JP5324384B2 - POLYMER, TIRE RUBBER COMPOSITION AND PNEUMATIC TIRE - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer capable of achieving both of a low fuel cost and wet grip performance, to provide a rubber composition for a tire, using the polymer, and to provide the pneumatic tire using the rubber composition for the tire as each member (especially tread) of the tire. <P>SOLUTION: The polymer is obtained by polymerizing a conjugated diene compound, or the conjugated diene compound and an aromatic vinyl compound by using a polymerization initiator obtained by reacting a lithium amide compound represented by general formula (I) with a silane compound represented by general formula (II) (wherein R<SP>1</SP>and R<SP>2</SP>are each independently 1-18C monovalent hydrocarbon which may have substituent amino or ether, or R<SP>1</SP>and R<SP>2</SP>may form a ring structure by bonding to each other; R<SP>3</SP>is 3-9C divalent hydrocarbon; and R<SP>4</SP>and R<SP>5</SP>are each independently 1-18C monovalent hydrocarbon). <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

The present invention relates to a polymer, a tire rubber composition using the polymer, and a pneumatic tire using the tire rubber composition.

In recent years, social demands for reducing carbon dioxide emissions have been increasing from the standpoints of resource and energy conservation and environmental protection. For this reason, automobiles are also required to improve fuel efficiency by improving tire rolling resistance with the aim of reducing carbon dioxide emissions, and further demands for improved driving safety (steering stability). Is also getting stronger. The tire characteristics depend on various factors such as the tire structure and materials used, but the performance of the rubber composition used for the tread part in contact with the road surface contributes to the tire characteristics such as low fuel consumption, safety, and durability. Is big. For this reason, many technical improvements of rubber for tire treads have been studied, proposed, and put into practical use.

In order to improve the performance, improvement of the formulation has been studied, and a formulation having a low hysteresis loss (good fuel economy) and high wet skid resistance (good wet grip performance) has been studied. However, the relationship between low hysteresis loss and high wet skid resistance is a contradiction, and it is difficult to achieve both.

Patent Document 1 discloses that low fuel consumption and wear resistance are improved by blending butadiene rubber modified with an aminosilane compound. However, there is still room for improvement in terms of both low fuel consumption and wet grip performance.

JP 2008-214608 A

The present invention solves the above-mentioned problems, a polymer capable of achieving both low fuel consumption and wet grip performance, a tire rubber composition using the polymer, and the tire rubber composition using the tire components (particularly, An object of the present invention is to provide a pneumatic tire used for a tread.

As a result of intensive studies to solve the above problems, the present inventor has found that the problems can be solved by the following method.
That is, the present invention uses a polymerization initiator obtained by reacting a lithium amide compound represented by the following general formula (I) and a silane compound represented by the following general formula (II), to provide a conjugated diene compound or a conjugated compound. The present invention relates to a polymer obtained by polymerizing a diene compound and an aromatic vinyl compound.

（Ｒ^１およびＲ^２は、それぞれ独立して炭素数１〜１８の一価の炭化水素基であり、該一価の炭化水素基は置換アミノ基またはエーテル基を有していてもよく、また、Ｒ^１及びＲ^２は互いに結合して環構造を形成してもよい。Ｒ^３は炭素数３〜９の二価の炭化水素基、Ｒ^４およびＲ^５はそれぞれ独立して炭素数１〜１８の一価の炭化水素基を示す。）

(R ¹ and R ² are each independently a monovalent hydrocarbon group having 1 to 18 carbon atoms, and the monovalent hydrocarbon group may have a substituted amino group or an ether group, , R ¹ and R ² may be bonded to each other to form a ring structure, R ³ is a divalent hydrocarbon group having 3 to 9 carbon atoms, and R ⁴ and R ⁵ are each independently 1 to 1 carbon atoms. 18 represents a monovalent hydrocarbon group.)

Moreover, it is preferable that the said polymer has modified | denatured with the compound which has the functional group containing the at least 1 sort (s) of atom selected from the group which the stop terminal of the said polymer consists of nitrogen, oxygen, and silicon.

The conjugated diene compound is preferably 1,3-butadiene or isoprene, and the aromatic vinyl compound is preferably styrene.

The present invention also relates to a tire rubber composition in which the content of the polymer in 100% by mass of the rubber component is 5% by mass or more.

The present invention also relates to a pneumatic tire produced using the tire rubber composition.

According to the present invention, using a polymerization initiator obtained by reacting the lithium amide compound represented by the general formula (I) and the silane compound represented by the general formula (II), a conjugated diene compound or Since it is a polymer obtained by polymerizing a conjugated diene compound and an aromatic vinyl compound, that is, a polymer containing a specific aminosilane structure, both low fuel consumption and wet grip performance can be achieved. Therefore, the rubber composition for tires using the polymer can be suitably applied to each member (particularly, tread) of the tire and can provide a tire having both low fuel consumption and wet grip performance.

(Polymer)
The polymer of the present invention is a conjugated diene compound using a polymerization initiator obtained by reacting a lithium amide compound represented by the above general formula (I) and a silane compound represented by the above general formula (II). Alternatively, it is a polymer obtained by polymerizing a conjugated diene compound and an aromatic vinyl compound.

In the general formula (I), R ¹ and R ² are each independently a monovalent hydrocarbon group having 1 to 18 carbon atoms, and the monovalent hydrocarbon group is a substituted amino group or an ether group. R ¹ and R ² may be bonded to each other to form a ring structure.

Examples of the monovalent hydrocarbon group having 1 to 18 carbon atoms include alkyl having 1 to 18 carbon atoms (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and further preferably 1 to 5 carbon atoms). Group, 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, and the like. Among these, the above alkyl group is preferable because of its availability.

The alkyl group and alkenyl group may be linear, branched or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, cyclopentyl group, cyclohexyl group, vinyl group, propenyl group, allyl group, hexenyl group, octenyl group, cyclopentenyl group Group, cyclohexenyl group and the like. Among the alkyl groups and alkenyl groups, an isopropyl group is more preferable because of availability.

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, and a naphthyl group.

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, and a naphthylmethyl group.

The hydrocarbon group may have a substituted amino group or an ether group, or may have all of them.

R ¹ and R ² may be bonded to each other to form a ring structure together with the nitrogen atom in the general formula (I). This ring structure may be a saturated or unsaturated hydrocarbon ring structure, or a saturated or unsaturated heterocyclic structure containing an oxygen atom (having an ether group).
Among these, from the viewpoint of easy availability, the ring is preferably a 4-membered ring to a 10-membered ring, and more preferably a 4-membered ring to an 8-membered ring.

Examples of the lithium amide compound represented by the general formula (I) include lithium dimethylamide, lithium methyl (ethyl) amide, lithium methyl (isopropyl) amide, lithium methyl (n-butyl) amide, lithium methyl (sec-butyl). ) Amide, lithium methyl (tert-butyl) amide, lithium methyl (pentyl) amide, lithium diethylamide, lithium ethyl (isopropyl) amide, lithium ethyl (n-butyl) amide, lithium ethyl (sec-butyl) amide, lithium ethyl ( tert-butyl) amide, lithium ethyl (pentyl) amide, lithium diisopropylamide, lithium isopropyl (n-butyl) amide, lithium isopropyl (sec-butyl) amide, lithium isopropyl (te t-butyl) amide, lithium isopropyl (pentyl) amide, lithium azetidine-1-id, lithium pyrrolidine-1-id, lithium piperidine-1-id, lithium azepan-1-id, lithium azocan-1-id Lithium 2-methylpyrrolidine-1-id, lithium 3-methylpyrrolidine-1-id, lithium 2-ethylpyrrolidine-1-id, lithium 2-methylpiperidine-1-id, lithium 3-methylpiperidine-1-id Lithium 4-methylpiperidine-1-id, lithium 3,5-dimethylpiperidine-1-id, lithium 2-methylpiperidine-1-id, lithium 1,3-oxazinane-3-id, lithium morpholine-4-id Lithium 1-methyltetrahydro-1H-pyrimidine-3-id, Um 4-methylpiperazin-1-Id, and the like. Of these, lithium diisopropylamide, lithium pyrrolidine-1-id, lithium azepan-1-id, and lithium morpholine-4-id are preferable.

In the general formula (II), R ³ represents a divalent hydrocarbon group having 3 to 9 carbon atoms, and R ⁴ and R ⁵ each independently represents a monovalent hydrocarbon group having 1 to 18 carbon atoms.

Examples of the divalent hydrocarbon group having 3 to 9 carbon atoms of R ³ include an alkylene group having 3 to 9 carbon atoms (preferably 3 to 7 carbon atoms, more preferably 3 carbon atoms), and 3 to 9 carbon atoms. An alkynylene group can be exemplified. Especially, the said alkylene group is preferable from the reason of availability and reactivity.

The alkylene group and alkynylene group may be linear, branched or cyclic, and examples thereof include n-propylene group, isopropylene group, n-butylene group, isobutylene group, sec-butylene group, tert-butylene group, pentylene group, hexylene group, octylene group, decylene group, dodecylene group, cyclopentylene group, cyclohexylene group, propenylene group, hexenylene group, octenylene group, cyclopentenylene group, cyclohexenylene group Etc. Among the alkylene groups and alkynylene groups, a straight chain is preferable because of availability and reactivity, and an n-propylene group and an n-butylene group are more preferable.

Examples of the monovalent hydrocarbon group having 1 to 18 carbon atoms of R ⁴ and R ⁵ include the same groups as R ¹ and R ² . Among these, for reasons of availability and reactivity, the number of carbon atoms is 1 to 18 (preferably 1 to 12 carbons, more preferably 1 to 8 carbons, still more preferably 1 to 5 carbons, and particularly preferably the number of carbons. 1-3) are preferred.

Examples of the silane compound represented by the general formula (II) include 1,1-dimethyl-1-silacyclopropane, 1-methyl-1-ethyl-1-silacyclopropane, 1,1-diethyl-1- Silacyclopropane, 1,1-dimethyl-1-silacyclobutane, 1-methyl-1-ethyl-1-silacyclobutane, 1,1-diethyl-1-silacyclobutane, 1,1-dimethyl-1-silacyclopentane 1-methyl-1-ethyl-1-silacyclopentane, 1,1-diethyl-1-silacyclopentane, 1,1-dimethyl-1-silacyclohexane, 1-methyl-1-ethyl-1-silacyclohexane 1,1-diethyl-1-silacyclohexane, 1,1-dimethyl-1-silacycloheptane, 1-methyl-1-ethyl-1-silacycloheptane Such as 1,1-di-1-sila-cycloheptane and the like. Of these, 1,1-dimethyl-1-silacyclobutane and 1-methyl-1-ethyl-1-silacyclopropane are preferable.

The method for preparing the polymerization initiator used in the present invention is not particularly limited as long as it is a method of contacting the lithium amide compound and the silane compound.
By bringing the lithium amide compound and the silane compound into contact with each other, a reaction represented by the following formula (III) proceeds to obtain a polymerization initiator containing a specific aminosilane structure. Since the polymerization initiator has such a structure, it is possible to obtain a modified polymer in which an amino group and a silyl group are introduced at the start terminal.

The method for preparing the polymerization initiator used in the present invention includes, for example, an organic solvent inert to the reaction, for example, a hydrocarbon solvent such as an aliphatic, alicyclic or aromatic hydrocarbon compound, the lithium amide compound, the silane A polymerization initiator can be prepared by dissolving each compound separately and dropping the lithium amide compound solution dropwise into the silane compound solution with stirring. In addition, -20-50 degreeC is preferable for the reaction temperature at the time of preparing a polymerization initiator.

The hydrocarbon solvent is preferably one having 3 to 8 carbon atoms, for example, propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, cyclohexane, propene, 1-butene, isobutene, trans-2- Examples include butene, cis-2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, benzene, toluene, xylene, and ethylbenzene. These may be used alone or in combination of two or more.

The molar ratio of the lithium amide compound to the silane compound (lithium amide compound / silane compound) in preparing the polymerization initiator is preferably 0.8 to 1.1, more preferably 0.9 to 1.05.

Examples of the conjugated diene compound used in the present invention include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 2-phenyl-1,3-butadiene, and 1,3-hexadiene. Can be mentioned. These may be used alone or in combination of two or more. Among these, 1,3-butadiene and isoprene are particularly preferable from the viewpoint of practicality such as availability of monomers. preferable.

Examples of the aromatic vinyl compound used in the present invention include styrene, α-methylstyrene, 1-vinylnaphthalene, 3-vinyltoluene, ethylvinylbenzene, divinylbenzene, 4-cyclohexylstyrene, 2,4,6-trimethylstyrene. Etc. These may be used singly or in combination of two or more. Among these, styrene is particularly preferable from the viewpoint of practicality such as availability of monomers. A conjugated diene compound and an aromatic vinyl compound may be used in combination.

As a method for producing the polymer of the present invention, as a polymerization initiator, polymerization obtained by reacting a lithium amide compound represented by the above general formula (I) with a silane compound represented by the above general formula (II) There is no restriction | limiting in particular except using an initiator, A conventionally well-known method can be used. During the polymerization reaction, a polymer having Li at the polymerization terminal represented by the following formula (IV) is generated.

Specifically, the method for producing a polymer of the present invention includes a conjugated diene compound or a conjugated compound in an organic solvent inert to the reaction, for example, a hydrocarbon solvent such as an aliphatic, alicyclic or aromatic hydrocarbon compound. A target polymer is obtained by polymerizing a diene compound and an aromatic vinyl compound using the above polymerization initiator in the presence of a randomizer as necessary.

As the hydrocarbon solvent, the same solvents as those used in the preparation of the polymerization initiator can be suitably used.

The randomizer is a microstructure control of a conjugated diene moiety in a polymer, for example, an increase in 1,2-bond in butadiene, an increase in 3,4-bond in isoprene, or a composition distribution of monomer units in the polymer. It is a compound having control, for example, randomization of butadiene units and styrene units in a butadiene-styrene copolymer.

There is no restriction | limiting in particular as a randomizer, Arbitrary things can be used from the well-known compound generally used as a conventional randomizer. For example, dimethoxybenzene, tetrahydrofuran, dimethoxyethane, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, bistetrahydrofurylpropane, triethylamine, pyridine, N-methylmorpholine, N, N, N ′, N′-tetramethylethylenediamine, 1,2-di Examples include ethers such as piperidinoethane and tertiary amines. Further, potassium salts such as potassium-t-amylate and potassium-t-butoxide, and sodium salts such as sodium-t-amylate can also be used. These randomizers may be used individually by 1 type, and may be used in combination of 2 or more type. Among these, tetrahydrofuran and N, N, N ′, N′-tetramethylethylenediamine are preferable because of easy availability.

The amount of randomizer used is preferably 0.01 mol or more and more preferably 0.05 mol or more with respect to 1 mol of the organolithium compound (polymerization initiator represented by the formula (III)). When the amount of the randomizer used is less than 0.01 mol, the effect of addition is small and it tends to be difficult to randomize. The amount of randomizer used is preferably 1000 mol or less, more preferably 500 mol or less, per 1 mol of the organolithium compound (polymerization initiator represented by formula (III)). When the amount of the randomizer used exceeds 1000 mol, the reaction rate of the monomer changes greatly, and conversely, it tends to be difficult to randomize.

A functional group may or may not be introduced at the terminating end of the polymer in the present invention. Among these, it is preferable to introduce a functional group for the purpose of improving the balance between the low fuel consumption of the rubber composition and the wet grip performance. When no functional group is introduced, for example, a polymerization terminator such as alcohol may be added to terminate the polymerization reaction. On the other hand, when introducing a functional group, for example, the polymerization end of the polymer represented by the above formula (IV) may be reacted with a modifier having a functional group to terminate the polymerization reaction.

As a method for modifying a polymer with a modifier, conventionally known methods such as those described in JP-B-6-53768 and JP-B-6-57767 can be used. For example, a polymer and a modifier may be brought into contact with each other, and a method in which a modifier is added to the prepared polymer solution to cause a reaction may be mentioned.

The modifier for introducing a functional group at the terminal end of the polymer is preferably a compound having a functional group containing at least one atom selected from the group consisting of nitrogen, oxygen, and silicon.
Examples of the functional group include amino group, amide group, alkoxysilyl group, isocyanate group, imino group, imidazole group, urea group, ether group, carbonyl group, carboxyl group, hydroxyl group, nitrile group, pyridyl group and the like. These functional groups may have a substituent. Among these, an amino group, an alkoxysilyl group, an ether group, a carbonyl group, a hydroxyl group, and a carboxyl group are preferable because the balance between the low fuel consumption and wet grip performance of the rubber composition is improved.

Examples of the modifier include 3-glycidoxypropyltrimethoxysilane, (3-triethoxysilylpropyl) tetrasulfide, 1- (4-N, N-dimethylaminophenyl) -1-phenylethylene, 1,1- Dimethoxytrimethylamine, 1,2-bis (trichlorosilyl) ethane, 1,3,5-tris (3-triethoxysilylpropyl) isocyanurate, 1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate, 1,3-dimethyl-2-imidazolidinone, 1,3-propanediamine, 1,4-diaminobutane, 1- [3- (triethoxysilyl) propyl] -4,5-dihydroimidazole, 1-glycidyl- 4- (2-pyridyl) piperazine, 1-glycidyl-4-phenylpiperazine, 1-glycidyl 4-methylpiperazine, 1-glycidyl-4-methylhomopiperazine, 1-glycidylhexamethyleneimine, 11-aminoundecyltriethoxysilane, 11-aminoundecyltrimethoxysilane, 1-benzyl-4-glycidylpiperazine, 2 -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (4-morpholinodithio) benzothiazole, 2- (6-aminoethyl) -3-aminopropyltrimethoxysilane, 2- (triethoxysilylethyl) ) Pyridine, 2- (trimethoxysilylethyl) pyridine, 2- (2-pyridylethyl) thiopropyltrimethoxysilane, 2- (4-pyridylethyl) thiopropyltrimethoxysilane, 2,2-diethoxy-1,6 -Diaza-2-silacyclooctane, 2, -Dimethoxy-1,6-diaza-2-silacyclooctane, 2,3-dichloro-1,4-naphthoquinone, 2,4-dinitrobenzenesulfonyl chloride, 2,4-tolylene diisocyanate, 2- (4- Pyridylethyl) triethoxysilane, 2- (4-pyridylethyl) trimethoxysilane, 2-cyanoethyltriethoxysilane, 2-tributylstannyl-1,3-butadiene, 2- (trimethoxysilylethyl) pyridine, 2- Vinylpyridine, 2- (4-pyridylethyl) triethoxysilane, 2- (4-pyridylethyl) trimethoxysilane, 2-laurylthioethylphenylketone, 3- (1-hexamethyleneimino) propyl (triethoxy) silane, 3- (1,3-Dimethylbutylidene) aminopropyltriethoxysila 3- (1,3-dimethylbutylidene) aminopropyltrimethoxysilane, 3- (2-aminoethylaminopropyl) trimethoxysilane, 3- (m-aminophenoxy) propyltrimethoxysilane, 3- (N , N-dimethylamino) propyltriethoxysilane, 3- (N, N-dimethylamino) propyltrimethoxysilane, 3- (N-methylamino) propyltriethoxysilane, 3- (N-methylamino) propyltrimethoxy Silane, 3- (N-allylamino) propyltrimethoxysilane, 3,4-diaminobenzoic acid, 3-aminopropyldimethylethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyl Tris (methoxydiethoxy) silane, 3-amino Lopyldiisopropylethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-diethylaminopropyltrimethoxy Silane, 3-diethoxy (methyl) silylpropyl succinic anhydride, 3- (N, N-diethylaminopropyl) triethoxysilane, 3- (N, N-diethylaminopropyl) trimethoxysilane, 3- (N, N-dimethyl) Aminopropyl) diethoxymethylsilane, 3- (N, N-dimethylaminopropyl) triethoxysilane, 3- (N, N-dimethylaminopropyl) trimethoxysilane, 3-triethoxysilylpropyl succinic anhydride, 3- Trier Xylsilylpropylacetic anhydride, 3-triphenoxysilylpropyl succinic anhydride, 3-triphenoxysilylpropyl acetic anhydride, 3-trimethoxysilylpropylbenzothiazole tetrasulfide, 3-hexamethyleneiminopropyltriethoxysilane, 3-mercaptopropyl Trimethoxysilane, (3-triethoxysilylpropyl) diethylenetriamine, (3-trimethoxysilylpropyl) diethylenetriamine, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4′- (Imidazol-1-yl) -acetophenone, 4- [3- (N, N-diglycidylamino) propyl] morpholine, 4-glycidyl-2,2,6,6-tetramethylpiperidinyloxy, 4-aminobutyl Tiltlyethoxysilane, 4-vinylpyridine, 4-morpholinoacetophenone, 4-morpholinobenzophenone, m-aminophenyltrimethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1- Propanamine, N- (1,3-dimethylbutylidene) -3- (trimethoxysilyl) -1-propanamine, N- (1-methylethylidene) -3- (triethoxysilyl) -1-propanamine, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxy Silane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-amino Ethyl) -11-aminoundecyltriethoxysilane, N- (2-aminoethyl) -11-aminoundecyltrimethoxysilane, N- (2-aminoethyl) -3-aminoisobutylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminoisobutylmethyldimethoxysilane, N- (3-diethoxymethylsilylpropyl) succinimide, N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole, N- (3 -Triethoxysilylpropyl) pyrrole, N- (3-trimethoxysilylpropyl) pyrrole, N-3- [amino (polypropyleneoxy)] aminopropyltrimethoxysilane, N- [5- (triethoxysilyl) -2- Aza-1-oxopentyl] caprolactam, N- [5- (trimethoxy Ryl) -2-aza-1-oxopentyl] caprolactam, N- (6-aminohexyl) aminomethyltriethoxysilane, N- (6-aminohexyl) aminomethyltrimethoxysilane, N-allyl-aza-2, 2-diethoxysilacyclopentane, N-allyl-aza-2,2-dimethoxysilacyclopentane, N- (cyclohexylthio) phthalimide, Nn-butyl-aza-2,2-diethoxysilacyclopentane, N -N-butyl-aza-2,2-dimethoxysilacyclopentane, N, N, N ', N'-tetraethylaminobenzophenone, N, N, N', N'-tetramethylthiourea, N, N, N ' , N′-tetramethylurea, N, N′-ethyleneurea, N, N′-diethylaminobenzophenone, N, N′-diethylaminobenzophenone N, N′-diethylaminobenzofuran, methyl N, N′-diethylcarbamate, N, N′-diethylurea, (N, N-diethyl-3-aminopropyl) triethoxysilane, (N, N-diethyl- 3-aminopropyl) trimethoxysilane, N, N-dioctyl-N′-triethoxysilylpropylurea, N, N-dioctyl-N′-trimethoxysilylpropylurea, methyl N, N-diethylcarbamate, N, N-diglycidylcyclohexylamine, N, N-dimethyl-o-toluidine, N, N-dimethylaminostyrene, N, N-diethylaminopropylacrylamide, N, N-dimethylaminopropylacrylamide, N-ethylaminoisobutyltriethoxysilane N-ethylaminoisobutyltrimethoxysilane, N Ethylaminoisobutylmethyldiethoxysilane, N-oxydiethylene-2-benzothiazolesulfenamide, N-cyclohexylaminopropyltriethoxysilane, N-cyclohexylaminopropyltrimethoxysilane, N-methylaminopropylmethyldimethoxysilane, N- Methylaminopropylmethyldiethoxysilane, N-vinylbenzylazacycloheptane, N-phenylpyrrolidone, N-phenylaminopropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-phenylaminomethyltriethoxysilane, N- Phenylaminomethyltrimethoxysilane, n-butylaminopropyltriethoxysilane, n-butylaminopropyltrimethoxysilane, N-methylaminopropyltrie Toxisilane, N-methylaminopropyltrimethoxysilane, N-methyl-2-piperidone, N-methyl-2-pyrrolidone, N-methyl-ε-caprolactam, N-methylindolinone, N-methylpyrrolidone, p- (2 -Dimethylaminoethyl) styrene, p-aminophenyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, (aminoethylamino) -3-isobutyldiethoxysilane, (aminoethyl) Amino) -3-isobutyldimethoxysilane, (aminoethylaminomethyl) phenethyltriethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, acrylic acid, diethyl adipate, acetamidopropyltrimethoxysilane, aminophen Nyltrimethoxysilane, aminobenzophenone, ureidopropyltriethoxysilane, ureidopropyltrimethoxysilane, ethylene oxide, octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride, glycidoxypropyltriethoxysilane, glycidoxypropyltrimethoxysilane , Glycerol tristearate, chlorotriethoxysilane, chloropropyltriethoxysilane, chloropolydimethylsiloxane, chloromethyldiphenoxysilane, diallyldiphenyltin, diethylaminomethyltriethoxysilane, diethylaminomethyltrimethoxysilane, diethyl (glycidyl) amine, diethyl , Dithiocarbamic acid 2-benzothiazoyl ester, diethoxydichlorosilane, ( (Cyclohexylaminomethyl) triethoxysilane, (cyclohexylaminomethyl) trimethoxysilane, diglycidylpolysiloxane, dichlorodiphenoxysilane, dicyclohexylcarbodiimide, divinylbenzene, diphenylcarbodiimide, diphenylcyanamide, diphenylmethane diisocyanate, diphenoxymethylchlorosilane, dibutyldichloro Tin, dimethyl (acetoxy-methylsiloxane) polydimethylsiloxane, dimethylaminomethyltriethoxysilane, dimethylaminomethyltrimethoxysilane, dimethyl (methoxy-methylsiloxane) polydimethylsiloxane, dimethylimidazolidinone, dimethylethyleneurea, dimethyldichlorosilane , Dimethylsulfoyl chloride, silsesquioxane Sorbitan trioleate, sorbitan monolaurate, titanium tetrakis (2-ethylhexoxide), tetraethoxysilane, tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraphenoxysilane, tetramethylthiuram disulfide, tetramethoxy Silane, triethoxyvinylsilane, tris (3-trimethoxysilylpropyl) cyanurate, triphenyl phosphate, triphenoxychlorosilane, triphenoxymethylsilicon, triphenoxymethylsilane, carbon dioxide, bis (triethoxysilylpropyl) amine, bis (tri Methoxysilylpropyl) amine, bis [3- (triethoxysilyl) propyl] ethylenediamine, bis [3- (trimethoxysilyl) propyl] Range amine, bis [3- (triethoxysilyl) propyl] urea, bis [(trimethoxysilyl) propyl] urea, bis (2-hydroxymethyl) -3-aminopropyltriethoxysilane, bis (2-hydroxymethyl) -3-aminopropyltrimethoxysilane, bis (2-ethylhexanoate) tin, bis (2-methylbutoxy) methylchlorosilane, bis (3-triethoxysilylpropyl) tetrasulfide, bisdiethylaminobenzophenone, bisphenol A diglycidyl Ether, bisphenoxyethanol fluorenediglycidyl ether, bis (methyldiethoxysilylpropyl) amine, bis (methyldimethoxysilylpropyl) -N-methylamine, hydroxymethyltriethoxysilane, vinyltri (2-ethylhexyloxy) silane, vinylbenzyldiethylamine, vinylbenzyldimethylamine, vinylbenzyltributyltin, vinylbenzylpiperidine, vinylbenzylpyrrolidine, pyrrolidine, phenyl isocyanate, phenylisothiocyanate, (phenylaminomethyl) methyldimethoxysilane, ( Phenylaminomethyl) methyldiethoxysilane, phthalic acid amide, hexamethylene diisocyanate, benzylidene aniline, polydiphenylmethane diisocyanate, polydimethylsiloxane, methyl-4-pyridyl ketone, methylcaprolactam, methyltriethoxysilane, methyltriphenoxysilane, Examples include methyl lauryl thiopropionate and silicon tetrachloride.

Among the above modifiers, the compounds represented by the following general formulas (V) to (VII) are preferable because the balance between the low fuel consumption and the wet grip performance of the rubber composition is improved.

（式中、Ｒ^６、Ｒ^７及びＲ^８は、同一若しくは異なって、アルキル基、アルコキシ基、シリルオキシ基、アセタール基、カルボキシル基、メルカプト基又はこれらの誘導体を表す。Ｒ^９及びＲ^１０は、同一若しくは異なって、水素原子、またはアルキル基を表す。ｒは整数を表す。）

(Wherein R ⁶ , R ⁷ and R ⁸ are the same or different and each represents an alkyl group, an alkoxy group, a silyloxy group, an acetal group, a carboxyl group, a mercapto group, or a derivative thereof. R ⁹ and R ¹⁰ are (The same or different, and represents a hydrogen atom or an alkyl group. R represents an integer.)

（式中、Ｒ^１１、Ｒ^１２及びＲ^１３は、同一若しくは異なって、アルキル基、アルコキシ基、シリルオキシ基、アセタール基、カルボキシル基、メルカプト基又はこれらの誘導体を表す。Ｒ^１４は、環状エーテル基を表す。ｐ及びｑは整数を表す。）

(Wherein R ¹¹ , R ¹² and R ¹³ are the same or different and each represents an alkyl group, an alkoxy group, a silyloxy group, an acetal group, a carboxyl group, a mercapto group or a derivative thereof. R ¹⁴ is a cyclic ether group. P and q represent integers.

（式中、Ｒ^１５、Ｒ^１６及びＲ^１７は、同一若しくは異なって、アルキル基、アルコキシ基、シリルオキシ基、アセタール基、カルボキシル基、メルカプト基又はこれらの誘導体を表す。ｓは整数を表す。）

(Wherein R ¹⁵ , R ¹⁶ and R ¹⁷ are the same or different and each represents an alkyl group, an alkoxy group, a silyloxy group, an acetal group, a carboxyl group, a mercapto group, or a derivative thereof. S represents an integer.)

In the compound represented by the formula (V), R ⁶ , R ⁷ and R ⁸ are the same or different and are an alkyl group, an alkoxy group, a silyloxy group, an acetal group, a carboxyl group (—COOH), a mercapto group (— SH) or derivatives thereof. Examples of the alkyl group include an alkyl group having 1 to 4 carbon atoms (preferably having 1 to 3 carbon atoms) such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a t-butyl group. Etc. Examples of the alkoxy group include alkoxy groups having 1 to 8 carbon atoms such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group and t-butoxy group (preferably having 1 to 6 carbon atoms). More preferably, C1-C4) etc. are mentioned. The alkoxy group includes a cycloalkoxy group (cycloalkoxy group having 5 to 8 carbon atoms such as cyclohexyloxy group) and an aryloxy group (aryloxy group having 6 to 8 carbon atoms such as phenoxy group and benzyloxy group). ) Is also included.

Examples of the silyloxy group include a silyloxy group substituted with an aliphatic group having 1 to 20 carbon atoms and an aromatic group (trimethylsilyloxy group, triethylsilyloxy group, triisopropylsilyloxy group, diethylisopropylsilyloxy group, t- Butyldimethylsilyloxy group, t-butyldiphenylsilyloxy group, tribenzylsilyloxy group, triphenylsilyloxy group, tri-p-xylylsilyloxy group, etc.).

Examples of the acetal group 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. 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. As R ⁶ , R ⁷ and R ⁸ , an alkoxy group and a silyloxy group are preferable because of availability and reactivity.

In the compound represented by the formula (V), examples of the alkyl group for R ⁹ and R ¹⁰ include the same groups as the alkyl groups for R ⁶ , R ^7, and R ⁸ .

As r (integer), 0-5 are preferable for the reason of availability. Furthermore, r is more preferably from 2 to 4, and most preferably 3. If r is 6 or more, the cost increases.

Specific examples of the compound represented by the formula (V) include 3- (N, N-dimethylamino) propyltriethoxysilane and 3- (N, N-dimethylamino) propyltrimethoxy exemplified as the modifier. Silane etc. are mentioned. Of these, 3- (N, N-dimethylamino) propyltrimethoxysilane is preferable.

In the compound represented by the formula (VI), R ¹¹ , R ¹² and R ¹³ are the same as R ⁶ , R ⁷ and R ⁸ in the compound represented by the formula (V).

In the compound represented by the above formula (VI), examples of the cyclic ether group of R ¹⁴ include oxirane group, oxetane group, oxolane group, oxane group, oxepane group, oxocan group, oxonan group, oxecan group, oxet group, A cyclic ether group having one ether bond such as an oxol group, a cyclic ether group having two ether bonds such as a dioxolane group, a dioxane group, a dioxepane group and a dioxecan group, and a cyclic ether group having three ether bonds such as a trioxane group Etc. Among these, a C2-C7 cyclic ether group having one ether bond is preferable, a C2-C4 cyclic ether group having one ether bond is more preferable, and an oxirane group is still more preferable. The cyclic ether group preferably has no unsaturated bond in the ring skeleton.

The p (integer) is preferably 0 to 5 for reasons of availability and reactivity. Further, p is more preferably from 2 to 4, and most preferably 3. If p is 6 or more, the cost increases.

q (integer) is preferably 0 to 5 for reasons of availability and reactivity. Furthermore, q is more preferably 1 to 3, and most preferably 1. If q is 6 or more, the cost increases.

Specific examples of the compound represented by the formula (VI) include 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane exemplified as the modifier. Of these, 3-glycidoxypropyltrimethoxysilane is preferable.

In the compound represented by the above formula (VII), R ¹⁵ , R ¹⁶ and R ¹⁷ are the same as R ⁶ , R ⁷ and R ⁸ in the compound represented by the above formula (V).

As s (integer), 0-5 are preferable from the reason of availability and reactivity. Furthermore, s is more preferably from 2 to 4, and most preferably 3. If s is 6 or more, the cost increases.

Specific examples of the compound represented by the formula (VII) include 3-triphenoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, and 3-diethoxy (methyl) silylpropyl exemplified as the modifier. And succinic anhydride. Of these, 3-triethoxysilylpropyl succinic anhydride is preferable.

In the present invention, after reacting the polymer and the modifier, if necessary, a known anti-aging agent or alcohol may be added for the purpose of stopping the polymerization reaction.

The weight average molecular weight (Mw) of the polymer is preferably 1.0 × 10 ⁵ or more, and more preferably 2.0 × 10 ⁵ or more. The weight average molecular weight of the polymer is preferably 2.0 × 10 ⁶ or less, more preferably 1.5 × 10 ⁶ or less, still more preferably 1.0 × 10 ⁶ or less, and particularly preferably 5.0 × 10 ⁵ or less. When the weight average molecular weight is less than 1.0 × 10 ⁵ , not only is the hysteresis loss large and it is difficult to obtain sufficient fuel efficiency, but the wear resistance also tends to decrease. On the other hand, when it exceeds 2.0 × 10 ⁶ , workability tends to be lowered.
In addition, a weight average molecular weight (Mw) is the value measured by the method as described in the below-mentioned Example.

The amount of styrene in the polymer is preferably 50% by mass or less, more preferably 45% by mass or less, and still more preferably 30% by mass or less. When it exceeds 50 mass%, there is a possibility that sufficient low flame retardancy may not be obtained. The amount of styrene in the polymer is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass or more. If it is less than 5% by mass, sufficient wet grip performance may not be obtained.
In addition, the amount of styrene is a value measured by the method described in Examples described later.

The vinyl content of the polymer is preferably 80% by mass or less, more preferably 75% by mass or less, still more preferably 60% by mass or less, and particularly preferably 50% by mass or less. If it exceeds 80% by mass, sufficient fuel economy may not be obtained. The vinyl content of the polymer is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 25% by mass or more, and particularly preferably 40% by mass or more. If it is less than 10% by mass, sufficient wet grip performance may not be obtained.
The vinyl content is a value measured by the method described in the examples below.

(Rubber composition for tire)
In the present invention, the above polymer is used as the rubber component. By using the above polymer as the rubber component, both low fuel consumption and wet grip performance can be achieved.

The content of the 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 15% by mass or more, and particularly preferably 20% by mass or more. If it is less than 5% by mass, there is a tendency that it is difficult to obtain an effect of improving fuel economy and wet grip performance.

In the present invention, a diene rubber can be used as a rubber component other than the polymer. Examples of the diene rubber include natural rubber (NR) and diene synthetic rubber. Examples of the diene synthetic rubber include isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR), acrylonitrile butadiene comb (NBR), chloroprene rubber (CR), butyl rubber (IIR), and the like. Of these, NR, BR, and SBR are preferable because they exhibit a good balance between grip performance and wear resistance. These rubbers may be used alone or in combination of two or more.

As the NR, for example, those commonly used in the tire industry such as SIR20, RSS # 3, TSR20 and the like can be used.

The BR is not particularly limited. For example, BR1220 manufactured by Nippon Zeon Co., Ltd., BR130B manufactured by Ube Industries, Ltd., BR150B having a high cis content such as BR150B, VCR412 manufactured by Ube Industries, Ltd. BR containing syndiotactic polybutadiene crystals can be used. In particular, the cis content of BR is preferably 95% by mass or more because low fuel consumption and wear resistance can be obtained in a good balance.

In the rubber composition of the present invention, it is preferable to blend carbon black or silica as a reinforcing agent.

Examples of carbon black that can be used include GPF, FEF, HAF, ISAF, and SAF, but are not particularly limited. By blending carbon black, it is possible to enhance the reinforcing property and improve the electrical conductivity, ozone resistance, and aging resistance. Carbon black may be used alone or in combination of two or more.

The nitrogen adsorption specific surface area (N ₂ SA) of carbon black is preferably 80 m ² / g or more, and more preferably 100 m ² / g or more. If it is less than 80 m < ² > / g, sufficient wet-grip performance cannot be obtained, and there is a possibility that the wear resistance is lowered. Further, the nitrogen adsorption specific surface area of the carbon black is preferably 280 meters ² / g or less, more preferably 250 meters ² / g, more preferably from 200 meters ² / g or less, and particularly preferably 150m ² / g. If it exceeds 280 m ² / g, the dispersibility is inferior and the wear resistance may be reduced.
In addition, the nitrogen adsorption specific surface area of carbon black is calculated | required by A method of JISK6217.

When the rubber composition contains carbon black, the content of carbon black 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 rubber component. If it is less than 1 part by mass, the wear resistance tends to decrease. The carbon black content is preferably 100 parts by mass or less, more preferably 90 parts by mass or less, and still more preferably 50 parts by mass or less. If it exceeds 100 parts by mass, the fuel efficiency tends to deteriorate.

The silica that can be used is not particularly limited, and examples thereof include dry process silica (anhydrous silicic acid), wet process silica (hydrous silicic acid), and the like, and wet process silica is preferable because it has many silanol groups. Silica may be used alone or in combination of two or more. By blending silica, the balance between low fuel consumption and wet grip performance is improved.

The nitrogen adsorption specific surface area (N ₂ SA) of the silica is preferably 50 m ² / g or more, more preferably 80 m ² / g or more, and still more preferably 120 m ² / g or more. If it is less than 50 m ² / g, the reinforcing effect is small, and the wear resistance tends to decrease. Further, N ₂ SA of silica is preferably 300 m ² / g or less, more preferably 250 m ² / g or less, and further preferably 210 m ² / g or less. When it exceeds 300 m ² / g, the dispersibility is poor, the hysteresis loss increases, and the fuel efficiency tends to decrease.
The nitrogen adsorption specific surface area of silica is a value measured by the BET method according to ASTM D3037-81.

The content of silica is 5 parts by mass or more, preferably 10 parts by mass or more, more preferably 15 parts by mass or more with respect to 100 parts by mass of the rubber component. If it is less than 5 parts by mass, the wear resistance tends to decrease. The silica content is preferably 150 parts by mass or less, more preferably 100 parts by mass or less, still more preferably 90 parts by mass or less, and particularly preferably 50 parts by mass or less. If it exceeds 150 parts by mass, the workability tends to deteriorate.

When the rubber composition contains carbon black and silica, the total content of carbon black and silica is preferably 15 parts by mass or more, more preferably 20 parts by mass or more, further preferably 100 parts by mass of the rubber component. Is 25 parts by mass or more. If it is less than 15 parts by mass, the wear resistance tends to decrease. The total content is preferably 100 parts by mass or less, more preferably 90 parts by mass or less, and still more preferably 70 parts by mass or less. If it exceeds 100 parts by mass, the processability may be reduced and sufficient fuel economy may not be obtained.

The rubber composition of the present invention preferably contains a silane coupling agent together with silica when silica is blended. Examples of the silane coupling agent include bis (3-triethoxysilylpropyl) tetrasulfide, bis- (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, and bis (2-triethoxy). Ethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercapto Ethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyltetraf, rufide, 3-triethoxysilylpropyl-N, N-dimethylthio Rubamoyl tetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazole tetrasulfide, 3-triethoxysilylpropyl bezothiazolyl tetrasulfide, 3-triethoxy Ethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyl Examples thereof include tetrasulfide and dimethoxymethylsilylpropylbenzothiazole tetrasulfide. Of these, bis (3-triethoxysilylpropyl) tetrasulfide and 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide are preferable from the viewpoint of improving reinforcing properties. These silane coupling agents may be used alone or in combination of two or more.

The content of the silane coupling agent is preferably 1 part by mass or more and more preferably 2 parts by mass or more with respect to 100 parts by mass of silica. If it is less than 1 part by mass, the viscosity of the unvulcanized rubber composition tends to be high and the processability tends to deteriorate. Further, the content of the silane coupling agent is preferably 20 parts by mass or less, and more preferably 15 parts by mass or less. When it exceeds 20 parts by mass, the blending effect of the silane coupling agent corresponding to the blending amount cannot be obtained, and the cost tends to increase.

In addition to the above components, the rubber composition of the present invention includes compounding agents conventionally used in the rubber industry, for example, inorganic and organic fillers such as clay, vulcanization acceleration aids such as stearic acid, and various anti-aging agents. In addition, an ozone deterioration inhibitor, zinc oxide, oil, softener, plasticizer, vulcanizing agent such as wax, sulfur or sulfur compound, vulcanization accelerator and the like can be appropriately blended as necessary.

The rubber composition of the present invention is produced by a general method. That is, it can be produced by a method of kneading the above components with a Banbury mixer, a kneader, an open roll or the like and then vulcanizing.

The rubber composition of the present invention can be suitably used for each member (particularly tread) of a pneumatic tire.

(Pneumatic tire)
The pneumatic tire of the present invention can be produced by a usual method using the rubber composition. That is, the rubber composition is extruded in accordance with the shape of each member (particularly tread) at an unvulcanized stage, molded by a normal method on a tire molding machine, and bonded together with other tire members, Form an unvulcanized tire. This unvulcanized tire can be heated and pressurized in a vulcanizer to produce a tire.

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 competitions, and the like, and particularly preferably used as a tire for passenger cars and a tire for motorcycles. The pneumatic tire obtained by the present invention can achieve both low fuel consumption and wet grip performance.

The present invention will be specifically described based on examples, but the present invention is not limited to these examples.

Hereinafter, various chemicals used in Production Examples 1 to 4 will be described together. In addition, the chemical | medical agent refine | purified according to the usual method as needed.
Lithium diisopropylamide: 1M lithium diisopropylamide manufactured by Kanto Chemical Co., Inc., n-hexane-tetrahydrofuran solution Pyrrolidine: Pyrrolidine hexamethyleneimine manufactured by Kanto Chemical Co., Ltd .: Hexamethyleneimine morpholine manufactured by Kanto Chemical Co., Inc .: Kanto Morpholine 1.6M n-butyllithium hexane solution manufactured by Chemical Co., Ltd .: 1.6M n-butyllithium hexane solution 1,1-dimethyl-1-silacyclobutane manufactured by Kanto Chemical Co., Ltd .: Shin-Etsu Silicone Co., Ltd. LS-700
n-hexane: n-hexane THF manufactured by Kanto Chemical Co., Ltd .: tetrahydrofuran manufactured by Kanto Chemical Co., Ltd.

(Production Example 1)
(Synthesis of polymerization initiator solution (1))
To a 200 ml container sufficiently purged with nitrogen, add 88 ml of n-hexane and 1.3 ml of 1,1-dimethyl-1-silacyclobutane, and add dropwise 10 ml of 1.0 M lithium diisopropylamide, n-hexane-tetrahydrofuran solution at 0 ° C. And the polymerization initiator (following formula (1)) solution (1) was obtained by stirring for 1 hour.

(Production Example 2)
(Synthesis of polymerization initiator solution (2))
To a 100 ml container thoroughly purged with nitrogen, add 40 ml of n-hexane, 0.83 ml of pyrrolidine, and 4 ml of THF, and dropwise add 6.25 ml of 1.6M n-butyllithium hexane solution at 0 ° C. A solution of the compound (lithium pyrrolidine-1-id) was prepared. Next, 44 ml of n-hexane and 1.3 ml of 1,1-dimethyl-1-silacyclobutane were added to a 200 ml container sufficiently purged with nitrogen, and a solution of the lithium amide compound prepared at 0 ° C. was added dropwise and stirred for 1 hour. Thus, a polymerization initiator (following formula (2)) solution (2) was obtained.

(Production Example 3)
(Synthesis of polymerization initiator solution (3))
To a 100 ml container sufficiently purged with nitrogen, add 40 ml of n-hexane, 1.13 ml of hexamethyleneimine, and 4 ml of THF, and drop 6.25 ml of 1.6M n-butyllithium hexane solution at 0 ° C., and stir for 1 hour. A solution of a lithium amide compound (lithium azepan-1-id) was prepared. Next, 44 ml of n-hexane and 1.3 ml of 1,1-dimethyl-1-silacyclobutane were added to a 200 ml container sufficiently purged with nitrogen, and a solution of the lithium amide compound prepared at 0 ° C. was added dropwise and stirred for 1 hour. As a result, a polymerization initiator (following formula (3)) solution (3) was obtained.

(Production Example 4)
(Synthesis of polymerization initiator solution (4))
Add 100 ml of n-hexane, 0.87 ml of morpholine, and 4 ml of THF to a 100 ml container thoroughly purged with nitrogen, drop dropwise 6.25 ml of 1.6M n-butyllithium hexane solution at 0 ° C., and stir for 1 hour to obtain lithium amide. A solution of the compound (lithium morpholine-4-id) was prepared. Next, 44 ml of n-hexane and 1.3 ml of 1,1-dimethyl-1-silacyclobutane were added to a 200 ml container sufficiently purged with nitrogen, and a solution of the lithium amide compound prepared at 0 ° C. was added dropwise and stirred for 1 hour. Thus, a polymerization initiator (following formula (4)) solution (4) was obtained.

Table 1 summarizes the reagents used in Production Examples 1 to 4 and the amounts used.

Hereinafter, various chemicals used in Production Examples 5 to 14 will be described together. In addition, the chemical | medical agent refine | purified according to the usual method as needed.
Butadiene: 1,3-butadiene styrene manufactured by Takachiho Chemical Co., Ltd .: Styrene isoprene manufactured by Kanto Chemical Co., Ltd .: Isoprene manufactured by Kanto Chemical Co., Ltd. n-hexane THF manufactured by Kanto Chemical Co., Ltd. : Tetrahydrofuran polymerization initiators (1) to (4) manufactured by Kanto Chemical Co., Ltd .: polymerization initiator solutions (1) to (4) prepared in the above production examples (1) to (4)
sec-Butyllithium: 1.0Msec-Butyllithium, hexane-cyclohexane solution modifier manufactured by Kanto Chemical Co., Ltd. (1): 3- (N, N-dimethylaminopropyl) trimethoxysilane (formula (A) V), R ⁶ , R ⁷ and R ⁸ = methoxy group, R ⁹ and R ¹⁰ = methyl group, r = 3)
Denaturant (2): 3-glycidoxypropyltrimethoxysilane manufactured by AMAX Co. (in formula (VI), R ¹¹ , R ¹² and R ¹³ = methoxy group, R ¹⁴ = oxirane group, p = 3, q = 1)
Denaturant (3): 3-triethoxysilylpropyl succinic anhydride manufactured by Azimax (in formula (VII), R ¹⁵ , R ¹⁶ and R ¹⁷ = ethoxy group, s = 3)
Isopropanol: Isopropanol 2,6-tert-butyl-p-cresol manufactured by Kanto Chemical Co., Ltd .: 2,6-tert-butyl-p-cresol methanol manufactured by Kanto Chemical Co., Ltd .: Methanol manufactured by Kanto Chemical Co., Inc.

(Production Example 5)
(Synthesis of polymer (1))
To a 2000 ml pressure-resistant container sufficiently purged with nitrogen, 1500 ml of n-hexane, 25 ml of styrene, 150 ml of butadiene, and 10 ml of THF were added, and 4.5 ml of the polymerization initiator solution (1) was added and stirred at 40 ° C. After 3 hours, 3 ml of isopropanol was added to terminate the polymerization. After adding 1 g of 2,6-tert-butyl-p-cresol to the reaction solution, reprecipitation treatment was performed with methanol, followed by heating and drying to obtain a polymer (1).

(Production Examples 6-9, 14)
(Synthesis of polymers (2) to (5) and (10))
According to the formulation shown in Table 2, polymers (2) to (5) and (10) were obtained in the same manner as for polymer (1).

(Production Example 10)
(Synthesis of polymer (6))
To a 2000 ml pressure-resistant container sufficiently purged with nitrogen, 1500 ml of n-hexane, 25 ml of styrene, 150 ml of butadiene, and 10 ml of THF were added, and 4.5 ml of the polymerization initiator solution (1) was added and stirred at 40 ° C. After 3 hours, 0.1 ml of the modifier (1) was added and stirred. After 30 minutes, 3 ml of isopropanol was added to stop the polymerization. After adding 1 g of 2,6-tert-butyl-p-cresol to the reaction solution, it was reprecipitated with methanol and dried by heating to obtain a polymer (6).

(Production Examples 11 to 13)
(Synthesis of polymers (7) to (9))
According to the formulation shown in Table 2, polymers (7) to (9) were obtained in the same manner as the polymer (6).

The following evaluation was performed about the obtained polymers (1)-(10). The results are shown in Table 2.

(Measurement of styrene content and vinyl content)
Measurement was performed using a nuclear magnetic resonance apparatus (JNM-ECA series) manufactured by JEOL.

(Measurement of weight average molecular weight (Mw))
Using gel permeation chromatograph (GPC) (GPC-8000 series, manufactured by Tosoh Corp., detector: differential refractometer, column: TSKGEL SUPERMALTPORE HZ-M, manufactured by Tosoh Corp.), a value converted from standard polystyrene. is there.

Hereinafter, various chemicals used in Examples and Comparative Examples will be described together.
NR: RSS # 3
BR: Ubepol BR150L manufactured by Ube Industries, Ltd. (cis content: 98% by mass)
Polymers (1) to (10): Polymers (1) to (10) prepared in Production Examples 5 to 14
Carbon Black: Show Black N220 (N ₂ SA: 111 m ² / g) manufactured by Cabot Japan
Silica: Ultrasil VN3 manufactured by Degussa (N ₂ SA: 175 m ² / g)
Silane coupling agent: Si69 ((bis (3-triethoxysilylpropyl) tetrasulfide) manufactured by Degussa)
Anti-aging agent: NOCRACK 6C (N-1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine) manufactured by Ouchi Shinsei Chemical Co., Ltd.
Stearic acid: Zinc stearate manufactured by NOF Corporation: Zinc Hua No. 1 manufactured by Mitsui Mining & Smelting Co., Ltd. Sulfur: Powdered sulfur-free vulcanization accelerator manufactured by Tsurumi Chemical Co., Ltd. (1): Emerging Ouchi NOXERA-NS manufactured by Chemical Industry Co., Ltd.
Vulcanization accelerator (2): Noxeller D manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.

Examples 1 to 9 and Comparative Example 1
According to the contents shown in Table 3, materials other than sulfur and a vulcanization accelerator were kneaded for 3 minutes at 150 ° C. using a Banbury mixer to obtain a kneaded product. Next, sulfur and a vulcanization accelerator were added to the obtained kneaded product, and kneaded for 5 minutes at 50 ° C. using an open roll to obtain an unvulcanized rubber composition. The obtained unvulcanized rubber composition was press vulcanized with a 0.5 mm thick mold at 170 ° C. for 20 minutes to obtain a vulcanized rubber composition.

The obtained unvulcanized rubber composition is molded into a tread shape, bonded to another tire member, molded into a tire, and vulcanized at 170 ° C. for 10 minutes to test tires (tire size: 195 / 65R15) Manufactured.

The following evaluation was performed using the obtained vulcanized rubber composition and test tire. Table 3 shows the test results.

(Low fuel consumption)
Using a spectrometer manufactured by Ueshima Seisakusho, tan δ was measured at a dynamic strain amplitude of 1%, a frequency of 10 Hz, and a temperature of 60 ° C. The reciprocal value of tan δ was expressed as an index with Comparative Example 1 being 100. The larger the index, the better the fuel efficiency.

(Wet grip performance (1))
Grip performance was evaluated using a flat belt friction tester (FR5010 type) manufactured by Ueshima Seisakusho. Using a cylindrical rubber test piece with a width of 20 mm and a diameter of 100 mm, the slip ratio of the sample with respect to the road surface is changed from 0 to 50% under the conditions of a speed of 20 km / hour, a load of 4 kgf, and a road surface temperature of 20 ° C. The maximum value of the coefficient of friction to be used was read. Comparative example 1 was taken as 100 and displayed as an index. The larger the index, the higher the wet grip performance.

(Wet grip performance (2))
On a test course with wet water and wet road surface, the tire is mounted on a 2000cc domestic FR vehicle, braked at a speed of 70km / h, and the distance traveled from braking the tire to stopping (braking distance) ), And the reciprocal value of the distance was expressed as an index with Comparative Example 1 as 100. The larger the index, the higher the wet grip performance.

As shown in Table 3, the examples in which the polymers (1) to (9) having a specific aminosilane structure were blended were compared to the comparative example in which the polymer (10) having no specific aminosilane structure was blended. It has been clarified that a rubber composition excellent in balance between low fuel consumption and wet grip performance can be provided.

Claims (5)

Using a polymerization initiator obtained by reacting a lithium amide compound represented by the following general formula (I) with a silane compound represented by the following general formula (II), a conjugated diene compound or a conjugated diene compound and an aromatic A polymer obtained by polymerizing a vinyl compound.

(R ¹ and R ² are each independently a monovalent hydrocarbon group having 1 to 18 carbon atoms, and the monovalent hydrocarbon group may have a substituted amino group or an ether group, , R ¹ and R ² may be bonded to each other to form a ring structure, R ³ is a divalent hydrocarbon group having 3 to 9 carbon atoms, and R ⁴ and R ⁵ are each independently 1 to 1 carbon atoms. 18 represents a monovalent hydrocarbon group.) The polymer according to claim 1, wherein a terminal end of the polymer is modified with a compound having a functional group containing at least one atom selected from the group consisting of nitrogen, oxygen, and silicon. The polymer according to claim 1 or 2, wherein the conjugated diene compound is 1,3-butadiene or isoprene, and the aromatic vinyl compound is styrene. The rubber composition for tires whose content of the polymer in any one of Claims 1-3 in 100 mass% of rubber components is 5 mass% or more. A pneumatic tire produced using the tire rubber composition according to claim 4.