the general formula (5), m represents an integer of 1 to 10, and preferably an integer of 1 to 5. In the formula, the symbol denotes a binding site.
Specific examples of the group represented by the above general formula (5) include2SH、＊-C2H4SH、＊-C3H6SH、＊-C4H8SH、＊-C5H10SH、＊-C6H12SH、＊-C7H14SH、＊-C8H16SH、＊-C9H18SH、＊-C10H20SH。
In the above general formula (2), R1Represents a C1-4 hydrocarbon group. As hydrocarbon radicals R1Examples thereof include methyl, ethyl, propyl and butyl.
The amount of the silane coupling agent is 5 to 18 mass%, preferably 6 to 15 mass%, based on the mass of the silica. By setting the amount of the silane coupling agent to 5% by mass or more of the amount of silica, the dispersion of silica can be improved. Further, by setting the amount of the silane coupling agent to 18 mass% or less of the amount of silica, condensation of the silane coupling agents can be suppressed, and a rubber composition having desired hardness and strength can be obtained.
The rubber composition for a tire produced in the present invention is necessarily blended with an aromatic oil together with silica and a silane coupling agent. Further, carbon black may be blended together with silica, a silane coupling agent, and an aromatic oil.
Examples of the carbon black include furnace blacks such as SAF, ISAF, HAF, FEF, GPF, HMF, and SRF, and 2 or more kinds of these may be used alone or in combination. The nitrogen adsorption specific surface area of the carbon black is not particularly limited, and is preferably 70m2/g～240m2(ii) g, more preferably 90m2/g～200m2The ratio of the acid to the acid is preferably in terms of/g. By making the nitrogen adsorption specific surface area of the carbon black 70m2At least one of the rubber composition and the rubber composition has mechanical properties and abrasion resistance. Further, the nitrogen adsorption specific surface area of carbon black was 240m2Lower than g, the low rolling resistance can be improved. In the present specification, the nitrogen adsorption specific surface area of carbon black is measured in accordance with JIS K6217-2.
The carbon black is preferably incorporated in an amount of 5 to 100 parts by mass, more preferably 10 to 80 parts by mass, per 100 parts by mass of the diene rubber. By setting the compounding amount of carbon black to 5 parts by mass or more, the mechanical properties and abrasion resistance of the rubber composition can be ensured. Further, by setting the compounding amount of carbon black to 100 parts by mass or less, low rolling resistance can be secured.
The rubber composition for a tire may contain a filler other than silica and carbon black. Examples of the other filler include calcium carbonate, magnesium carbonate, talc, clay, alumina, aluminum hydroxide, titanium oxide, and calcium sulfate. These may be used alone or in combination of 2 or more.
As the aromatic oil, for example, an aromatic oil having a mass percentage of aromatic hydrocarbons of 15 mass% or more, which is determined in accordance with ASTM D2140, is suitably used. That is, the aromatic oil preferably contains aromatic hydrocarbons, paraffin hydrocarbons (paraffin), and naphthene hydrocarbons in the molecular structure thereof, and the content ratio of the aromatic hydrocarbons is 15 mass% or more, and more preferably 17 mass% or more. The content ratio of the aromatic hydrocarbon in the aromatic oil is preferably 70% by mass or less, and more preferably 65% by mass or less.
Commercially available products of aromatic oils include, for example, S エキストラクト 4 manufactured by Showa シェル oil Co., Ltd, AC-12 manufactured by Yoghurt, AC-460, AH-16, AH-24, AH-58, プロセス NC300S manufactured by ジャパンエナジー Co., Ltd, プロセス X-140 and the like.
The amount of the aromatic oil blended in the rubber composition for a tire is 3 to 50 parts by mass, preferably 5 to 40 parts by mass, and more preferably 10 to 30 parts by mass, per 100 parts by mass of the diene rubber. By setting the amount of the aromatic oil to 3 parts by mass or more, low rolling resistance can be ensured. Further, by setting the blending amount of the aromatic oil to 50 parts by mass or less, good hardness can be secured.
The rubber composition for a tire produced in the present invention may contain a silica dispersant together with silica and a silane coupling agent. Examples of the dispersant for silica include amine compounds, silane compounds, epoxy compounds, guanidine compounds, and the like. Preferably, at least 1 selected from the group consisting of amine compounds, silane compounds and guanidine compounds is used.
Examples of the amine compound include cyclic amine compounds. The cyclic amine compound preferably includes piperidine derivatives, piperazine derivatives, morpholine derivatives, thiomorpholine derivatives, and the like. The cyclic amine compound may have a silicon atom and an enamine structure (N-C ═ C).
The piperazine derivative, morpholine derivative and thiomorpholine derivative each preferably has a structure having a piperazine ring, a morpholine ring, a thiomorpholine ring, and a hydrocarbon group having 3 to 30 carbon atoms bonded directly to a carbon atom or a nitrogen atom forming the ring or bonded via another organic group. Examples of the other organic group include a carbonyl group, an oxyalkylene group, a polyoxyalkylene group, and an oxygen-containing 2-valent hydrocarbon group.
Examples of the hydrocarbon group having 3 to 30 carbon atoms include aliphatic hydrocarbon groups (including straight-chain, branched, and cyclic), aromatic hydrocarbon groups, and combinations thereof. Among these, from the viewpoint of further improving processability, an aliphatic hydrocarbon group is preferable, and a saturated aliphatic hydrocarbon group is more preferable. Further, from the viewpoint of further excellent processability, a hydrocarbon group having 8 to 22 carbon atoms is preferable. The hydrocarbon group having 3 to 30 carbon atoms is preferably composed of only carbon atoms and hydrogen atoms. The hydrocarbon group having 3 to 30 carbon atoms is preferably a 1-valent hydrocarbon group. The cyclic amine compound 1 may have 1 or more hydrocarbon groups having 3 to 30 carbon atoms per molecule, and preferably has 1 or 2 hydrocarbon groups per molecule.
The piperazine derivative can be preferably represented by the following formula (I).
Figure BDA0002826543430000121
In the formula (I), X3、X4、X5、X6Independently of each other, a hydrogen atom or a monovalent hydrocarbon group of 3 to 30 carbon atoms, X1、X2Independently of one another, are selected from the group consisting of hydrogen atomsA1-R2、-R2、-(R3-O)n-H, 1 of sulfone-based protecting group and carbamate-based protecting group, X1、X2At least 1 of which is-A1-R2or-R2。-R2Is a C3-30 valent hydrocarbon group, A1Is carbonyl or-R4(OH)-O-。R3Is a 2-valent hydrocarbon group of 2 to 3 carbon atoms, R4Is a 3-valent hydrocarbon group having 3 to 30 carbon atoms. n is a number of 1 to 10, preferably 1 to 5. The 1-valent hydrocarbon group having 3 to 30 carbon atoms in the formula (I) is preferably a linear, branched or cyclic aliphatic hydrocarbon group.
In the above formula (I), examples of the sulfone-based protecting group include methanesulfonyl, toluenesulfonyl and nitrobenzenesulfonyl (nosyl group). Examples of the urethane-based protecting group include a tert-butoxycarbonyl group, an allyloxycarbonyl group, a benzyloxycarbonyl group and a 9-fluorenylmethyloxycarbonyl group.
Examples of the piperazine derivative include compounds represented by the following formulae.
Figure BDA0002826543430000131
In the above formula, R independently of one another represents-C12H25or-C13H27。
Figure BDA0002826543430000141
In the above formula, n is a number of 2 to 10, preferably 2 to 5.
Figure BDA0002826543430000142
In the above formula, R represents-C12H25or-C13H27These piperazine derivatives may be used in combination.
The morpholine derivative and the thiomorpholine derivative are preferably represented by the following formula (II).
Figure BDA0002826543430000143
In the formula (I), X3、X4、X5、X6、X7Independently of each other, a hydrogen atom or a C3-30 valent hydrocarbon group, X1is-A1-R2or-R2。-R2Is a C3-30 valent hydrocarbon group, A1Is carbonyl or-R4(OH)-O-，R4Is a 3-valent hydrocarbon group having 3 to 30 carbon atoms. In the formula (I), the C3-30 monovalent hydrocarbon group is preferably a linear, branched or cyclic aliphatic hydrocarbon group.
Examples of the morpholine derivative include compounds represented by the following formulae.
Figure BDA0002826543430000151
In the above formula, R represents-C12H25or-C13H27These morpholine derivatives may be used in combination.
Examples of the thiomorpholine derivative include compounds in which an oxygen atom in a ring of the morpholine derivative is replaced with a sulfur atom.
The method for producing the cyclic amine compound containing the piperazine derivative, morpholine derivative and thiomorpholine derivative is not particularly limited, and can be obtained by a usual production method. For example, the compound can be obtained by reacting at least 1 kind selected from piperazine, morpholine and thiomorpholine which may have substituents, and a hydrocarbon compound having 3 to 30 carbon atoms of at least 1 kind selected from a halogen atom (chlorine, bromine, iodine, etc.), an acid halide group (acid chloride group, acid bromide group, acid iodide group, etc.) and a glycidyloxy group, if necessary, in a solvent. The substituents are the same as described above. The hydrocarbon compound has a hydrocarbon group having 3 to 30 carbon atoms as described above. Further, as a method for producing a piperazine derivative having a (poly) oxyalkyl group, for example, a method in which a piperazine derivative having a hydroxyl group is reacted with an alkylene oxide in the presence of a metal alkoxide can be cited.
In the rubber composition for a tire, the amount of the cyclic amine compound blended is preferably 0.5 parts by mass or more, more preferably 0.5 to 10 parts by mass, and still more preferably 0.8 to 5 parts by mass, per 100 parts by mass of the diene rubber. By setting the amount of the cyclic amine compound to 0.5 parts by mass or more, the rolling resistance can be reduced and the wet grip performance can be improved when the tire is manufactured.
Examples of the silane-based compound include alkylalkoxysilanes, such as monoalkyltrialkoxysilanes, dialkyldialkoxysilanes, and trialkylmonoalkoxysilanes. Among them, alkyltrialkoxysilanes are preferable, and alkyltriethoxysilane is more preferable. By blending the alkylalkoxysilane, aggregation of silica and increase in viscosity of the rubber composition can be suppressed, and wet grip performance can be further improved.
The alkyltriethoxysilane preferably has an alkyl group having 3 to 20 carbon atoms, more preferably an alkyl group having 7 to 20 carbon atoms. Examples of the alkyl group having 3 to 20 carbon atoms include a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an eicosyl group. Among them, from the viewpoint of compatibility with the diene rubber, an alkyl group having 8 to 10 carbon atoms is more preferable, and an octyl group or nonyl group is further preferable.
The amount of the alkyltriethoxysilane blended is preferably 0.5 to 10 mass%, more preferably 2 to 6 mass%, based on the amount of the silica blended. If the amount of the alkyltriethoxysilane is less than 0.5% by mass, the effect of inhibiting aggregation of silica and the effect of inhibiting increase in viscosity of the rubber composition cannot be sufficiently obtained. Further, if the amount of the alkyltriethoxysilane blended exceeds 10 mass%, the retention of the rubber composition on the roll increases. Further, the rolling resistance of the rubber composition may become large, and the abrasion resistance may be lowered.
The rubber composition for a tire of the present invention may contain various additives generally used in rubber compositions for a tire, such as a vulcanization or crosslinking agent, a vulcanization accelerator, an antioxidant, a plasticizer, a processing aid, a liquid polymer, a terpene resin, and a thermosetting resin, within a range not to impair the object of the present invention. Such additives can be kneaded by a general method to prepare a rubber composition, and used for vulcanization or crosslinking. The amount of these additives may be a conventional general amount unless the object of the present invention is not impaired.
The present invention will be further described with reference to the following examples, but the scope of the present invention is not limited to these examples.
Examples
Rubber compositions 10 to 19 having the compositions shown in table 4 were produced by different production methods. The rubber compositions prepared in the following examples and comparative examples had the compounding of the corresponding rubber compositions in Table 4 shown in the column of "recipe of rubber composition" in tables 1 to 3. The compounding of the rubber compositions in table 4 describes the compounding amount with respect to 100 parts by mass of the diene rubber (SBR and/or modified SBR), and describes the abbreviations of the respective components and whether or not they are charged into the mixer in which mixing step of the first stage and the final stage. For the first-stage mixing, the total amount of each component described in the column of "first-stage mixing" in table 4 was repeatedly charged and kneaded in a mixer (internal banbury mixer with a capacity of 1.7 liters, manufactured by kyoto steel company) in the order of "1 st charge", "2 nd charge" and "3 rd charge" shown in tables 1 to 3 to obtain a kneaded product, which was discharged from the mixer and cooled. After cooling, the kneaded mixture was put into a mixer again, and the ingredients described in the column "mixing at the final stage" in Table 4 were put and mixed, thereby preparing rubber compositions by 19 production methods (examples 1-1 to 1-14, Standard example 1, and comparative examples 1-1 to 1-4).
The temperature of the banbury mixer was adjusted to 60 ℃ and the mixing of the respective raw materials was started at normal temperature (23 ℃). In the first-stage mixing, as mixing conditions, the mixing time and the temperature after completion of mixing of the 1 st input of the components and the mixing initial temperature of the 2 nd input of the components are shown in tables 1 and 2. The mixing time of the components to be added at the 2 nd and 3 rd times was set to 1 minute. The kneaded product obtained in the first mixing step was cooled to 23 ℃ by air cooling outside the machine, and mixing with a vulcanizing agent was performed in a banbury mixer for 1.5 minutes.
The obtained rubber composition for a tire was vulcanized at 170 ℃ for 10 minutes using a mold (inner dimension; length 150mm, width 150mm, thickness 2mm) having a predetermined shape to prepare a vulcanized rubber test piece. The obtained vulcanized rubber test piece was used to measure wet performance, rolling resistance and abrasion resistance by the test methods shown below.
Wet road performance
The dynamic viscoelasticity of the vulcanized rubber test piece obtained was measured under the conditions of a tensile strain rate of 10. + -. 2%, a frequency of 20Hz, a temperature of 0 ℃ and a temperature of 60 ℃ using a viscoelasticity spectrophotometer manufactured by Wako K.K., to determine tan. delta. (0 ℃). The obtained results are shown in the columns of "wet performance" in tables 1 to 3 as an index in which the value of standard example 1 is 100. The larger the index of wet grip performance, the larger the tan. delta. (0 ℃ C.) and the more excellent the wet grip performance.
Hardness of
The resulting vulcanized rubber test piece was measured at a temperature of 20 ℃ by means of a type A durometer in accordance with JIS K6253. The results obtained are used as a standard example1The value of (d) is expressed in the column of "hardness" in tables 1 to 3 as an index of 100. The larger the index, the higher the hardness. Further, it shows that the steering stability is excellent when the tire is manufactured.
[ Table 1]
Figure BDA0002826543430000191
[ Table 2]
Figure BDA0002826543430000201
[ Table 3]
Figure BDA0002826543430000211
[ Table 4]
Figure BDA0002826543430000221
In table 4, the kinds of raw materials used are as follows.
SBR 1: styrene-butadiene rubber (unmodified product), Nipol 1502 manufactured by Japan ゼオン Co., Ltd
Modified SBR 1: epoxy-modified styrene-butadiene rubber (Nipol NS616, manufactured by Nippon ゼオン Co., Ltd.)
Carbon black 1(CB 1): キャボットジャパン (ショウブラック N339 available from society of Ltd.)
Silica 1: ソルベイ ZEOSIL PREMIUM 200MP (CTAB adsorption specific surface area 203 m)2/g)
Silica 2: ソルベイ ZEOSIL 1165MP (CTAB adsorption specific surface area is 160 m)2/g)
Stearic acid 1: stearic acid manufactured by Ningyou Co
Anti-aging agent 1: santoflex 6PPD, made by Solutia Europe
Anti-aging agent 2: PILNOX TDQ manufactured by Nocil Limited
Silane coupling agent 1: sulfide-based silane coupling agent, Si69 available from エボニックデグサ Co., Ltd., bis (triethoxysilylpropyl) tetrasulfide
Aromatic oil 1: s エキストラクト 4 of Showa シェル oil society
Zinc oxide 1: 3 kinds of zinc oxide produced by the same chemical industry society
Sulfur 1: fine sulfur (sulfur content 95.24 mass%) is added to Jinhua stamp-pad ink produced by Hejian chemical industry Co
Vulcanization accelerator 1: sumitomo chemical ソクシノール D-G (DPG)
Vulcanization accelerator 2: ノクセラー CZ-G (CZ) manufactured by Danei new chemical industries
As is clear from tables 1 to 3, it was confirmed that the rubber compositions obtained by the production methods of examples 1-1 to 1-14 can improve the wet performance (tan. delta. at 0 ℃ C.) and the hardness. In examples 1-11 to 1-14 in which the amount of silica was large, the wet performance (tan. delta. at 0 ℃) and the hardness were improved as compared with comparative examples 1-4 in which the amount of silica was increased in the standard example 1.
On the other hand, in the rubber composition obtained in comparative example 1-1, in the first stage of mixing, the silica was added and mixed only for the 1 st time and the silane coupling agent was not added for the 1 st time to the mixer, and therefore, the silica and the silane coupling agent did not react sufficiently, and the wet performance and the abrasion resistance could not be improved. Since the rubber composition obtained in comparative example 1-2 contained a large amount of aromatic oil, the hardness could not be sufficiently maintained even if silica, a silane coupling agent, and aromatic oil were added and mixed in the first mixing step 1 time in the mixer. In the rubber compositions obtained in comparative examples 1 to 3, only silica and a silane coupling agent were charged and mixed in the 1 st time of the mixing in the mixer in the first stage of the mixing, and the aromatic oil was not charged in the 1 st time, so that the wet performance was deteriorated. In the rubber compositions obtained in comparative examples 1 to 4, only silica and an aromatic oil were charged and mixed in the 1 st time of the first-stage mixing in the mixer, and the silane coupling agent was not charged in the 1 st time, so that the wet performance was deteriorated.
Rubber compositions 20 to 22 having the compositions shown in Table 7 were produced by different production methods. The rubber compositions prepared in the following examples and comparative examples had the compounding of the corresponding rubber compositions in Table 7 shown in the column of "recipe of rubber composition" in tables 5 to 6. The compounding amounts of the rubber compositions in table 7 are described with respect to 100 parts by mass of the diene rubber (SBR), and the abbreviations of the respective components and whether or not the components are charged into the mixer in any mixing step of the first stage, the second stage and the final stage are described. In the production of the rubber compositions other than examples 2 to 3 and comparative examples 2 to 3, in the first-stage mixing, all the amounts of the respective components described in the column of "first-stage mixing" in table 7 were charged into a mixer (internal banbury mixer having a capacity of 1.7 liters, manufactured by shenkou steel works) in the order of "1 st charge", "2 nd charge" and "3 rd charge" shown in tables 5 to 6, and kneaded to obtain a kneaded product, which was discharged from the mixer and cooled. After cooling, the kneaded mixture was put into a mixer again, and the ingredients described in the column "mixing at the final stage" in Table 7 were put into the mixer and mixed, thereby preparing a rubber composition by the production method 9 (examples 2-1, 2-2, 2-4 to 2-7, reference example 2, and comparative examples 2-1 to 2-2). In the production of the rubber compositions of examples 2 to 3 and comparative examples 2 to 3, in the first-stage mixing, the total amount of the components except for the coupling agent 1 and zinc oxide described in the column of "first-stage mixing" in table 7 was charged into a mixer (internal banbury mixer having a capacity of 1.7 liters, manufactured by shenkou steel works) in the order of "1 st charge", "2 nd charge" and "3 rd charge" shown in tables 5 to 6, kneaded to obtain a kneaded product, and the kneaded product was discharged from the mixer and cooled. After cooling, the kneaded mixture is again put into the mixer, and as the second-stage mixing, the coupling agent or zinc oxide is put into the mixer and kneaded to obtain a kneaded mixture, which is discharged from the mixer and cooled. After cooling, the kneaded mixture was put into the mixer again, and the ingredients described in the column entitled "mixing at the final stage" in Table 7 were put into the mixer and mixed, thereby preparing rubber compositions of examples 2 to 3 and comparative examples 2 to 3.
The temperature of the banbury mixer was adjusted to 60 ℃ and the mixing of the respective raw materials was started at normal temperature (23 ℃). In the first-stage mixing, as mixing conditions, the mixing time and the temperature after completion of mixing of the 1 st input of the components and the mixing initial temperature of the 2 nd input of the components are shown in tables 5 and 6. The mixing time of the components to be added at the 2 nd and 3 rd times was set to 1 minute. The kneaded material obtained in the first mixing step was cooled with air outside the machine until it became 23 ℃. In the second-stage mixing of examples 2 to 3 and comparative examples 2 to 3, the mixing time was set to 3 minutes as the mixing conditions, and the kneaded material obtained in the second-stage mixing was cooled by air passing through the outside of the machine until it became 23 ℃. The mixing after compounding the vulcanizing agents (mixing at the final stage) was carried out for 1.5 minutes by using a Banbury mixer.
The mooney viscosity of the obtained rubber composition for a tire was measured by the following method. Further, a rubber composition for a tire was vulcanized at 170 ℃ for 10 minutes using a mold (inner dimension; length 150mm, width 150mm, thickness 2mm) of a predetermined shape to prepare a vulcanized rubber test piece. The obtained vulcanized rubber test piece was used to measure wet performance, rolling resistance and abrasion resistance by the test methods shown below.
Mooney viscosity (processability)
According to JIS K6300-1: 2001, the Mooney viscosity of the rubber composition obtained was measured by using a Mooney viscometer using an L-shaped rotor under the conditions of a preheating time of 1 minute, a rotation time of 4 minutes of the rotor and 100 ℃. The results are shown in the columns of "workability" in tables 5 to 6, which are indicated by an index in which the value of Standard example 2 is 100. When the Mooney viscosity index is 95 or less, it means that the Mooney viscosity is low and the processability is good.
Wet road Property and Rolling resistance [ tan. delta. at 0 ℃ and 60 ]
The dynamic viscoelasticity of the vulcanized rubber test piece obtained was measured under the conditions of a tensile strain rate of 10. + -. 2%, a frequency of 20Hz, a temperature of 0 ℃ and a temperature of 60 ℃ using a viscoelasticity spectrophotometer manufactured by Wako K.K., to determine tan. delta. (0 ℃) and tan. delta. (60 ℃). The obtained results are shown in the columns of "wet performance" and "rolling resistance" in tables 5 to 6 as indexes in which the values of standard example 2 are 100, respectively. When the wet performance index is 110 or more, it means that tan. delta. (0 ℃ C.) is large and wet grip performance is excellent. When the index of rolling resistance is 95 or less, it shows that tan δ (60 ℃ C.) is small, heat build-up is low, and rolling resistance is small when a tire is produced.
[ Table 5]
Figure BDA0002826543430000261
[ Table 6]
Figure BDA0002826543430000271
[ Table 7]
Figure BDA0002826543430000281
In table 7, the kinds of raw materials used are as follows.
SBR 2: styrene-butadiene rubber (unmodified product), Nipol 1502 manufactured by Japan ゼオン Co., Ltd
Silica 3: ローディア ZEOSIL PREMIUM 200MP, CTAB adsorption specific surface area 203m2/g
Silane coupling agent 2: sulfide-based silane coupling agent, Si69 available from エボニックデグサ Co., Ltd., bis (triethoxysilylpropyl) tetrasulfide
Silane coupling agent 3: the silane coupling agent represented by the general formula (1) is represented by the following formula, NXT silane manufactured by モメンティブ (Momentive Performance Material).
(CH3CH2O)3-Si-C3H6-S-C(O)-C6H12CH3
Carbon black 2(CB 2): キャボットジャパン (ショウブラック N339 available from society of Ltd.)
Aromatic oil 2: s エキストラクト 4 of Showa シェル oil society
Zinc oxide 2: 3 kinds of zinc oxide produced by the same chemical industry society
Stearic acid 2: stearic acid manufactured by Ningyou Co
Anti-aging agent 3: santoflex 6PPD, made by Solutia Europe
Anti-aging agent 4: PILNOX TDQ manufactured by Nocil Limited
Sulfur 2: fine sulfur (sulfur content 95.24 mass%) is added to Jinhua stamp-pad ink produced by Hejian chemical industry Co
Vulcanization accelerator 3: sumitomo chemical ソクシノール D-G (DPG)
Vulcanization accelerator 4: ノクセラー CZ-G (CZ) manufactured by Danei new chemical industries
As is clear from Table 6, it was confirmed that the rubber compositions obtained by the production methods of examples 2-1 to 2-7 can improve wet grip performance (tan. delta. at 0 ℃), low rolling resistance (tan. delta. at 60 ℃), and processability.
As is clear from table 5, in the method for producing the rubber composition of comparative example 2-1, the silane coupling agent charged 2 nd time was changed to the silane coupling agent 3 represented by the general formula (1) in the method for producing the rubber composition of the standard example, but the temperature of the mixer increased by the charging of the SBR1 st time, similarly to the method for producing the standard example. In the production method of comparative example 2-1, the effect of improving the wet performance of the rubber composition was inferior to that of the rubber compositions obtained in examples 2-1 to 2-7. In the method for producing the rubber composition of comparative example 2-2, the silane coupling agent charged at the 1 st time is not represented by the general formula (1), and therefore the effect of improving the wet performance and the rolling resistance of the rubber composition is inferior to those of the rubber compositions obtained in examples 2-1 to 2-7. In the method for producing the rubber compositions of comparative examples 2 to 3, zinc oxide was charged and mixed in the second mixing step, and therefore, the workability was poor.

Claims (7)

1. A method for producing a rubber composition for a tire, characterized in that the rubber composition contains 30 to 220 parts by mass of silica and 3 to 50 parts by mass of an aromatic oil per 100 parts by mass of a diene rubber, and a silane coupling agent in an amount of 5 to 18% by mass relative to the amount of silica,
in the production method, the silica, the silane coupling agent, and the aromatic oil are put together into a mixer and mixed, and then the diene rubber is put into and kneaded.
2. The method for producing a rubber composition for a tire according to claim 1, wherein carbon black is put together with the silica, the silane coupling agent, and the aromatic oil and mixed.
3. The method for producing a rubber composition for a tire as claimed in claim 1 or 2, wherein the silica has a CTAB specific surface area of 150m2/g～300m2/g。
4. The method for producing a rubber composition for a tire according to any one of claims 1 to 3, wherein the diene rubber contains 40% by mass or more of the modified diene rubber per 100% by mass of the diene rubber.
5. The method for producing a rubber composition for a tire according to any one of claims 1 to 4, wherein the silane coupling agent is represented by general formula (1),
(CpH2p+1)t(CpH2p+1O)3-t-SiCqH2q-S-C(O)-CrH2r+1…(1)
in the formula (1), p represents an integer of 1 to 3, q represents an integer of 1 to 3, r represents an integer of 1 to 15, and t represents an integer of 0 to 2.
6. The method for producing a rubber composition for a tire according to any one of claims 1 to 5, wherein zinc oxide is added and mixed together with the diene rubber.
7. The method for producing a rubber composition for a tire according to any one of claims 1 to 6, wherein a first-stage mixing step of mixing the silica, the silane coupling agent and the diene rubber and a final-stage mixing step of mixing the vulcanization-based compounding agent thereafter are performed, and the mixing completion temperature in the first-stage mixing step is 150 ℃ or higher.
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JP2005041926A (en) * 2003-07-23 2005-02-17 Sumitomo Rubber Ind Ltd Rubber composition and tire using the same
JP2014189650A (en) * 2013-03-27 2014-10-06 Sumitomo Rubber Ind Ltd Rubber composition for tire, and pneumatic tire
JP2016191018A (en) * 2015-03-31 2016-11-10 東洋ゴム工業株式会社 Method for producing rubber composition, rubber composition and pneumatic tire

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* Cited by examiner, † Cited by third party
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JP2005041926A (en) * 2003-07-23 2005-02-17 Sumitomo Rubber Ind Ltd Rubber composition and tire using the same
JP2014189650A (en) * 2013-03-27 2014-10-06 Sumitomo Rubber Ind Ltd Rubber composition for tire, and pneumatic tire
JP2016191018A (en) * 2015-03-31 2016-11-10 東洋ゴム工業株式会社 Method for producing rubber composition, rubber composition and pneumatic tire

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