WO2012144541A1 - Composition de caoutchouc pour bandages et pneu pneumatique - Google Patents

Composition de caoutchouc pour bandages et pneu pneumatique Download PDF

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Publication number
WO2012144541A1
WO2012144541A1 PCT/JP2012/060531 JP2012060531W WO2012144541A1 WO 2012144541 A1 WO2012144541 A1 WO 2012144541A1 JP 2012060531 W JP2012060531 W JP 2012060531W WO 2012144541 A1 WO2012144541 A1 WO 2012144541A1
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group
branched
rubber composition
diene polymer
silica
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PCT/JP2012/060531
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English (en)
Japanese (ja)
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里美 山内
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住友ゴム工業株式会社
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
    • C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
    • C08C19/44—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups of polymers containing metal atoms exclusively at one or both ends of the skeleton
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives

Definitions

  • the present invention relates to a rubber composition for tires and a pneumatic tire using the same.
  • a method of replacing carbon black with silica is known.
  • a rubber composition blended with silica tends to have a low dry grip performance, and when traveling, the rubber stiffness decreases and the dry grip performance tends to further decrease.
  • Silica has a hydrophilic silanol group on its surface, so it has a lower affinity with rubber (especially natural rubber, butadiene rubber, styrene butadiene rubber, etc. often used for tires) and wear resistance than carbon black. There was a tendency to be inferior in terms of property and mechanical strength (tensile strength and elongation at break).
  • Patent Document 1 discloses a rubber composition containing specific silica (linear silica) and capable of improving wet grip performance and dry grip performance while maintaining low fuel consumption. However, there is room for improvement in terms of improving fuel economy, wet grip performance, dry grip performance, wear resistance, and workability.
  • the present invention provides a rubber composition for a tire that solves the above-described problems and can improve fuel economy, wet grip performance, dry grip performance, wear resistance, and processability, and a pneumatic tire using the same. Objective.
  • the present invention includes a diene polymer and silica
  • the diene polymer is a modified diene polymer obtained by reacting the following (A) and (B):
  • the silica has three or more particles adjacent to one particle as the branched particle X
  • the average length L 1 between the branched particles XX including the branched particle X is 30 to 400 nm.
  • the present invention relates to a tire rubber composition.
  • A represents a branched or unbranched alkylene group, a branched or unbranched arylene group, or a derivative thereof.
  • the present invention also relates to a tire rubber composition obtained by kneading a modified diene polymer obtained by reacting the above (A) and (B) with silica sol.
  • the compound represented by the above formula (1) is a compound represented by the following formula (2).
  • the modifying agent is preferably a compound represented by the following formula (3).
  • R 3 and R 4 are the same or different and each represents a hydrocarbon group having 1 to 10 carbon atoms, and the hydrocarbon group is selected from the group consisting of ethers and tertiary amines.
  • R 5 and R 6 may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group being an ether, and 3 It may have at least one group selected from the group consisting of a tertiary amine, R 7 represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group is an ether, a tertiary amine, an epoxy And at least one group selected from the group consisting of carbonyl, and halogen, n represents an integer of 1 to 6.)
  • the modifiers introduced at both ends of the active conjugated diene polymer are the same.
  • the content of the diene polymer in 100% by mass of the rubber component is preferably 5% by mass or more.
  • the conjugated diene monomer is preferably 1,3-butadiene and / or isoprene, and the aromatic vinyl monomer is preferably styrene.
  • the modified diene polymer is preferably a modified styrene butadiene rubber obtained by polymerizing 1,3-butadiene and styrene.
  • the silica preferably has an average aspect ratio L 1 / D of 3 to 100 between the branched particles XX including the branched particles X when the average primary particle diameter is D.
  • the tire rubber composition preferably contains 5 to 150 parts by mass of the silica with respect to 100 parts by mass of the rubber component.
  • the tire rubber composition is preferably used as a tread rubber composition.
  • the present invention also relates to a pneumatic tire using the rubber composition.
  • the present invention since it is a tire rubber composition containing a specific modified diene polymer and a specific silica, low fuel consumption, wet grip performance, dry grip performance, wear resistance, workability Can be improved. Further, since it is a tire rubber composition obtained by kneading a specific modified diene polymer and silica sol, low fuel consumption, wet grip performance, dry grip performance, abrasion resistance And processability can be improved. Therefore, the pneumatic tire excellent in the above-mentioned performance can be provided by using these rubber compositions for each member of the tire such as a tread.
  • FIG. 3 is a schematic diagram of a branched particle X.
  • FIG. Outline of average primary particle diameter of silica, average length of XX between branched particles including branched particle X (L 1 ), and average length of XX between branched particles not including branched particle X (L 2 ) It is a schematic diagram.
  • the rubber composition for tires of the present invention includes a diene polymer and silica, and the diene polymer is obtained by reacting the following (A) and (B) with a modified diene polymer (hereinafter referred to as “diene polymer”). , Also referred to as a modified diene polymer), and when the above-mentioned silica has three or more particles adjacent to one particle as the branched particle X, the inter-branched particle XX including the branched particle X
  • the average length L 1 is 30 to 400 nm (structure silica (linear silica)).
  • A represents a branched or unbranched alkylene group, a branched or unbranched arylene group, or a derivative thereof.
  • the polymer chain obtained by the polymerization reaction (above (A) (Active conjugated diene polymer)) has both ends as living polymer ends. Therefore, both ends of the active conjugated diene polymer (A) can be modified with the modifier (B), and the modified diene polymer obtained by modifying both ends of (A) with the above (B) Compared with the case where only one end is modified, excellent fuel economy, wet grip performance, dry grip performance, and wear resistance can be obtained, and these performances can be improved in a well-balanced manner.
  • a method for introducing functional groups (modifying groups) at both ends a method in which polymerization is performed using a polymerization initiator having a functional group, and a modifier is further reacted at the polymerization ends can be considered.
  • the functional group of the polymerization initiator is present at one end, and the functional group due to the modifier is present at the other end.
  • the functional group of the polymerization initiator generally has a weak interaction with silica, the balance between low fuel consumption, wet grip performance, dry grip performance, and wear resistance is poor.
  • the functional group which a polymerization initiator has is easy to detach
  • the polarity of the functional group possessed by the polymerization initiator when the polarity of the functional group possessed by the polymerization initiator is high, it can coordinate to the end of the living polymer to affect the reaction between the polymerization end and the modifier, and any functional group can be introduced to the end of the polymerization. Can not.
  • (A) is obtained by using (C) as a polymerization initiator, the polymer chain extends in two directions by the polymerization reaction, and there are two living polymer terminals. A functional group can be introduced. Therefore, by blending the modified diene polymer obtained by reacting the above (A) and (B), rubber excellent in fuel economy, wet grip performance, dry grip performance, and wear resistance balance performance A composition is obtained.
  • the occluder rubber (rubber which is encapsulated in the silica aggregate and cannot be distorted) produced by the aggregation of the silica particles is reduced, and the local stress concentration, that is, the local Distortion is reduced.
  • extension of a tire (at the time of low distortion) can be reduced, and rolling resistance can be reduced.
  • the structure silica is oriented in the tread circumferential direction of the tire when the tire is highly stretched (during high strain) such as during sudden braking or sharp turning. As a result, the rubber in the vicinity of the structure silica is abruptly distorted and the hysteresis loss is increased, thereby improving the dry grip performance.
  • the improvement effect of each can be synergistically enhanced by the combined use of the modified diene polymer and the structure silica.
  • the processability may be lowered.
  • the processability can be improved by using the modified diene polymer in combination with the structure silica.
  • the rubber composition containing the structure silica of the present invention can be produced, for example, by kneading the modified diene polymer and silica sol.
  • the diene polymer is a modified diene polymer obtained by reacting (A) and (B).
  • (A) is an active conjugated diene polymer having an alkali metal end obtained by polymerizing a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer in the presence of (C).
  • the active conjugated diene polymer has two alkali metal terminals.
  • (C) is a chemical species obtained by reacting a compound represented by the following formula (1) with an organic alkali metal compound.
  • R 1 and R 2 are the same or different and each represents a hydrogen atom, a branched or unbranched alkyl group, a branched or unbranched aryl group, a branched or unbranched alkoxy group, a branched or unbranched silyloxy group, branched or Represents an unbranched acetal group, carboxyl group (—COOH), mercapto group (—SH) or a derivative thereof, and A represents a branched or unbranched alkylene group, a branched or unbranched arylene group or a derivative thereof. .
  • Examples of the branched or unbranched alkyl group for R 1 and R 2 include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, iso-butyl group, sec-butyl group, tert- 1 to 30 carbon atoms such as butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, etc. (preferably 1 to 8 carbon atoms, more preferably 1 to 3 carbon atoms) 4, more preferably an alkyl group having 1 to 2 carbon atoms.
  • the alkyl group includes a group in which a hydrogen atom of the alkyl group is substituted with an aryl group (such as a phenyl group).
  • Examples of the branched or unbranched aryl group for R 1 and R 2 include those having 6 to 18 carbon atoms (preferably 6 to 8 carbon atoms) such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a biphenyl group.
  • An aryl group is mentioned.
  • the aryl group includes a group in which a hydrogen atom of the aryl group is substituted with an alkyl group (such as a methyl group).
  • Examples of the branched or unbranched alkoxy group for R 1 and R 2 include 1 to 8 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a t-butoxy group. And an alkoxy group (preferably having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms).
  • the alkoxy group includes a cycloalkoxy group (such as a cycloalkoxy group having 5 to 8 carbon atoms such as a cyclohexyloxy group), an aryloxy group (an aryloxy group having 6 to 8 carbon atoms such as a phenoxy group and a benzyloxy group), etc. ) Is also included.
  • a cycloalkoxy group such as a cycloalkoxy group having 5 to 8 carbon atoms such as a cyclohexyloxy group
  • an aryloxy group an aryloxy group having 6 to 8 carbon atoms such as a phenoxy group and a benzyloxy group
  • Examples of the branched or unbranched silyloxy group of R 1 and R 2 include, for example, a silyloxy group substituted with an aliphatic group or aromatic group having 1 to 20 carbon atoms (trimethylsilyloxy group, triethylsilyloxy group, triisopropylsilyl group).
  • a silyloxy group substituted with an aliphatic group or aromatic group having 1 to 20 carbon atoms trimethylsilyloxy group, triethylsilyloxy group, triisopropylsilyl group.
  • Examples of the branched or unbranched acetal group of R 1 and R 2 include groups represented by —C (RR ′) — OR ′′ and —O—C (RR ′) — OR ′′.
  • Examples of the former include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, an isopropoxymethyl group, a t-butoxymethyl group, and a neopentyloxymethyl group.
  • the latter includes a methoxymethoxy group, an ethoxy group, and the like.
  • a methoxy group, propoxymethoxy group, i-propoxymethoxy group, n-butoxymethoxy group, t-butoxymethoxy group, n-pentyloxymethoxy group, n-hexyloxymethoxy group, cyclopentyloxymethoxy group, cyclohexyloxymethoxy group, etc. Can be mentioned.
  • R 1 and R 2 are preferably a hydrogen atom, a branched or unbranched alkyl group, or a branched or unbranched aryl group. This can improve the balance of fuel efficiency, wet grip performance, dry grip performance, and wear resistance. Moreover, it is preferable that R 1 and R 2 are the same group because the polymer can be grown uniformly in two directions.
  • Examples of the branched or unbranched alkylene group of A include, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, and a dodecylene group.
  • alkylene group having 1 to 30 carbon atoms such as a group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group and octadecylene group.
  • Examples of the derivative of the alkylene group of A include an alkylene group substituted with an aryl group or an arylene group.
  • arylene group of A a phenylene group, a tolylene group, a xylylene group, a naphthylene group etc. are mentioned, for example.
  • Examples of the derivative of the arylene group of A include an arylene group substituted with an alkylene group.
  • a branched or unbranched arylene group is preferable, and a phenylene group (a compound represented by the following formula (2)) is more preferable. This can improve the balance of fuel efficiency, wet grip performance, dry grip performance, and wear resistance.
  • R 1 and R 2 in the formula (2) are the same as R 1 and R 2 in the formula (1).
  • Specific examples of the compound represented by the above formula (1) or (2) include 1,2-divinylbenzene, 1,3-divinylbenzene, 1,4-divinylbenzene, 1,2-diisopropenylbenzene, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, 1,2-diisobutenylbenzene, 1,3-diisobutenylbenzene, 1,4-diisobutenylbenzene, 1,3-phenylenebis (1 -Vinylbenzene), 1,4-phenylenebis (1-vinylbenzene), 1,1'-methylenebis (2-vinylbenzene), 1,1'-methylenebis (3-vinylbenzene), 1,1'-methylenebis (4-vinylbenzene) and the like. These may be used alone or in combination of two or more. Of these, 1,3-divinylbenzene, 1,3-diiso
  • Examples of the organic alkali metal compound used in the present invention include hydrocarbon compounds containing an alkali metal such as lithium, sodium, potassium, rubidium, and cesium. Of these, lithium or sodium compounds having 2 to 20 carbon atoms are preferred. Specific examples thereof include, for example, ethyl lithium, n-propyl lithium, iso-propyl lithium, n-butyl lithium, sec-butyl lithium, t-octyl lithium, n-decyl lithium, phenyl lithium, 2-naphthyl lithium, 2 -Butyl-phenyllithium, 4-phenyl-butyllithium, cyclohexyllithium, 4-cyclopentyllithium, 1,4-dilithio-butene-2 and the like. Among these, n-butyllithium or sec-butyllithium is preferable in that the reaction proceeds rapidly to give a polymer having a narrow molecular weight distribution.
  • the method for preparing (C) is not particularly limited as long as it is a method in which the compound represented by the above formula (1) is brought into contact with the organic alkali metal compound.
  • the compound represented by the formula (1) and the organic alkali metal compound are separately dissolved in an organic solvent inert to the reaction, for example, a hydrocarbon solvent, and represented by the formula (1).
  • (C) can be prepared by dropping the organic alkali metal compound solution into the compound solution with stirring.
  • the reaction temperature for preparing (C) is preferably 40 to 60 ° C.
  • the hydrocarbon solvent does not deactivate the organic alkali metal compound (alkali metal catalyst), and the suitable hydrocarbon solvent is selected from aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons.
  • propane having 2 to 12 carbon atoms propane having 2 to 12 carbon atoms, n-butane, iso-butane, n-pentane, iso-pentane, n-hexane, cyclohexane, propene, 1-butene, iso-butene, trans-2-butene, Examples thereof include cis-2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, benzene, toluene, xylene, and ethylbenzene.
  • these solvents can be used in mixture of 2 or more types.
  • conjugated diene monomer used in the present invention examples include 1,3-butadiene, isoprene, 1,3-pentadiene (piperine), 2,3-dimethyl-1,3-butadiene, 1,3-hexadiene and the like. Of these, 1,3-butadiene and isoprene are preferred from the viewpoint of the physical properties of the resulting polymer and the availability for industrial implementation.
  • aromatic vinyl monomer used in the present invention examples include styrene, ⁇ -methylstyrene, vinyl toluene, vinyl naphthalene, divinyl benzene, trivinyl benzene, divinyl naphthalene and the like.
  • styrene is preferred from the viewpoint of the physical properties of the polymer obtained and the availability for industrial implementation.
  • the monomer only a conjugated diene monomer may be used, or a conjugated diene monomer and an aromatic vinyl monomer may be used in combination.
  • the ratio by mass of the conjugated diene monomer / aromatic vinyl monomer is preferably 50/50 to 90/10, more preferably 55/45 to 85/15. It is. If the ratio is less than 50/50, the polymer rubber becomes insoluble in the hydrocarbon solvent, and uniform polymerization may not be possible. On the other hand, if the ratio exceeds 90/10, the strength of the polymer rubber may be reduced. May decrease.
  • the modified diene polymer is preferably obtained by copolymerizing a conjugated diene monomer and an aromatic vinyl monomer, and is obtained by copolymerizing 1,3-butadiene and styrene (modified styrene butadiene rubber). Is particularly preferred.
  • a modified copolymer fuel economy, wet grip performance, dry grip performance, and wear resistance can be improved.
  • low-fuel-consumption property, wet grip performance, dry grip performance, abrasion resistance, and workability can be suitably improved by using together with the structure silica.
  • hydrocarbon solvent As a hydrocarbon solvent, the thing similar to the case of the preparation of said (C) can be used conveniently.
  • the randomizer is a microstructure control of a conjugated diene moiety in a polymer, for example, an increase in 1,2-bonds in butadiene, a 3,4-bond in isoprene, or a control of the composition distribution of monomer units in the polymer. It is a compound having an action such as randomization of butadiene units and styrene units in a butadiene-styrene copolymer.
  • ether compounds or tertiary amines are preferred from the viewpoint of industrial availability.
  • ether compounds include cyclic ethers such as tetrahydrofuran, tetrahydropyran, and 1,4-dioxane; aliphatic monoethers such as diethyl ether and dibutyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, Examples thereof include aliphatic ethers such as diethylene glycol dibutyl ether; aromatic ethers such as diphenyl ether and anisole.
  • tertiary amine compounds include triethylamine, tripropylamine, tributylamine, N, N, N ′, N′-tetramethylethylenediamine, N, N-diethylaniline, pyridine, quinoline, etc. Can give.
  • (B) is a modifier having a functional group.
  • (B) is preferably a compound having a functional group containing at least one atom selected from the group consisting of nitrogen, oxygen and silicon.
  • functional groups include amino groups, amide groups, alkoxysilyl groups, isocyanate groups, imino groups, imidazole groups, urea groups, ether groups (especially epoxy groups), carbonyl groups, carboxyl groups, hydroxyl groups, nitrile groups, pyridyls. Group, diglycidylamino group and the like. These functional groups may have a substituent. Of these, amino groups, alkoxysilyl groups, ether groups (particularly epoxy groups), carbonyl groups, hydroxyl groups, carboxyl groups, and diglycidylamino groups are preferred because of their high reactivity with silica.
  • (B) is preferably a compound represented by the following formula (3). Moreover, it is preferable that (B) to be used is one type (the modifiers introduced at both ends of (A) are the same). By using only one type of (B), the same functional group can be introduced at both ends of (A), and the reactivity with silica is stabilized by forming uniform polymer ends.
  • the compound represented by the following formula (3) is a polyfunctional compound having two or more epoxy groups.
  • a hydroxyl group can be introduced into the polymer chain by reacting the active terminal of the active conjugated diene polymer (A) with an epoxy group.
  • the polyfunctional compound since the polyfunctional compound has two or more epoxy groups in the molecule, one polyfunctional compound reacts with the active terminal of a plurality of active conjugated diene polymers (A), so that two or more The polymer chains can be coupled. Therefore, a modified diene polymer having three or more sites (terminals and the like) modified with the polyfunctional compound can also be obtained. By increasing the number of modified sites (terminals, etc.) of the modified diene polymer, the balance between fuel efficiency, wet grip performance, dry grip performance, and wear resistance can be improved.
  • R 3 and R 4 are the same or different and each represents a hydrocarbon group having 1 to 10 carbon atoms, and the hydrocarbon group is selected from the group consisting of ethers and tertiary amines.
  • R 5 and R 6 may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group being an ether, and 3 It may have at least one group selected from the group consisting of a tertiary amine, R 7 represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group is an ether, a tertiary amine, an epoxy And at least one group selected from the group consisting of carbonyl, and halogen, n represents an integer of 1 to 6.
  • R 3 and R 4 are preferably an alkylene group having 1 to 10 carbon atoms (preferably having 1 to 3 carbon atoms).
  • R 5 and R 6 are preferably a hydrogen atom.
  • R 7 is a hydrocarbon group having 3 to 20 carbon atoms (preferably 6 to 10 carbon atoms, more preferably 8 carbon atoms), and is a cycloalkyl group, cycloalkylene group, cycloalkane represented by the following formula or the like.
  • a triyl group is preferable, and a cycloalkylene group is more preferable.
  • N is preferably 2 to 3.
  • Examples of the compound represented by the above formula (3) include tetraglycidylmetaxylenediamine, tetraglycidylaminodiphenylmethane, tetraglycidyl-p-phenylenediamine, diglycidylaminomethylcyclohexane, tetraglycidyl-1,3-bisaminomethyl. Cyclohexane or the like is preferably used.
  • the diene polymer (modified diene polymer) is obtained by reacting (A) and (B) in an organic solvent inert to the reaction, such as a hydrocarbon solvent.
  • hydrocarbon solvent As a hydrocarbon solvent, the thing similar to the case of the preparation of said (C) can be used conveniently.
  • the amount of the modifier (B) having a functional group is preferably 0.1 to 10 mol, more preferably 0.5 to 2 mol, relative to 1 mol of the organic alkali metal compound.
  • the amount is less than 0.1 mol, the effect of improving the fuel efficiency is small. Conversely, when the amount exceeds 10 mol, (B) remains in the polymerization solvent. This is economically undesirable because it requires a separation step.
  • the reaction temperature and reaction time can be selected in a wide range. In general, the temperature is from room temperature (25) to 80 ° C. for several seconds to several hours.
  • the reaction may be performed by bringing (A) and (B) into contact.
  • a method of polymerizing a diene polymer using (C) and adding a predetermined amount of (B) to the polymer solution For example, it can be exemplified as a preferred embodiment, but is not limited to this method.
  • a coupling agent represented by the general formula R a MX b may be added before or after the reaction of (A) and (B) (wherein R is an alkyl group, an alkenyl group, A cycloalkenyl group or an aromatic hydrocarbon group, M is a silicon or tin atom, X is a halogen atom, a is an integer of 0 to 2, and b is an integer of 2 to 4.
  • the amount of the coupling agent is preferably 0.03 to 0.4 mol, more preferably 0.05 to 0.3 mol, per mol of the organic alkali metal compound (alkali metal catalyst) used. When the amount used is less than 0.03, the effect of improving the workability is small. Conversely, when the amount exceeds 0.4 mol, the alkali metal terminal reacting with the modifier having a functional group is reduced, and the fuel efficiency is improved. The effect is reduced.
  • the modified diene polymer can be coagulated by a coagulation method used in the production of rubber by ordinary solution polymerization such as addition of a coagulant or steam coagulation, and can be separated from the reaction solvent.
  • the solidification temperature is not limited at all.
  • a diene polymer (modified diene polymer) is obtained by drying the coagulated product separated from the reaction solvent.
  • a band drier, an extrusion drier, etc. used in normal synthetic rubber production can be used, and the drying temperature is not limited at all.
  • the Mooney viscosity (ML 1 + 4 ) (100 ° C.) of the diene polymer is preferably 10 to 200, more preferably 20 to 150.
  • the upper limit is more preferably 100 or less, and particularly preferably 75 or less.
  • Mooney viscosity is less than 10
  • mechanical properties such as the tensile strength of the vulcanizate may be reduced.
  • the viscosity exceeds 200, the miscibility is poor when used in combination with other rubbers. Processing operability may deteriorate, and the mechanical properties of the resulting vulcanizate of the rubber composition may deteriorate.
  • the Mooney viscosity can be measured by the method described in the examples.
  • the vinyl content of the conjugated diene part of the diene polymer is not particularly limited, but is preferably 10 to 70 mol%, more preferably 15 to 60 mol%.
  • the lower limit is more preferably 35 mol% or more, particularly preferably 40 mol% or more, and most preferably 50 mol% or more. If it is less than 10 mol%, the glass transition temperature of the polymer will be low, and when used as a polymer for tires, the grip performance may be inferior. On the other hand, if it exceeds 70 mol%, the glass transition temperature of the polymer will be low. The temperature rises and the resilience may be inferior.
  • the vinyl content (1,2-bond butadiene unit amount) can be measured by infrared absorption spectrum analysis.
  • the content of the diene polymer in 100% by mass of the rubber component is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 40% by mass or more, and particularly preferably 60% by mass or more. If it is less than 5% by mass, sufficient fuel economy, wet grip performance, dry grip performance, wear resistance, and processability may not be obtained.
  • the content of the diene polymer may be 100% by mass, but is preferably 90% by mass or less.
  • other rubber components may be used in combination with the diene polymer.
  • examples of other rubber components include natural rubber (NR), butadiene rubber (BR), styrene butadiene rubber (SBR), styrene isoprene butadiene rubber (SIBR), ethylene propylene diene rubber (EPDM), chloroprene rubber (CR), Examples include acrylonitrile butadiene rubber (NBR).
  • a rubber component may be used independently and may use 2 or more types together.
  • NR and BR are preferable because of the improvement in rubber strength, high wear resistance, and high crack growth resistance. Further, when NR or BR is used together with the diene polymer, the effect of improving wet grip performance, wear resistance, and workability is great by the combined use with the structure silica.
  • the NR is not particularly limited, and for example, those commonly used in the tire industry such as SIR20, RSS # 3, TSR20 and the like can be used.
  • the content of NR in 100% by mass of the rubber component is preferably 5% by mass or more, more preferably 10% by mass or more. If it is less than 5% by mass, fuel economy and wear resistance may be reduced.
  • the NR content is preferably 40% by mass or less, more preferably 30% by mass or less. If it exceeds 40% by mass, the dry grip performance may be lowered.
  • the BR is not particularly limited.
  • BR containing a syndiotactic polybutadiene crystal such as can be used.
  • BR having a cis content of 95% by mass or more is preferable because it has a low glass transition temperature (Tg) and is advantageous for low temperature characteristics.
  • the content of BR in 100% by mass of the rubber component is preferably 5% by mass or more, more preferably 10% by mass or more. If it is less than 5% by mass, fuel economy and wear resistance may be reduced.
  • the BR content is preferably 40% by mass or less, more preferably 30% by mass or less. If it exceeds 40 mass%, wet grip performance, dry grip performance, and workability may be deteriorated.
  • the structure silica (linear silica) used in the present invention has three or more particles adjacent to one particle (hereinafter referred to as a branched particle X), and the branched particle X and a particle adjacent thereto. As a result, a branched structure is formed.
  • the branched particle X is a particle X of the particles in FIG. 1 which is a schematic explanatory diagram of the branched particle, and is adjacent to three or more other particles.
  • structure silica what has a branched structure (for example, FIG. 2) and what does not have are mentioned, However, Since the structured silica which does not have a branched structure will aggregate immediately, it does not exist substantially.
  • the average length (L 1 in FIG. 2) between the branched particles XX including the branched particles X of the structure silica is 30 nm or more, preferably 40 nm or more. If it is less than 30 nm, there is a tendency that the dry grip performance cannot be sufficiently improved.
  • L 1 is 400 nm or less, preferably 200 nm or less, more preferably 100 nm or less. When it exceeds 400 nm, hysteresis loss increases and fuel efficiency tends to deteriorate.
  • the average primary particle size of the structure silica (D, see FIG. 2 which is a schematic explanatory diagram of structure silica containing branched particles) is preferably 5 nm or more, more preferably 7 nm or more. If it is less than 5 nm, the hysteresis loss increases and the fuel efficiency tends to deteriorate. Further, D is preferably 1000 nm or less, more preferably 100 nm or less, and still more preferably 18 nm or less. If it exceeds 1000 nm, the dry grip performance tends not to be sufficiently improved.
  • the average aspect ratio (L 1 / D) of the XX between the branched particles including the branched particle X of the structure silica is preferably 3 or more, more preferably 4 or more. If it is less than 3, there is a tendency that the dry grip performance cannot be sufficiently improved.
  • L 1 / D is preferably 100 or less, more preferably 30 or less. When L 1 / D exceeds 100, hysteresis loss increases and fuel efficiency tends to deteriorate.
  • silica D, L 1 and L 1 / D can be measured by observation with a transmission electron microscope of silica dispersed in a vulcanized rubber composition.
  • L 1 / D is 5.
  • the content of the structure silica is preferably 5 parts by mass or more, more preferably 45 parts by mass or more, and still more preferably 65 parts by mass or more with respect to 100 parts by mass of the rubber component. If it is less than 5 mass parts, there exists a tendency for the effect which mix
  • the content of the structure silica is preferably 150 parts by mass or less, more preferably 120 parts by mass or less, and still more preferably 100 parts by mass or less. When it exceeds 150 parts by mass, the rigidity of the rubber composition increases, and the workability and wet grip performance tend to deteriorate.
  • silane coupling agent in the rubber composition of the present invention, it is preferable to use a silane coupling agent together with the structure silica.
  • the silane coupling agent include sulfide, mercapto, vinyl, amino, glycidoxy, nitro, and chloro silane coupling agents.
  • a sulfide system is preferable because the effects of the present invention can be obtained satisfactorily.
  • bis (3-triethoxysilylpropyl) tetrasulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3- Triethoxysilylpropyl) disulfide and bis (2-triethoxysilylethyl) disulfide are preferred, and bis (3-triethoxysilylpropyl) disulfide is more preferred.
  • the content of the silane coupling agent is preferably 1 part by mass or more, more preferably 3 parts by mass or more with respect to 100 parts by mass of the structure silica. If it is less than 1 part by mass, the dry grip performance and workability tend not to be improved sufficiently.
  • the content of the silane coupling agent is preferably 20 parts by mass or less, more preferably 12 parts by mass or less. When it exceeds 20 parts by mass, there is a tendency that an effect commensurate with the increase in cost cannot be obtained.
  • the rubber composition of the present invention includes compounding agents conventionally used in the tire industry, such as reinforcing fillers such as carbon black, various softening agents, various anti-aging agents, waxes, and stearic acid.
  • Vulcanizing agents such as zinc oxide and sulfur, various vulcanization accelerators, and the like can be blended.
  • the rubber composition of the present invention preferably contains carbon black.
  • carbon black is not particularly limited, and for example, GPF, HAF, ISAF, SAF and the like can be used.
  • the nitrogen adsorption specific surface area (N 2 SA) of carbon black is preferably 30 m 2 / g or more, more preferably 70 m 2 / g or more, and still more preferably 100 m 2 / g or more.
  • N 2 SA is less than 30 m 2 / g, there is a tendency that sufficient reinforcing properties cannot be obtained.
  • N 2 SA is preferably 250 meters 2 / g or less of carbon black, more preferably not more than 150m 2 / g, 125m 2 / g or less is more preferable.
  • N 2 SA is more than 250 meters 2 / g, the viscosity of the unvulcanized becomes very high, processability tends to be deteriorated. In addition, fuel efficiency tends to deteriorate.
  • the nitrogen adsorption specific surface area of carbon black is measured according to JIS K6217-2: 2001.
  • Carbon black has a dibutyl phthalate (DBP) oil absorption of preferably 70 ml / 100 g or more, more preferably 90 ml / 100 g or more.
  • the DBP oil absorption of carbon black is preferably 160 ml / 100 g or less, more preferably 117 ml / 100 g or less. By making it within this range, fuel economy, wet grip performance, dry grip performance, and wear resistance can be improved in a well-balanced manner.
  • the DBP oil absorption of carbon black is measured according to JIS K6217-4: 2001.
  • the content of carbon black is preferably 5 parts by mass or more, more preferably 8 parts by mass or more with respect to 100 parts by mass of the rubber component.
  • the amount is less than 5 parts by mass, the effect of blending carbon black may not be sufficiently obtained.
  • the content of carbon black is preferably 20 parts by mass or less, more preferably 15 parts by mass or less. If it exceeds 20 parts by mass, the fuel efficiency tends to deteriorate.
  • vulcanization accelerators examples include sulfenamide, thiazole, thiuram, thiourea, guanidine, dithiocarbamic acid, aldehyde-amine or aldehyde-ammonia, imidazoline, or xanthate vulcanization accelerators. Agents. Of these, sulfenamide vulcanization accelerators are preferred because the effects of the present invention can be obtained satisfactorily.
  • sulfenamide vulcanization accelerator examples include N-tert-butyl-2-benzothiazolylsulfenamide (TBBS), N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), N, N And '-dicyclohexyl-2-benzothiazolylsulfenamide (DZ).
  • TBBS N-tert-butyl-2-benzothiazolylsulfenamide
  • CBS N-cyclohexyl-2-benzothiazolylsulfenamide
  • DZ N And '-dicyclohexyl-2-benzothiazolylsulfenamide
  • CBS is preferable because the effects of the present invention can be obtained satisfactorily, and it is more preferable to use CBS and N, N′-diphenylguanidine in combination.
  • the above components are kneaded using a rubber kneader such as a Banbury mixer or an open roll, and then vulcanized. It can be manufactured by a method or the like.
  • knead the silica sol together with a rubber component containing the modified diene polymer in a rubber kneading apparatus from the viewpoint that the rubber composition of the present invention in which structure silica is formed can be easily produced.
  • a final kneading step in which the kneaded product obtained by the base kneading step, the vulcanizing agent, and the vulcanization accelerator are kneaded at 30 to 70 ° C. (preferably 40 to 60 ° C.) for 3 to 10 minutes;
  • a vulcanization step of vulcanizing the unvulcanized rubber composition obtained by the finish kneading step at 150 to 190 ° C. (preferably 160 to 180 ° C.) for 5 to 30 minutes is more preferable.
  • the preferable compounding amount (silica conversion) of silica sol is the same as that of the above-mentioned structure silica.
  • a structure silica such as the base kneading step
  • L 1 of structure silica tends to likely too long, toluene It is preferable to knead without using.
  • silica sol refers to a colloidal solution in which silica is dispersed in a solvent.
  • the silica sol is not particularly limited, but a colloidal solution in which elongated silica is dispersed in a solvent is preferable because a structure silica can be suitably formed.
  • a colloidal solution in which elongated silica is dispersed in an organic solvent (organo Silica sol) is more preferable.
  • the elongated silica means a silica (secondary particle) having a chain shape in which a plurality of primary particles such as a spherical shape and a granular shape are connected. It may be linear or branched.
  • the solvent for dispersing silica is not particularly limited, but alcohols such as methanol and isopropanol are preferable, and isopropanol is more preferable.
  • the average particle diameter of primary particles constituting silica (secondary particles) contained in the silica sol is preferably 1 to 100 nm, more preferably 5 to 80 nm.
  • the average particle size of the primary particles was determined by visually measuring the particle size (average diameter) of 50 primary particles in a photograph taken with a transmission electron microscope JEM2100FX manufactured by JEOL. .
  • the average diameter of the primary particles is an average value of thicknesses (diameters) measured at arbitrary 50 locations of the silica (secondary particles) in the electron micrograph.
  • silica (secondary particles) has a constriction and a bead shape, it can be obtained as an average value of the diameters of 50 bead beads in an electron micrograph.
  • each rosary has a major axis and a minor axis, that is, when each rosary is elongated, the minor axis is measured.
  • the average particle diameter of silica (secondary particles) contained in the silica sol is preferably 20 to 300 nm, more preferably 30 to 150 nm.
  • the average particle diameter of silica (secondary particles) can be measured by a dynamic light scattering method, and specifically, can be measured by the following method.
  • the average particle diameter of silica (secondary particles) was measured with a laser particle analysis system ELS-8000 (cumulant analysis) manufactured by Otsuka Electronics Co., Ltd.
  • the measurement conditions are a temperature of 25 ° C., an angle between incident light and a detector of 90 °, and the number of integrations of 100 times.
  • the measurement concentration was usually about 5 ⁇ 10 ⁇ 3 mass%.
  • the silica (secondary particles) can be obtained by, for example, the method described in claim 2 of the pamphlet of International Publication No. 00/15552 and the disclosure of the specification related thereto, Patent No. 2803134, Patent No. 2926915 It can manufacture according to the method etc. as described in the disclosure part of claim
  • the rubber composition of the present invention can be used for each member of a tire, and in particular, can be suitably used for a tread (particularly a cap tread).
  • the pneumatic tire of the present invention is produced by a usual method using the rubber composition. That is, if necessary, a rubber composition containing various additives is extruded in accordance with the shape of each member of the tire (especially, the tread (cap tread)) at an unvulcanized stage, and is applied to the tire molding machine. Then, after forming by an ordinary method and pasting together with other tire members to form an unvulcanized tire, the tire can be manufactured by heating and pressing in a vulcanizer.
  • the pneumatic tire of the present invention is preferably used as a tire for passenger cars, a tire for trucks and buses, a tire for motorcycles, a tire for competition, and the like, and more preferably used as a tire for passenger cars.
  • Production Example 1 (Preparation of polymerization initiator) Add 10 ml of 1,3-divinylbenzene in hexane (1.6 M) to a 100 ml pressure-resistant container thoroughly purged with nitrogen, and drop 20 ml of n-butyllithium hexane solution (1.6 M) at 0 ° C. A polymerization initiator solution was obtained by stirring for a period of time.
  • Production Example 2 (Preparation of diene polymer (modified diene polymer)) To a 1000 ml pressure vessel fully purged with nitrogen, add 600 ml of cyclohexane, 0.12 mol of styrene, 0.8 mol of 1,3-butadiene, 0.7 mmol of N, N, N ′, N′-tetramethylethylenediamine, and further manufacture 1.5 ml of the polymerization initiator solution obtained in Example 1 was added and stirred at 40 ° C. Three hours later, 1.0 mmol of tetraglycidyl-1,3-bisaminomethylcyclohexane as a modifier was added and stirred.
  • Mooney viscosity Heated by preheating for 1 minute using a Mooney viscosity tester in accordance with JIS K 6300-1 “Unvulcanized rubber-Physical properties-Part 1: Determination of viscosity and scorch time using Mooney viscometer” Under the temperature condition of 100 ° C., the small rotor was rotated, and the Mooney viscosity (ML 1 + 4/100 ° C.) of the diene polymer after 4 minutes was measured. The numbers after the decimal point are rounded off. As a result, the Mooney viscosity of the diene polymer was 60.
  • the vinyl content of the diene polymer was measured by infrared absorption spectrum analysis. As a result, the vinyl content of the diene polymer was 57 mol%.
  • Diene polymer Diene polymer SBR prepared in Production Example 2 above: S15 coupled with E15 (a compound having an epoxy group (tetraglycidyl-1,3-bisaminomethylcyclohexane) manufactured by Asahi Kasei Chemicals Corporation) -SBR, styrene unit amount: 23% by mass, vinyl unit amount: 64% by mass, terminal group: OH (one-end modified SBR))
  • BR Nipol BR1220 (cis content: 97% by mass) manufactured by Nippon Zeon Co., Ltd.
  • NR RSS # 3 Carbon black: Seast N220 manufactured by Mitsubishi Chemical Corporation (N220, N 2 SA: 114 m 2 / g, DBP oil absorption: 114 ml / 100 g)
  • silica sol elongated isopropanol-dispersed silica sol (average particle diameter of silica (secondary particles) measured by dynamic light scattering method): 40 to 100 nm), silica content: 15% by mass) (the amounts shown in Table 2 indicate the amount of silica in the organosilica sol)
  • Aroma oil Process X-140 manufactured by JX Nippon Oil & Energy Anti-aging agent: Antigen 6C (N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine) manufactured by Sumitomo Chemical Co., Ltd.
  • Wax Sunnock N manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
  • Sulfur Powder sulfur vulcanization accelerator manufactured by Karuizawa Sulfur Co., Ltd. (1): Noxeller CZ (N-cyclohexyl-2-benzothiazolylsulfenamide) manufactured by Ouchi Shinsei Chemical Co., Ltd.
  • a sample was cut out from the tread of the test tire, and the silica dispersed in the sample was observed with a transmission electron microscope.
  • the average primary particle diameter (D) of silica and the distance between the branched particles XX including the branched particles X were measured.
  • the average aspect ratio of the XX between the branched particles including the branched particle X (L 1 / D)
  • the average aspect ratio (L 2 / D) of XX between the branched particles not including the branched particle X was calculated.
  • the numerical value was an average value obtained by measuring 30 locations.
  • the test tire was mounted on a passenger car equipped with 1800 cc-class ABS, the amount of decrease in groove depth after traveling 30000 km in an urban area was measured, and the travel distance when the groove depth decreased by 1 mm was calculated. Furthermore, the abrasion resistance index of Comparative Example 5 was set to 100, and the amount of decrease in the groove depth of each formulation was displayed as an index according to the following formula. In addition, it shows that it is excellent in abrasion resistance, so that an abrasion resistance index
  • (Abrasion resistance index) (travel distance when the groove depth is reduced by 1 mm in each formulation) / (travel distance when the groove of the tire of Comparative Example 5 is reduced by 1 mm) ⁇ 100
  • Mooney viscosity About the obtained unvulcanized rubber composition, it measured at 130 degreeC according to the measuring method of the Mooney viscosity based on JISK6300.
  • the Mooney viscosity (ML 1 + 4 ) of Comparative Example 5 was set to 100, and indexed by the following formula (Mooney viscosity index). The larger the index, the lower the Mooney viscosity and the better the processability.
  • (Mooney viscosity index) (ML 1 + 4 of Comparative Example 5) / (ML 1 + 4 of each formulation) ⁇ 100

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Tires In General (AREA)
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Abstract

La présente invention concerne : une composition de caoutchouc pour bandages, qui est capable d'améliorer les économies de consommation de carburant, les performances d'adhérence humide, les performances d'adhérence à sec, la résistance à l'usure et l'aptitude au façonnage ; et un pneu pneumatique qui utilise la composition de caoutchouc pour des bandages. La présente invention concerne une composition de caoutchouc pour bandages, qui contient un polymère de diène et de la silice. Le polymère de diène est un polymère de diène modifié qui est obtenu par réaction de la substance (A) et la substance (B) décrites ci-dessous. Lorsqu'une particule de silice ayant trois particules ou plus adjacentes à celle-ci est considérée comme une particule de branche (X), la silice a une longueur moyenne (L1) entre les particules de branche X-X comprenant les particules de branche X de 30 à 400 nm. (A) un polymère de diène conjugué actif ayant une extrémité de métal alcalin, ledit polymère de diène conjugué actif étant obtenu par polymérisation d'un monomère de diène conjugué ou un monomère de diène conjugué et un monomère de vinyle aromatique en présence de la substance (C) décrite ci-dessous (B) un agent modificateur ayant un groupe fonctionnel (C) une espèce chimique qui est obtenue par réaction d'un composé représenté par la formule (1) avec un composé de métal alcalin organique.
PCT/JP2012/060531 2011-04-20 2012-04-19 Composition de caoutchouc pour bandages et pneu pneumatique WO2012144541A1 (fr)

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EP3854843A4 (fr) * 2018-09-20 2022-06-29 Bridgestone Corporation Composition de caoutchouc et pneu

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JP2007154158A (ja) * 2005-11-14 2007-06-21 Sumitomo Rubber Ind Ltd ゴム組成物およびそれをトレッドに用いた空気入りタイヤ
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EP3854843A4 (fr) * 2018-09-20 2022-06-29 Bridgestone Corporation Composition de caoutchouc et pneu

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