Rubber composition and tire

Abstract

The object of the present invention is to provide a rubber composition which can achieve both reinforcement and low loss at a high level. The rubber composition comprises a rubber component, carbon black, and silica, and is characterized in that the CTAB adsorption specific surface area of ​​the silica is 250 m 2 / g or more, and when measured by disc centrifuge particle size analysis, the aggregate diameter (D CPS ) and primary particle size (D I ) satisfies the relationship 700 ≥ D CPS 3 / D I 3 ≥300(1), the rubber component comprises at least one rubber selected from natural rubber and polyisoprene rubber and at least one rubber selected from modified butadiene rubber and modified styrene / butadiene rubber, and the mass content of the carbon black relative to the total mass content of the carbon black and the silica is 70% or more.

Description

Technical Field

[0001] The present invention relates to a rubber composition and a tire. Background Art

[0002] Generally, pneumatic tires are required to have high performance that can simultaneously meet multiple performance requirements. Among them, tire components such as treads are strongly expected to suppress the rolling resistance of the tire while being excellent in wear resistance. However, these properties are inconsistent with each other, so there have been many trials and errors so far.

[0003] In the rubber composition applied to the tread of the tire, silica is one of the commonly used reinforcing fillers. However, generally, increasing the content of silica improves the reinforcement of the tire, which can improve the wear resistance to a certain extent, but tends to deteriorate the low loss property. If the content of silica is too high, the viscosity of the unvulcanized rubber may increase to a degree beyond the necessary level, thereby deteriorating the processability.

[0004] Therefore, in order to simultaneously achieve both reinforcement and low loss properties of the rubber composition, for example, PTL 1 discloses a technology for improving the dispersibility of silica by using in combination silica having a CTAB specific surface area of ​​a predetermined value or more and a BET specific surface area of ​​a predetermined value or more and a mercapto group-containing silane coupling agent.

[0005] Prior art literature

[0006] Patent Literature

[0007] PTL 1: JP2011140612A Summary of the invention

[0008] Problem that the invention aims to solve

[0009] However, although the technology of PTL 1 can obtain a certain low loss property by utilizing the effect of a silane coupling agent, the particle size of silica is large, and further improvement in reinforcement is required.

[0010] Therefore, it is possible to contribute to providing a rubber composition which achieves both reinforcement and low loss properties at a high level, and a tire which achieves both reinforcement and low loss properties at a high level.

[0011] Solutions for solving problems

[0012] The present inventors have conducted research to solve the above problems and found that reducing the particle size (primary particle size) of silica improves the reinforcement of the rubber composition compared with the past, and increasing the aggregate morphology of silica obtains excellent low loss without reducing the reinforcement. The present inventors also found that including a specific modified rubber in the rubber component can improve the dispersibility of silica, which can further improve the reinforcement and low loss, and optimizing the content ratio of carbon black in the filler can further improve the reinforcement.

[0013] The present invention provides:

[0014] A rubber composition comprising a rubber component and silicon dioxide, wherein the CTAB adsorption specific surface area of ​​the silicon dioxide is 250 m 2 / g or more; the diameter (D) of the aggregate morphology of the silica measured by disc centrifugal particle size analysis CPS ) and primary particle size (D I )satisfy:

[0015] 700≥D CPS 3 / D I 3 ≥300 (1);

[0016] The rubber component comprises at least one selected from natural rubber and polyisoprene rubber, and at least one selected from modified butadiene rubber and modified styrene butadiene rubber;

[0017] The mass content of carbon black relative to the total mass content of carbon black and silicon dioxide is 70% or more; and

[0018] At least one selected from the group consisting of modified butadiene rubber and modified styrene butadiene rubber is modified by at least one selected from the group consisting of a hydrocarbyloxysilane compound represented by formula (IV), a hydrocarbyloxysilane compound represented by formula (V), a hydrocarbyloxysilane compound represented by formula (III), a coupling agent represented by formula (VI), a coupling agent represented by formula (VII), lithium amide represented by formula (VIII), and vinyl pyridine:

[0019]

[0020] [where: q1+q2=3 (where q1 is an integer from 0 to 2, and q2 is an integer from 1 to 3); R 31 represents a divalent aliphatic group or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms; R 32and R 33 Each independently represents a hydrolyzable group, a monovalent aliphatic group or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms; R 34 represents a monovalent aliphatic group or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when q1 is 2, they may be the same or different; and R 35 represents a monovalent aliphatic group or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when q2 is 2 or more, they may be the same or different];

[0021]

[0022] [wherein: r1+r2=3 (wherein r1 is an integer from 1 to 3, and r2 is an integer from 0 to 2); R 36 represents a divalent aliphatic group or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms; R 37 represents dimethylaminomethyl, dimethylaminoethyl, diethylaminomethyl, diethylaminoethyl, methylsilyl(methyl)aminomethyl, methylsilyl(methyl)aminoethyl, methylsilyl(ethyl)aminomethyl, methylsilyl(ethyl)aminoethyl, dimethylsilylaminomethyl, dimethylsilylaminoethyl, a monovalent aliphatic group or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when r1 is 2 or more, they may be the same or different; and R 38 represents a hydrocarbyloxy group having 1 to 20 carbon atoms, a monovalent aliphatic group or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when r2 is 2, they may be the same or different];

[0023]

[0024] [Among them: A 1 represents a monovalent group having at least one functional group selected from (thio)epoxy, (thio)isocyanate, (thio)ketone, (thio)aldehyde, imine, amide, trialkyl isocyanurate, (thio)carboxylate, metal salt of (thio)carboxylic acid, carboxylic anhydride, carboxylic acid halide, and dihydrocarbonate carbylester; R 1 Represents a single bond or a divalent inactive hydrocarbon group; R 2 and R 3Each independently represents a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms; n is an integer of 0 to 2; when there are multiple R 2 When R 2 Can be the same or different. When there are multiple OR 3 When, OR 3 can be the same or different and contain no active protons and onium salts in the molecule];

[0025]

[0026] [Where: R 12 , R 13 , and R 14 Each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms; R 15 , R 16 , R 17 , R 18 , and R 20 Each independently represents an alkyl group having 1 to 20 carbon atoms; R 19 and R 22 Each independently represents an alkylene group having 1 to 20 carbon atoms; R 21 represents an alkyl group or trialkylsilyl group having 1 to 20 carbon atoms; m represents an integer of 1 to 3; p represents 1 or 2; when there are multiple R 12 ~R 22 , m and p are independent of each other; i, j, and k each independently represent an integer of 0 to 6, wherein (i+j+k) is an integer of 3 to 10; and A represents a hydrocarbon group or an organic group having 1 to 20 carbon atoms, the organic group having at least one atom selected from the group consisting of oxygen atoms, nitrogen atoms, silicon atoms, sulfur atoms, and phosphorus atoms and having no active hydrogen];

[0027] (R 3 ) a ZX b …(VII)

[0028] [Wherein: Z represents tin or silicon; (R 3 ) is selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms; X represents chlorine or bromine; a is 0 to 3, b is 1 to 4, wherein a+b=4];

[0029] (AM)Li(Q) y …(VIII)

[0030] [Wherein: y is 0 or 0.5 to 3; (Q) is a solubilizing component selected from hydrocarbons, ethers, amines, and mixtures thereof; and (AM) is of the general formula [I]:

[0031]

[0032] (where R 1 independently represents an alkyl group, a cycloalkyl group, or an aralkyl group having 1 to 12 carbon atoms),

[0033] Or general formula [II]:

[0034]

[0035] (wherein (R2) represents: an alkylene group having 3 to 16 methylene groups; a substituted alkylene group having a straight chain or branched alkyl group, cycloalkyl group, bicycloalkyl group, aryl group, or aralkyl group having 1 to 12 carbon atoms as a substituent; an oxydiethylene group; or an N-alkylamino-alkylene group)].

[0036] The above configuration can achieve both reinforcement and low loss properties at a high level.

[0037] In addition, for the rubber composition of the present invention, it is more preferred that at least one selected from the modified butadiene rubber and the modified styrene butadiene rubber is modified by at least one selected from the group consisting of: N,N-bis(trimethylsilyl)-3-[diethoxy(methyl)silyl]propylamine; N-(1,3-dimethylbutylene)-3-triethoxysilyl-1-propylamine; tetrakis(3-trimethoxysilylpropyl)-1,3-propylenediamine; tin tetrachloride; a reactant of hexamethyleneimine and n-butyllithium; 4-vinylpyridine; and 2-vinylpyridine. This is because the reinforcing property and the low loss property can be further improved.

[0038] In the rubber composition of the present invention, the total content of carbon black and silica is preferably 40 to 100 parts by mass based on 100 parts by mass of the rubber component, because both reinforcement and low loss properties can be achieved at a higher level.

[0039] The tire of the present invention includes the rubber composition of the present invention described above.

[0040] The above configuration can achieve both reinforcement and low loss properties at a high level.

[0041] Effects of the Invention

[0042] The present invention can provide a rubber composition that achieves both reinforcement and low loss properties at a high level. The present invention can also provide a tire that achieves both reinforcement and low loss properties at a high level. DETAILED DESCRIPTION

[0043] One of the disclosed embodiments is described in detail below.

[0044] <Rubber Composition>

[0045] The rubber composition of the present invention is a rubber composition including a rubber component, carbon black, and silica.

[0046] The respective components constituting the rubber composition are described below.

[0047] (Rubber component)

[0048] The rubber composition of the present invention includes a rubber component.

[0049] The rubber component includes at least one selected from natural rubber (NR) and polyisoprene rubber (IR), and at least one selected from modified butadiene rubber (modified BR) and modified styrene butadiene rubber (modified SBR).

[0050] Including at least one selected from modified BR and modified SBR can improve the interaction with silica and improve the dispersibility of silica, thereby further improving the reinforcing property and low loss property of the rubber component. Including at least one selected from NR and IR can increase the elastic modulus of the rubber component and improve the reinforcing property.

[0051] A rubber component other than the above-mentioned rubber may be appropriately contained depending on the desired properties. For example, it is preferred that a diene rubber is contained from the viewpoint that excellent reinforcing properties and low loss properties can be obtained.

[0052] Here, in addition to the above-mentioned natural rubber (NR) and polyisoprene rubber (IR), types of diene rubber include butadiene rubber (BR), styrene butadiene rubber (SBR), styrene isoprene butadiene rubber (SIBR), chloroprene rubber (CR), acrylonitrile butadiene rubber (NBR), etc.

[0053] Types of non-diene rubbers include ethylene propylene diene rubber (EPDM), ethylene propylene rubber (EPM), butyl rubber (IIR), and the like.

[0054] One of these rubbers may be used alone, or two or more of these rubbers may be blended and used. This rubber may be unmodified rubber or modified rubber.

[0055] Furthermore, the rubber component preferably contains 40% by mass or more of at least one selected from natural rubber and polyisoprene rubber, and more preferably contains 50% by mass or more of at least one selected from natural rubber and polyisoprene rubber, because the reinforcing property of the rubber composition can be further improved.

[0056] From the viewpoint of maintaining the low loss property at a high level, the content of at least one selected from natural rubber and polyisoprene rubber is preferably 90% by mass or less, preferably 85% by mass or less, and more preferably 80% by mass or less.

[0057] The position of the modified functional group in the modified butadiene rubber and the modified styrene butadiene rubber is not particularly limited, and may be, for example, at the end of the main chain, in the main chain, or only within 1 / 4 of the total chain length from the end of the main chain. The number of the modified functional groups is also not particularly limited, and may be appropriately selected according to the purpose.

[0058] At least one selected from modified butadiene rubber and modified styrene butadiene rubber is modified by at least one selected from the group consisting of the following hydrocarbyloxysilane compounds represented by formulas (IV), (V), and (III), coupling agents represented by formulas (VI) and (VII), lithium amide represented by formula (VIII), and vinyl pyridine.

[0059]

[0060] Where: q1+q2=3 (where q1 is an integer from 0 to 2, and q2 is an integer from 1 to 3); R 31 represents a divalent aliphatic group or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms; R 32 and R 33 Each independently represents a hydrolyzable group, a monovalent aliphatic group or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms; R 34 represents a monovalent aliphatic group or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when q1 is 2, they may be the same or different; and R 35 represents a monovalent aliphatic group or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when q2 is 2 or more, they may be the same or different.

[0061]

[0062] Where: r1+r2=3 (where r1 is an integer from 1 to 3, and r2 is an integer from 0 to 2); R 36 represents a divalent aliphatic group or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms; R 37represents dimethylaminomethyl, dimethylaminoethyl, diethylaminomethyl, diethylaminoethyl, methylsilyl(methyl)aminomethyl, methylsilyl(methyl)aminoethyl, methylsilyl(ethyl)aminomethyl, methylsilyl(ethyl)aminoethyl, dimethylsilylaminomethyl, dimethylsilylaminoethyl, a monovalent aliphatic group or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when r1 is 2 or more, they may be the same or different; and R 38 represents a hydrocarbonoxy group having 1 to 20 carbon atoms, a monovalent aliphatic group or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when r2 is 2, they may be the same or different.

[0063]

[0064] Among them: A 1 represents a monovalent group having at least one functional group selected from (thio)epoxy, (thio)isocyanate, (thio)ketone, (thio)aldehyde, imine, amide, trialkyl isocyanurate, (thio)carboxylate, metal salt of (thio)carboxylic acid, carboxylic anhydride, carboxylic acid halide, and dialkyl carbonate; R 1 Represents a single bond or a divalent inactive hydrocarbon group; R 2 and R 3 Each independently represents a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms; n is an integer of 0 to 2; when there are multiple R 2 When R 2 Can be the same or different. When there are multiple OR 3 When, OR 3 They can be the same or different and do not contain active protons and onium salts in the molecule.

[0065] In formula (III), in A 1 Among the functional groups of the present invention, imine includes ketimine, aldimine and amidine, and (thio)carboxylic acid ester includes unsaturated carboxylic acid ester such as acrylate and methacrylate. The metal of the metal salt of (thio)carboxylic acid may include alkali metal, alkaline earth metal, Al, Sn, Zn, etc. 1 The divalent inactive hydrocarbon group in may preferably include an alkylene group having 1 to 20 carbon atoms. The alkylene group may be any of a linear, branched, or cyclic type, but in particular, a linear alkylene group is preferred. Examples of the linear alkylene group include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, and the like. 2 and R 3It may include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, etc. Here, the above-mentioned alkyl group and alkenyl group may be any of a linear, branched, or cyclic type, and their examples include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a cyclopentyl group, a cyclohexyl group, a vinyl group, an allyl group, a hexenyl group, an octenyl group, a cyclopentenyl group, a cyclohexenyl group, etc. The aryl group may have a substituent such as a lower alkyl group on the aromatic ring, and examples thereof include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, etc. In addition, the aralkyl group may have a substituent such as a lower alkyl group on the aromatic ring, and examples thereof include a benzyl group, a phenethyl group, a naphthyl group, etc. n is an integer of 0 to 2, but is preferably 0, and the molecule must not contain active protons and onium salts.

[0066] The hydrocarbyloxysilane compound represented by the formula (III) may preferably include, for example, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, (2-glycidoxyethyl)methyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4 As the (thio)epoxy-containing hydrocarbonoxysilane compounds, there are 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl(methyl)dimethoxysilane, 2-(3,4-epoxycyclohexyl)trimethoxysilane, and compounds obtained by replacing the epoxy groups in such compounds with thioepoxy groups, but among them, 3-glycidoxypropyltrimethoxysilane and 2-(3,4-epoxycyclohexyl)trimethoxysilane are particularly preferred.

[0067] As the imine group-containing hydrocarbyloxysilane compound, it may preferably include N-(1,3-dimethylbutylene)-3-(triethoxysilyl)-1-propylamine, N-(1-methylethylidene)-3-(triethoxysilyl)-1-propylamine, N-ethylidene-3-(triethoxysilyl)-1-propylamine, N-(1-methylpropylidene)-3-(triethoxysilyl)-1-propylamine, N-(4-N,N-dimethylaminobenzylidene)-3-(triethoxysilyl)-1-propylamine, N-(cyclohexylene)-3-(triethoxysilyl)-1-propylamine, The present invention relates to trimethoxysilyl compounds, methyldiethoxysilyl compounds, ethyldiethoxysilyl compounds, methyldimethoxysilyl compounds, ethyldimethoxysilyl compounds, etc., but among them, N-(1-methylpropylene)-3-(triethoxysilyl)-1-propylamine and N-(1,3-dimethylbutylene)-3-(triethoxysilyl)-1-propylamine are particularly preferred.

[0068]

[0069] Where: R 12 , R 13 , and R 14 Each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms; R 15 , R 16 , R 17 , R 18 , and R 20 Each independently represents an alkyl group having 1 to 20 carbon atoms; R 19 and R 22 Each independently represents an alkylene group having 1 to 20 carbon atoms; R 21 represents an alkyl group or trialkylsilyl group having 1 to 20 carbon atoms; m represents an integer of 1 to 3; p represents 1 or 2; when there are multiple R 12 ~R 22 , m and p, they are independent of each other; i, j, and k each independently represent an integer from 0 to 6, wherein (i+j+k) is an integer from 3 to 10; and A represents a hydrocarbon group and an organic group having 1 to 20 carbon atoms, wherein the organic group has at least one atom selected from the group consisting of oxygen atoms, nitrogen atoms, silicon atoms, sulfur atoms, and phosphorus atoms and does not have active hydrogen.

[0070] Here, it is preferred that the coupling agent represented by formula (VI) is at least one selected from the group consisting of tetrakis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-1,3-propylenediamine, tetrakis(3-trimethoxysilylpropyl)-1,3-propylenediamine, and tetrakis(3-trimethoxysilylpropyl)-1,3-bisaminomethylcyclohexane. In this case, the reinforcing property can be further improved.

[0071] (R 3 ) a ZX b …(VII)

[0072] Where: Z represents tin or silicon; (R 3 ) is selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms; X represents chlorine or bromine; a is 0 to 3, b is 1 to 4, wherein a+b=4.

[0073] Here, the coupling agent represented by formula (VII) is preferably tin tetrachloride, (R 3 )SnCl 3 , (R 3 ) 2 SnCl 2 , (R 3 ) 3 SnCl, etc., among which tin tetrachloride is particularly preferred.

[0074] (AM)Li(Q) y …(VIII)

[0075] Wherein: y is 0 or 0.5 to 3; (Q) is a solubilizing component selected from hydrocarbons, ethers, amines, and mixtures thereof; and (AM) is the general formula [I]:

[0076]

[0077] (where (R 1 ) independently represents an alkyl group, a cycloalkyl group, or an aralkyl group having 1 to 12 carbon atoms), or the general formula [II]:

[0078]

[0079] (where (R 2 ) represents: an alkylene group having 3 to 16 methylene groups; a substituted alkylene group having a straight chain or branched alkyl group, cycloalkyl group, bicycloalkyl group, aryl group, or aralkyl group having 1 to 12 carbon atoms as a substituent; an oxydiethylene group; or an N-alkylamino-alkylene group).

[0080] The presence of Q in formula (VIII) enables lithium amide to be dissolved in hydrocarbon solvents. Q comprises a diene or vinyl aromatic polymer or copolymer having a degree of polymerization of 3 to about 300 polymerized units. These polymers and copolymers include polybutadiene, polystyrene, polyisoprene and their copolymers. Other examples of Q include polar ligands (e.g., tetrahydrofuran (THF), tetramethylethylenediamine (TMEDA) etc.).

[0081] In addition, the lithium amide represented by formula (VIII) may be a mixture thereof and an organic alkali metal. The organic alkali metal is preferably selected from the group consisting of 4 )M、(R 5 )OM、(R 6 )C(O)OM、(R 7 )(R 8 )NM, and (R 9 )SO 3 M represents a compound, and herein, (R 4 )、(R 5 )、(R 6 )、(R 7 )、(R 8 ), and (R 9 ) are each selected from alkyl, cycloalkyl, alkenyl, aryl, and phenyl groups having about 1 to about 12 carbon atoms. The metal component M is selected from Na, K, Rb, and Cs. M is preferably Na or K. In addition, the mixture may also preferably contain an organic alkali metal in a mixing ratio of about 0.5 to about 0.02 equivalents per 1 equivalent of lithium in lithium amide. In particular, when obtaining a target polymer having a high styrene content, (E) is preferably used.

[0082] In the mixture of lithium amide and organic alkali metal, a chelating agent can be used as an auxiliary agent to prevent inhomogeneous polymerization. Available chelating agents include, for example, tetramethylethylenediamine (TMEDA), oxolanyl cyclic acetals, and cyclic oligomeric oxolanyl alkanes. In particular, cyclic oligomeric oxolanyl alkanes are preferred, and a specific example thereof is 2,2-bis(tetrahydrofuranyl)propane.

[0083] The vinyl pyridine includes, for example, 2-vinyl pyridine and 4-vinyl pyridine.

[0084] In addition, it is preferred that, among the various modifiers described above, at least one selected from the modified butadiene rubber and the modified styrene butadiene rubber is modified by at least one selected from the group consisting of N,N-bis(trimethylsilyl)-3-[diethoxy(methyl)silyl]propylamine, N-(1,3-dimethylbutylene)-3-triethoxysilyl-1-propylamine, 3-glycidoxypropyltrimethoxysilane, tetrakis(3-trimethoxysilylpropyl)-1,3-propylenediamine, tin tetrachloride, a reactant of hexamethyleneimine and n-butyllithium, 4-vinylpyridine, and 2-vinylpyridine. This is because more excellent reinforcing properties and low loss properties can be achieved.

[0085] From the viewpoint of achieving both reinforcement and low loss properties at a higher level, the total content of at least one selected from modified butadiene rubber and modified styrene butadiene rubber in the rubber component is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 25% by mass or more, and particularly preferably 30% by mass or more. From the viewpoint of processability of the rubber composition, the total content of at least one selected from modified butadiene rubber and modified styrene butadiene rubber is 60% by mass or less, preferably 50% by mass or less, and more preferably 45% by mass or less.

[0086] (Silicon Dioxide)

[0087] The rubber composition of the present invention further comprises silica in addition to the above-mentioned rubber component.

[0088] The CTAB adsorption specific surface area of ​​silica (CTAB) is 250 m 2 / g or more, and the diameter (D CPS ) and primary particle size (D I )satisfy:

[0089] 700≥D CPS 3 / D I 3 ≥300 (1).

[0090] The diameter (D CPS ) is not particularly limited, and a commercially available analyzer can be used to measure D CPS. For example, a disc centrifugal particle size distribution analyzer CPSDisc Centrifuge from CPS Instruments can be used. The measurement conditions are to add silica to water at a ratio of 3 wt% and ultrasonically treat to obtain a silica suspension. For this sample, the particle size distribution can be measured using a disc centrifugal particle size distribution analyzer at a rotation speed of 20,000 rpm. There may be variations in the measurement, so when comparing silica, corrections can be made appropriately.

[0091] The primary particle size can be calculated as:

[0092] D I =6000 / (CTAB×ρ) (2)

[0093] ρ:2.2g / cm 3 .

[0094] In the past, in order to improve low heat generation, wear resistance and fatigue crack resistance, lowstructuring has been carried out to reduce the degree of development of the aggregate structure of carbon black, wear resistance and fatigue crack resistance have been improved by making carbon black have a fine particle size, and heat degradation has been suppressed by widening the distribution of aggregate morphology. However, even when the morphology of carbon black is controlled in that way, wear resistance and fatigue crack resistance are easily deteriorated. This is believed to be due to the increase in large particle components by widening the distribution of aggregate morphology of carbon black.

[0095] In contrast, in the present invention, a vulcanized rubber excellent in reinforcement can be obtained without sacrificing wear resistance and fatigue crack resistance. The reason for this is not yet certain, but it is presumed to be due to the following reasons.

[0096] Heat generation in vulcanized rubber usually occurs when fillers such as carbon black and silica contained in vulcanized rubber rub against each other in rubber. Therefore, as mentioned above, in an environment where the large particle component of carbon black increases, low heat generation tends to deteriorate. Therefore, it is considered that by using silica with a fine particle size such as a primary particle size satisfying formula (2), silica with a fine particle size enters the gap between carbon black to maintain a state with low heat generation without affecting the aggregation of particles, and rubber interacts strongly with carbon black and silica in a destruction area such as wear and cracking of vulcanized rubber, which can improve reinforcement.

[0097] However, it is considered that when the particle size of silica is too small, the low heat generation property is reduced. Therefore, in the present invention, silica satisfies the above-mentioned condition of formula (1), so compared with conventional silica, the particle size (primary particle size) of silica is reduced to improve the reinforcing property, and at the same time, the increase in the aggregate morphology of silica can effectively suppress the deterioration of the low loss property, which can take into account both the reinforcing property and the low loss property of the rubber composition at a high level.

[0098] When D CPS 3 / D I 3 When D is less than 300, the particle size of silica is not small enough and the aggregate form of silica is not large enough, so it is impossible to achieve both reinforcement and low loss properties at a high level. CPS 3 / D I 3 When it exceeds 700, the particle size of silicon dioxide becomes too small, thereby reducing the low loss property.

[0099] In order to improve the reinforcing property of the tire, it is effective to reduce the particle size (primary particle size) of silica contained in the rubber composition, but as the particle size of silica decreases, the distance between the aggregates (aggregate morphology) of silica decreases, which increases the network effect, thereby deteriorating the low loss property. Therefore, in the present invention, the primary particle size (D I ) improves the reinforcement of the rubber composition and increases the diameter (D CPS ) can suppress the deterioration of low-loss properties due to the reduction in the distance between aggregates, thereby achieving excellent low-loss properties without reducing the reinforcement.

[0100] Here, the type of silica is not particularly limited, and includes, for example, wet silica, colloidal silica, calcium silicate, aluminum silicate, and the like.

[0101] In the above-mentioned silica, the silica is preferably wet silica, and in such wet silica, the silica is more preferably precipitated silica. This is because such silica has high dispersibility and can further improve the low loss and reinforcement of the rubber composition. Precipitated silica is a silica obtained by growing primary particles of silica in the early stage of manufacture as the reaction of the reaction solution is advanced at a relatively high temperature in a neutral to alkaline pH range, and then controlling the reaction solution on the acidic side to aggregate the primary particles.

[0102] From the viewpoint of achieving high reinforcing properties, the CTAB adsorption specific surface area (cetyltrimethylammonium bromide adsorption specific surface area) of silica needs to be 250 m 2 / g or more, and from a similar viewpoint, preferably 251m 2 / g or more, more preferably 252m 2 / g or more, and more preferably 253m 2 From the viewpoint of more reliably suppressing the deterioration of low-loss properties, the CTAB adsorption specific surface area of ​​silica is preferably 290 or less, more preferably 285 or less, further preferably 282 or less, and particularly preferably 270 or less.

[0103] The CTAB adsorption specific surface area means a value measured in accordance with ASTM D 3765-92. However, the CTAB adsorption specific surface area is obtained by setting the adsorption cross-sectional area of ​​hexadecyltrimethylammonium bromide per molecule on the silica surface to 0.35 nm. 2 , the specific surface area (m 2 / g).

[0104] The content of silica is not particularly limited and can be appropriately selected according to the desired performance. However, from the viewpoint that both reinforcement and low loss properties can be achieved at a higher level, the content of silica is preferably 5 to 50 parts by mass, more preferably 5 to 40 parts by mass, and further preferably 5 to 30 parts by mass relative to 100 parts by mass of the rubber component.

[0105] (Carbon Black)

[0106] The rubber composition of the present invention further comprises carbon black in addition to the above-mentioned rubber component and silica.

[0107] Here, carbon black is not particularly limited. For example, any hard carbon and soft carbon produced by an oil furnace method can be used. Among them, from the viewpoint of achieving more excellent low loss and reinforcement, it is preferred to use carbon black of GPF, FEF, SRF, HAF, ISAF, IISAF, or SAF grade.

[0108] The content of carbon black is preferably 20 to 60 parts by mass, more preferably 25 to 55 parts by mass, and particularly preferably 30 to 50 parts by mass relative to 100 parts by mass of the rubber component. Setting the content of carbon black to 20 parts by mass or more relative to 100 parts by mass of the rubber component can obtain high reinforcement, and setting the content of carbon black to 60 parts by mass or less can improve low loss properties.

[0109] Furthermore, in the rubber composition of the present invention, from the viewpoint that both reinforcement and low loss properties can be achieved at a higher level, the total content of carbon black and silica is preferably 40 to 100 parts by mass and more preferably 40 to 80 parts by mass relative to 100 parts by mass of the rubber component. Setting the total content of carbon black and silica to 40 parts by mass or more relative to 100 parts by mass of the rubber component can obtain more excellent reinforcement, and setting the total content of carbon black and silica to 100 parts by mass or less relative to 100 parts by mass of the rubber component can surely suppress the deterioration of low loss properties.

[0110] In the present invention, the ratio of the mass content of carbon black to the total mass content of carbon black and silica (mass content of carbon black / (mass content of carbon black + mass content of silica)) needs to be 70% or more, preferably 80% or more. This can surely improve the reinforcing property of the rubber composition of the present invention.

[0111] From the viewpoint of suppressing deterioration of low-loss properties, it is preferred that the mass content of carbon black is 95% or less relative to the total mass content of carbon black and silica.

[0112] Furthermore, in the rubber composition of the present invention, the nitrogen adsorption specific surface area (N 2 SA) is preferably 115m 2 / g or less, more preferably 110, further preferably 100 or less, further preferably 93m 2 / g or less, more preferably 83m 2 / g or less, more preferably 73m 2 / g or less, and particularly preferably 69m 2 This is because the use of silicon dioxide satisfying the conditions of the above formula (1) in combination can achieve both reinforcement and low loss properties at a higher level.

[0113] (Other components)

[0114] The rubber composition of the present invention may further include other components in addition to the above-mentioned rubber component, carbon black, and silica within a range not impairing the effects of the present invention.

[0115] Other components may suitably include additives commonly used in the rubber industry, such as fillers other than carbon black and silica, thermoplastic resins, antioxidants, crosslinking accelerators, crosslinking agents, crosslinking aids, antiozonants, and surfactants.

[0116] Fillers other than carbon black and silica include, for example, inorganic compounds represented by:

[0117] nM·xSiO Y ·zH 2 O(I)

[0118] [Wherein, M is at least one selected from the group consisting of metals selected from aluminum, magnesium, titanium, calcium and zirconium, oxides or hydroxides of these metals, hydrates thereof, and carbonates of these metals; and n, x, y and z are integers of 1 to 5, integers of 0 to 10, integers of 2 to 5, and integers of 0 to 10, respectively.]

[0119] The inorganic compound of formula (I) may include aluminum oxide (Al 2 O 3 ) such as γ-alumina and α-alumina; monohydrated alumina (Al 2 O 3 ·H 2 O) such as boehmite and diaspore; aluminum hydroxide [Al(OH) 3 ] such as gibbsite and bayerite; aluminum carbonate [Al 2 (CO 3 ) 3 ]、Magnesium hydroxide [Mg(OH) 2 ], magnesium oxide (MgO), magnesium carbonate (MgCO 3 )、Talc(3MgO·4SiO 2 ·H 2 O), attapulgite (5MgO·8SiO 2 9H 2 O), titanium dioxide (TiO 2 )、TiO 2n-1 ), calcium oxide (CaO), calcium hydroxide [Ca(OH) 2 ]、MgO·Al 2 O 3 ), clay (Al 2 O 3 ·2SiO 2 ), kaolin (Al 2 O 3 ·2SiO 2 ·2H 2 O), pyrophyllite (Al 2 O 3 ·4SiO 2 ·H 2 O), bentonite (Al 2 O 3 ·4SiO 2 ·2H 2 O), magnesium silicate (Mg 2 SiO 4 MgSiO 3 Calcium aluminum silicate (Al 2 O 3 ·CaO·2SiO 2etc.), calcium magnesium silicate (CaMgSiO 4 ), calcium carbonate (CaCO 3 ), zirconium oxide (ZrO 2 ), zirconium hydroxide [ZrO(OH) 2 ·nH 2 O], zirconium carbonate [Zr(CO 3 ) 2 ], hydrogen to correct the charge like various zeolites, crystalline aluminosilicates containing alkali metals or alkaline earth metals, etc.

[0120] It is preferable that the rubber composition of the present invention further includes a thermoplastic resin. When the rubber composition is used for a tire, the inclusion of a thermoplastic resin can further improve the low loss property and can also improve the braking performance.

[0121] In addition, the content of the thermoplastic resin is not particularly limited, but is preferably 5 to 50 parts by mass based on 100 parts by mass of the rubber component.

[0122] The type of thermoplastic resin is not particularly limited and includes, for example, C5-based resin, C9-based resin, C5-C9-based resin, dicyclopentadiene-based resin, rosin-based resin, alkylphenol-based resin, or terpenephenol-based resin.

[0123] Here, C5 series resin means C5 series synthetic petroleum resin, which is obtained by using AlCl 3 and BF 3 Solid polymers obtained by polymerizing a C5 fraction using a Friedel-Crafts catalyst such as cyclopentadiene, 1,3-pentadiene, and 1-pentene. Specifically, copolymers mainly composed of isoprene, cyclopentadiene, 1,3-pentadiene, and 1-pentene, copolymers of 2-pentene and dicyclopentadiene, and polymers mainly composed of 1,3-pentadiene are listed.

[0124] C9 series resin means C9 series synthetic petroleum resin, which is obtained by using AlCl 3 and BF 3 A solid polymer obtained by polymerizing a C9 fraction using a Friedel-Crafts catalyst such as . Specifically, copolymers mainly composed of indene, methylindene, α-methylstyrene, vinyltoluene, etc. are listed.

[0125] In addition, C5-C9 series resin means C5-C9 series synthetic petroleum resin, which is obtained by using AlCl 3 and BF 3A solid polymer obtained by polymerizing a C5-C9 fraction with a Friedel-Crafts catalyst such as styrene, vinyltoluene, α-methylstyrene, indene, etc. For example, it includes copolymers mainly composed of styrene, vinyltoluene, α-methylstyrene, indene, etc. In the present invention, as the C5-C9 resin, from the viewpoint of compatibility with the rubber component, a resin having a small amount of components above C9 is preferred. Here, "a small amount of components above C9" means that the components above C9 are less than 50% by mass in the total amount of the resin, and preferably 40% by mass or less.

[0126] The dicyclopentadiene resin refers to a petroleum resin using dicyclopentadiene in a C5 fraction as a main raw material, and includes, for example, product name "MARUKAREZ M" series (M-890A, M-845A, M-990A, etc.) from Maruzen Petrochemical Co., Ltd.

[0127] Rosin-based resins include gum rosin, tall oil rosin and wood rosin as natural resin rosins, which are contained in raw rosin or tall oil, and rosin derivatives and modified rosin derivatives as modified rosins, for example, polymerized rosin and partially hydrogenated rosin thereof; glycerol ester rosin and partially hydrogenated rosin and fully hydrogenated rosin thereof; pentaerythritol ester rosin and partially hydrogenated rosin and polymerized rosin thereof.

[0128] The alkylphenol-based resin means a phenol-based resin having an alkyl group, and includes, for example, an alkylphenol-acetylene resin such as p-tert-butylphenol-acetylene resin, and an alkylphenol formaldehyde resin having a low degree of polymerization.

[0129] In addition, the terpene-phenol resin is a resin that can be obtained by reacting terpenes and various phenols using a Friedel-Crafts catalyst or by further condensing them with formalin. The terpenes as a raw material are not particularly limited, but are preferably monoterpene hydrocarbons such as α-pinene and limonene, more preferably monoterpene hydrocarbons including α-pinene, and particularly preferably α-pinene. In the present invention, a terpene-phenol resin having a high ratio of a phenol component is preferred. One or more of these resins may be used together.

[0130] In addition, it is preferred that the rubber composition includes a novolac type phenolic resin as the phenolic resin. Including the novolac type phenolic resin can increase the elastic modulus in the rubber composition without using a curing agent and without reducing wet performance, thereby improving handling stability.

[0131] As the antioxidant, known antioxidants can be used, and the antioxidant is not particularly limited. It can include, for example, phenolic antioxidants, imidazole antioxidants, and amine antioxidants. One or more of these antioxidants can be used together.

[0132] As a crosslinking accelerator, a known crosslinking accelerator can be used, and the crosslinking accelerator is not particularly limited. It includes, for example, thiazole-based vulcanization accelerators such as 2-mercaptobenzothiazole and dibenzothiazole disulfide; sulfenamide-based vulcanization accelerators such as N-cyclohexyl-2-benzothiazole sulfenamide and N-tert-butyl-2-benzothiazole sulfenamide; guanidine-based vulcanization accelerators such as diphenylguanidine; thiuram-based vulcanization accelerators such as tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, tetrakis (dodecylthiuram), tetraoctylthiuram disulfide, tetrabenzylthiuram disulfide, and tetrapentamethylenethiuram tetrasulfide; dithiocarbamate-based vulcanization accelerators such as zinc dimethyldithiocarbamate; and zinc dialkyldithiophosphate. One or more of these crosslinking accelerators can be used together.

[0133] The crosslinking agent is also not particularly limited. It includes, for example, sulfur and bismaleimide compounds. One or more of these crosslinking agents can be used together.

[0134] The types of bismaleimide compounds can include, for example, N, N'-o-phenylene bismaleimide, N, N'-m-phenylene bismaleimide, N, N'-p-phenylene bismaleimide, N, N'-(4, 4'-diphenylmethane) bismaleimide, 2, 2-bis-[4-(4-maleimide phenoxy) phenyl] propane, and bis(3-ethyl-5-methyl-4-maleimide phenyl) methane. In the present invention, N, N'-m-phenylene bismaleimide and N, N'-(4, 4'-diphenylmethane) bismaleimide can be preferably used.

[0135] Crosslinking aids include, for example, zinc oxide (ZnO) and fatty acids. The fatty acid may be any of saturated or unsaturated, linear or branched fatty acids, and the number of carbon atoms of the fatty acid is not particularly limited, but the fatty acid includes, for example, fatty acids having 1 to 30 carbon atoms, preferably 15 to 30 carbon atoms, more specifically, cycloalkane acids, such as cyclohexane acid (cyclohexanecarboxylic acid) and alkylcyclopentanes having side chains; saturated fatty acids, such as caproic acid, octanoic acid, decanoic acid (including branched carboxylic acids such as neodecanoic acid), dodecanoic acid, tetradecanoic acid, hexadecanoic acid and octadecanoic acid (stearic acid); unsaturated fatty acids such as methacrylic acid, oleic acid, linoleic acid, and linolenic acid; and resin acids, such as rosin, tall oil acid and abietic acid. One of them may be used alone, or two or more of them may be used together. In the present invention, zinc oxide or stearic acid may be preferably used.

[0136] The method for producing the rubber composition of the present invention is not particularly limited, and the rubber composition can be obtained by compounding and kneading the respective components constituting the rubber composition (rubber component, silica, and other components).

[0137] <Tires>

[0138] The tire of the present invention uses the above-mentioned rubber composition. The tire obtained by using the rubber composition as a tire material can have excellent reinforcement and low loss properties.

[0139] In the tire of the present invention, specifically, the above-mentioned rubber composition is applied to any member, but among these tire members, it is particularly preferred that the rubber composition is applied to the tread. The tire using the rubber composition for the tread can achieve both reinforcement and low loss at a high level. The gas filling the tire of the present invention includes ordinary air or air with a changed oxygen partial pressure, or an inert gas such as nitrogen.

[0140] Example

[0141] The present invention is described in more detail below with reference to Examples, but the present invention is not limited to the following Examples in any way.

[0142] <Example 1 and Comparative Examples 1 to 3>

[0143] According to the compositions shown in Table 1, samples of the rubber compositions of Examples and Comparative Examples were produced by compounding and kneading in a conventional manner.

[0144] <Evaluation>

[0145] The following evaluations were performed on each sample of the rubber composition in Examples and Comparative Examples.

[0146] (1) Enhancement (dynamic storage modulus)

[0147] The rubber composition of each sample was vulcanized at 145°C for 33 minutes to obtain a vulcanized rubber. A sheet having a thickness of 2 mm, a width of 5 mm, and a length of 40 mm was cut out from the vulcanized rubber obtained as a sample. For this sample, a spectrometer (manufactured by Ueshima Seisakusho Co., Ltd.) was used to measure the dynamic storage modulus (E') at a temperature of 24°C, a strain of 5%, and a frequency of 52 Hz.

[0148] The obtained dynamic storage modulus (E') was expressed by an index when the value of Example 1 was 100. The larger the index value, the larger the dynamic storage modulus, indicating excellent reinforcement. The evaluation results are shown in Table 1.

[0149] (2) Low loss

[0150] The rubber composition of each sample was vulcanized at 160° C. for 15 minutes to obtain a vulcanized rubber. For the obtained vulcanized rubber, a spectrometer (manufactured by Ueshima Seisakusho Co., Ltd.) was used to measure the loss tangent (tan δ) at a temperature of 24° C., a dynamic strain of 1%, and a frequency of 52 Hz. The reciprocal of the difference between the tan δ of 3% strain and 0.1% strain was taken and indexed.

[0151] The evaluation was expressed by an index when the reciprocal of the difference in tan δ of the sample of Example 1 was 100. The larger the index value, the more excellent the low loss property. The evaluation results are shown in Table 1.

[0152] (3) Overall evaluation

[0153] The evaluation values ​​(index values) of the above-mentioned reinforcing property and low loss property are added together to calculate the total evaluation.

[0154] Regarding the total evaluation, a numerical value of 180 or more means that both reinforcement and low loss properties are achieved at a high level.

[0155] Table 1

[0156]

[0157] *0 Modified BR is manufactured under the following conditions

[0158] In a dry, nitrogen-substituted pressure-resistant glass container with a volume of 900 mL, 283 g of cyclohexane, 50 g of 1,3-butadiene monomer, 0.0057 mmol of 2,2-di(tetrahydrofuranyl)propane, and 0.513 mmol of hexamethyleneimine were injected as cyclohexane solutions, 0.57 mmol of n-butyl lithium (BuLi) was added thereto, and then polymerization was carried out in a 50°C hot water bath equipped with a stirring device for 4.5 hours. The polymerization conversion rate was almost 100%. 0.100 mmol of tin tetrachloride was added to the polymerization system as a cyclohexane solution and stirred at 50°C for 30 minutes. After that, 0.5 mL of a 5% by mass isopropanol solution of 2,6-di-tert-butyl-p-cresol (BHT) was further added to terminate the reaction, and it was dried according to a conventional method to obtain a modified BR. In the modified BR obtained, the vinyl bond content of the butadiene part was 14% and the coupling efficiency was 65%.

[0159] *1Asahi Kasei Corp. "Diene NF35R"

[0160] *2 "SEAST 7HM" manufactured by Tokai Carbon Co., Ltd.

[0161] *3 "Premium SW MP" manufactured by Solvay, CTAB adsorption specific surface area: 250m 2 / g, primary particle size (D I ): 10.91 nm, diameter of the aggregate morphology measured by disk centrifugation particle size analysis (D CPS ): 82nm, 6000 / CTAB / ρ=10.91, D CPS 3 / D I 3 :424.7

[0162] *4 "Nipsil AQ" manufactured by Tosoh Silica Corporation, CTAB adsorption specific surface area: 155 m 2 / g, primary particle size (D I ): 17.6 nm, diameter of the aggregate morphology measured by disk centrifugation particle size analysis (D CPS ): 76nm, 6000 / CTAB / ρ=17.60, D CPS 3 / D I 3 :80.4

[0163] ** For the diameter of silica aggregates (D CPS ) and primary particle size (D I ), silica was added to water at a ratio of 3 wt % and ultrasonically treated to obtain a silica suspension, and then, for this sample, the particle size distribution was measured using a disc centrifugal particle size distribution analyzer CPS Disc Centrifuge from CPS Instruments at a rotation speed of 20,000 rpm.

[0164] *5 "ABC-856" manufactured by Shin-Etsu Chemical Co., Ltd.

[0165] *9N-cyclohexyl-2-benzothiazolesulfenamide, manufactured by Ouchi Shinko Chemical Industrial Co., Ltd. (NOCCELER is a registered trademark in Japan, other countries, or both) CZ-G"

[0166] From the results in Table 1, it is found that the sample of Example 1 shows more excellent low loss property and dynamic storage modulus value and has a higher total value than the samples of the comparative examples.

[0167] Industrial Applicability

[0168] The present invention provides a rubber composition that has both high-level reinforcement and low-loss properties. The present invention also provides a tire that has both high-level reinforcement and low-loss properties.

Claims

1. A rubber composition comprising a rubber component, carbon black, and silica, wherein The CTAB adsorption specific surface area of ​​the silicon dioxide is 250 m 2 / g or more; The diameter (D) of the aggregate morphology of the silica measured by disk centrifuge particle size analysis CPS ) and primary particle size (D I )satisfy: 700≥D CPS 3 / D I 3 ≥300 (1); The rubber component comprises at least one selected from natural rubber and polyisoprene rubber, and at least one selected from modified butadiene rubber and modified styrene butadiene rubber; The mass content of the carbon black relative to the total mass content of the carbon black and the silicon dioxide is greater than 70%; The content of the carbon black is 20 to 60 parts by mass relative to 100 parts by mass of the rubber component; and The at least one selected from the group consisting of modified butadiene rubber and modified styrene butadiene rubber is modified by at least one selected from the group consisting of a hydrocarbyloxysilane compound represented by formula (IV), a hydrocarbyloxysilane compound represented by formula (V), a hydrocarbyloxysilane compound represented by formula (III), a coupling agent represented by formula (VI), a coupling agent represented by formula (VII), lithium amide represented by formula (VIII), and vinyl pyridine: in: q1+q2=3, wherein q1 is an integer from 0 to 2, and q2 is an integer from 1 to 3; R 31 represents a divalent aliphatic group or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms; R 32 and R 33 Each independently represents a hydrolyzable group, a monovalent aliphatic group or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms; R 34 represents a monovalent aliphatic group or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, when q1 is 2, R 34 may be the same or different; and R 35 represents a monovalent aliphatic group or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when q2 is 2 or more, R 35 Can be the same or different; Where: r1+r2=3, wherein r1 is an integer from 1 to 3, and r2 is an integer from 0 to 2; R 36 represents a divalent aliphatic group or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms; R 37 represents dimethylaminomethyl, dimethylaminoethyl, diethylaminomethyl, diethylaminoethyl, methylsilyl(methyl)aminomethyl, methylsilyl(methyl)aminoethyl, methylsilyl(ethyl)aminomethyl, methylsilyl(ethyl)aminoethyl, dimethylsilylaminomethyl, dimethylsilylaminoethyl, a monovalent aliphatic group or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when r1 is 2 or more, R 37 may be the same or different; and R 38 represents a hydrocarbon group having 1 to 20 carbon atoms, a monovalent aliphatic group or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when r2 is 2, R 38 Can be the same or different; Among them: A 1 represents a monovalent group having at least one functional group selected from epoxy, thioepoxy, isocyanate, thioisocyanate, ketone, thioketone, aldehyde, thioaldehyde, imine, amide, trialkyl isocyanurate, carboxylate, thiocarboxylate, metal salt of carboxylic acid, metal salt of thiocarboxylic acid, carboxylic anhydride, carboxylic acid halide, and dialkyl carbonate; R 1 Represents a single bond or a divalent inactive hydrocarbon group; R 2 and R 3 Each independently represents a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms; n is an integer of 0 to 2; when there are multiple R 2 When R 2 Can be the same or different. When there are multiple OR 3 When, OR 3 can be the same or different and contain no active protons and onium salts in the molecule; Where: R 12 , R 13 , and R 14 Each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms; R 15 , R 16 , R 17 , R 18 , and R 20 Each independently represents an alkyl group having 1 to 20 carbon atoms; R 19 and R 22 Each independently represents an alkylene group having 1 to 20 carbon atoms; R 21 represents an alkyl group or trialkylsilyl group having 1 to 20 carbon atoms; m represents an integer of 1 to 3; p represents 1 or 2; when there are multiple R 12 ~R 22 , m and p, they are independent of each other; i, j, and k each independently represent an integer of 0 to 6, wherein (i+j+k) is an integer of 3 to 10; and A represents a hydrocarbon group or an organic group having 1 to 20 carbon atoms, the organic group having at least one atom selected from the group consisting of oxygen atoms, nitrogen atoms, silicon atoms, sulfur atoms, and phosphorus atoms and having no active hydrogen; (R3) a ZX b …(VII) wherein: Z represents tin or silicon; (R3) is selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms; X represents chlorine or bromine; a is 0 to 3, b is 1 to 4, wherein a+b=4; (AM)Li(Q) y …(VIII) Wherein: y is 0 or 0.5 to 3; (Q) is a solubilizing component selected from hydrocarbons, ethers, amines, and mixtures thereof; and (AM) is the general formula [I]: wherein R1 independently represents an alkyl group, a cycloalkyl group, or an aralkyl group having 1 to 12 carbon atoms, Or general formula [II]: Wherein (R2) represents: an alkylene group having 3 to 16 methylene groups; a substituted alkylene group having a straight chain or branched alkyl group, cycloalkyl group, bicycloalkyl group, aryl group, or aralkyl group having 1 to 12 carbon atoms as a substituent; an oxydiethylene group; or an N-alkylamino-alkylene group.

2. The rubber composition according to claim 1, wherein the at least one selected from the group consisting of modified butadiene rubber and modified styrene butadiene rubber is modified by at least one selected from the group consisting of: N,N-bis(trimethylsilyl)-3-[diethoxy(methyl)silyl]propylamine; N-(1,3-dimethylbutylene)-3-triethoxysilyl-1-propylamine; 3-glycidoxypropyltrimethoxysilane; tetrakis(3-trimethoxysilylpropyl)-1,3-propylenediamine; tin tetrachloride; a reactant of hexamethyleneimine and n-butyllithium; 4-vinylpyridine; and 2-vinylpyridine. 3 . The rubber composition according to claim 1 , wherein the total content of the carbon black and the silica is 40 to 100 parts by mass relative to 100 parts by mass of the rubber component.

4. A tire comprising the rubber composition according to any one of claims 1 to 3.

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