JP7175746B2 - Rubber composition and tire - Google Patents

Description

The present invention relates to rubber compositions and tires.

In recent years, from the viewpoint of safety during vehicle travel, there has been a demand for improved wet grip performance (grip performance on wet road surfaces such as in rainy weather).

As a method for improving wet grip performance, there is a method of blending silica into the rubber component of the tread portion of the tire. However, since the affinity between silica and the rubber component is low and the silica aggregates with each other, there is a problem that the silica is not uniformly dispersed in the rubber component.

Patent Document 1 describes a rubber composition for tires containing a rubber component containing an aromatic vinyl-diene copolymer, silica, an aromatic vinyl monomer, a low molecular weight aromatic vinyl-diene rubber, and cerium oxide. It has been shown to have excellent wet grip performance.

However, even if the rubber composition of Patent Document 1 is used, it cannot be said that the wet grip performance of the tire is necessarily sufficiently improved, and there is also the drawback that the types of rubber components are limited.

JP 2017-75245 A

An object of the present invention is to provide a rubber composition for tires having excellent wet grip performance.

Another object of the present invention is to provide a tire exhibiting excellent wet grip performance.

The present inventors have made intensive studies to solve the above problems, and found that the wet grip performance of the obtained tire is improved by blending a specific pyrazolone-based compound into a rubber composition containing silica. Found it.

That is, the present invention provides a rubber composition, a method for producing the rubber composition, and a tire shown below.
Section 1.
A rubber composition comprising the following components (a), (b) and (c):
Component (a) a rubber component,
Component (b) at least one compound selected from the group consisting of compounds represented by formula (1), compounds represented by formula (2), and salts of the compounds;
Component (c) Silica.

（式（１）中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は同一又は異なって、水素原子、アルキル基、アラルキル基、アリール基、又は複素環基を示す。Ｒ^３とＲ^４とは互いに結合してアルキリデン基を形成してもよく、Ｒ^２、Ｒ^３及びＲ^４のいずれか２つが互いに結合してアルキレン基を形成してもよい。これら各基は、それぞれ１個以上の置換基を有していてもよい。）

(In formula (1), R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group. R ³ and R ⁴ are Any two of R ² , R ³ and R ⁴ may combine with each other to form an alkylene group, and each of these groups may be combined with one or more substituents. You may have a group.)

（式（２）中、Ｒ^５、Ｒ^７及びＲ^８は同一又は異なって、水素原子、アミノ基、アルキル基、アラルキル基、アリール基、又は複素環基を示し、Ｒ^６はアルキル基、アラルキル基、アリール基、又は複素環基を示す。これら各基は、それぞれ１個以上の置換基を有していてもよい。）
項２．
前記成分（ｂ）が式（１）により表される化合物である、項１に記載のゴム組成物。
項３．
前記成分（ａ）１００質量部に対して、前記成分（ｃ）を５～１２０質量部含む、項１又は２に記載のゴム組成物。
項４．
更に成分（ｄ）炭化水素系ポリマーを含む項１～３のいずれかに記載のゴム組成物。
項５．
項１～４のいずれかに記載のゴム組成物を用いて作製されたタイヤ。
項６．
前記成分（ａ）、（ｂ）及び（ｃ）を含む原料成分を混合する工程（Ａ）を含む、ゴム組成物の製造方法。
項７．
前記工程（Ａ）において更に前記成分（ｄ）を混合する、項６に記載のゴム組成物の製造方法。
項８．
前記工程（Ａ）が、前記成分（ａ）、及び（ｂ）を混合する工程（Ａ－１）、並びに工程（Ａ－１）で得られた混合物及び前記成分（ｃ）を混合する工程（Ａ－２）からなる、項６に記載の製造方法。
項９．
前記工程（Ａ－１）において更に前記成分（ｄ）を混合する、項８に記載のゴム組成物の製造方法。

(In Formula (2), R ⁵ , R ⁷ and R ⁸ are the same or different and represent a hydrogen atom, an amino group, an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group, and R ⁶ is an alkyl group, an aralkyl group, aryl group, or heterocyclic group, each of which may have one or more substituents.)
Section 2.
Item 1. The rubber composition according to item 1, wherein the component (b) is a compound represented by formula (1).
Item 3.
Item 3. The rubber composition according to Item 1 or 2, comprising 5 to 120 parts by mass of the component (c) with respect to 100 parts by mass of the component (a).
Section 4.
4. The rubber composition according to any one of Items 1 to 3, further comprising component (d) a hydrocarbon polymer.
Item 5.
A tire produced using the rubber composition according to any one of Items 1 to 4.
Item 6.
A method for producing a rubber composition, comprising a step (A) of mixing raw material components including the components (a), (b) and (c).
Item 7.
7. The method for producing a rubber composition according to item 6, wherein the component (d) is further mixed in the step (A).
Item 8.
The step (A) comprises a step (A-1) of mixing the components (a) and (b), and a step of mixing the mixture obtained in the step (A-1) and the component (c) ( Item 6, comprising A-2).
Item 9.
Item 9. The method for producing a rubber composition according to Item 8, wherein the component (d) is further mixed in the step (A-1).

ADVANTAGE OF THE INVENTION This invention can provide the rubber composition for tires which has the outstanding wet grip performance, and the manufacturing method of this rubber composition.

INDUSTRIAL APPLICABILITY The present invention can provide a tire exhibiting excellent wet grip performance.

The present invention will be described in detail below.

(1. Rubber composition)
The rubber composition of the present invention contains the following components (a), (b) and (c).
Component (a) a rubber component,
Component (b) at least one compound selected from the group consisting of compounds represented by formula (1), compounds represented by formula (2), and salts of the compounds;
Component (c) Silica.

（式（１）中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は同一又は異なって、水素原子、アルキル基、アラルキル基、アリール基、又は複素環基を示す。Ｒ^３とＲ^４とは互いに結合してアルキリデン基を形成してもよく、Ｒ^２、Ｒ^３及びＲ^４のいずれか２つが互いに結合してアルキレン基を形成してもよい。これら各基は、それぞれ１個以上の置換基を有していてもよい。）

(In formula (1), R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group. R ³ and R ⁴ are Any two of R ² , R ³ and R ⁴ may combine with each other to form an alkylene group, and each of these groups may be combined with one or more substituents. You may have a group.)

（式（２）中、Ｒ^５、Ｒ^７及びＲ^８は同一又は異なって、水素原子、アミノ基、アルキル基、アラルキル基、アリール基、又は複素環基を示し、Ｒ^６はアルキル基、アラルキル基、アリール基、又は複素環基を示す。これら各基は、それぞれ１個以上の置換基を有していてもよい。）

(In Formula (2), R ⁵ , R ⁷ and R ⁸ are the same or different and represent a hydrogen atom, an amino group, an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group, and R ⁶ is an alkyl group, an aralkyl group, aryl group, or heterocyclic group, each of which may have one or more substituents.)

(1.1. Component (a): rubber component)
The rubber component of the rubber composition of the present invention is not particularly limited, and examples include natural rubber (NR), synthetic diene rubber, mixtures of natural rubber and synthetic diene rubber, and other non-diene rubbers. is mentioned.

Examples of natural rubber include natural rubber latex, technical grade rubber (TSR), smoked sheet (RSS), gutta-percha, Eucommia-derived natural rubber, guayule-derived natural rubber, Russian dandelion-derived natural rubber, etc. Further, these natural rubbers are modified. Modified natural rubbers such as epoxidized natural rubber, methacrylic acid-modified natural rubber, halogen-modified natural rubber, deproteinized natural rubber, maleic acid-modified natural rubber, sulfonic acid-modified natural rubber, and styrene-modified natural rubber are also used in the present invention. Contained in natural rubber.

Synthetic diene rubbers include styrene-butadiene copolymer rubber (SBR), butadiene rubber (BR), isoprene rubber (IR), nitrile rubber (NBR), chloroprene rubber (CR), ethylene-propylene-diene ternary copolymer Polymer rubbers (EPDM), styrene-isoprene-styrene triblock copolymers (SIS), styrene-butadiene-styrene triblock copolymers (SBS), etc., and modified synthetic diene rubbers thereof can be mentioned. Modified synthetic diene-based rubbers include diene-based rubbers obtained by modification techniques such as main chain modification, single-end modification, and both-end modification. Here, the modified functional group of the modified synthetic diene rubber includes various functional groups such as an epoxy group, an amino group, an alkoxysilyl group, and a hydroxyl group. It may be contained in rubber.

The method for producing the synthetic diene rubber is not particularly limited, and examples thereof include emulsion polymerization, solution polymerization, radical polymerization, anionic polymerization, and cationic polymerization. Also, there is no particular limitation on the glass transition point of the synthetic diene rubber.

Moreover, the ratio of cis/trans/vinyl in the double bond portion of natural rubber and synthetic diene rubber is not particularly limited, and any ratio can be suitably used. Also, the number average molecular weight and molecular weight distribution of the diene rubber are not particularly limited, but a number average molecular weight of 500 to 3,000,000 and a molecular weight distribution of 1.5 to 15 are preferred. A wide range of known rubbers can be used as the non-diene rubber.

A rubber component can be used individually by 1 type or in mixture (blend) of 2 or more types. Among them, preferable rubber components are natural rubber, IR, SBR, BR, or a mixture of two or more selected from these, more preferably natural rubber, SBR, BR, or a mixture of two or more selected from these. .

The content of component (a) in the total 100% by mass of components (a), (b), (c), and (d) in the tire rubber composition is preferably 30 to 99% by mass. , more preferably 35 to 98% by mass. When the component (a) is contained in an amount of 30% by mass or more, elasticity can be imparted to the rubber composition. On the other hand, when the component (a) contained in the tire rubber composition is 99% by mass or less, it is possible to reduce the cost of the rubber composition and, as a result, improve the economic efficiency.

When a mixture of natural rubber, SBR, and BR is used, the mixing ratio of the rubber components is 40 to 100% by mass of natural rubber, 10 to 80% by mass of SBR, and 5 to 5% of BR out of 100% by mass of the rubber component. 40% by mass is preferable, and 60 to 90% by mass of natural rubber, 20 to 60% by mass of SBR, and 10 to 25% by mass of BR in 100% by mass of the rubber component are particularly preferable.

(1.2. Component (b): Compound Represented by Formula (1) or (2) or Salt of the Compound)
The rubber composition of the present invention comprises a compound represented by the following formula (1), a salt thereof (compound (1)), a compound represented by the following formula (2), and a salt thereof (compound (2)). One or more selected from the group.

（式（１）中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は同一又は異なって、水素原子、アルキル基、アラルキル基、アリール基、又は複素環基を示す。Ｒ^３とＲ^４とは互いに結合してアルキリデン基を形成してもよく、Ｒ^２、Ｒ^３及びＲ^４のいずれか２つが互いに結合してアルキレン基を形成してもよい。これら各基は、それぞれ１個以上の置換基を有していてもよい。）

(In formula (1), R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group. R ³ and R ⁴ are Any two of R ² , R ³ and R ⁴ may combine with each other to form an alkylene group, and each of these groups may be combined with one or more substituents. You may have a group.)

（式（２）中、Ｒ^５、Ｒ^７及びＲ^８は同一又は異なって、水素原子、アミノ基、アルキル基、アラルキル基、アリール基、又は複素環基を示し、Ｒ^６はアルキル基、アラルキル基、アリール基、又は複素環基を示す。これら各基は、それぞれ１個以上の置換基を有していてもよい。）

(In Formula (2), R ⁵ , R ⁷ and R ⁸ are the same or different and represent a hydrogen atom, an amino group, an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group, and R ⁶ is an alkyl group, an aralkyl group, aryl group, or heterocyclic group, each of which may have one or more substituents.)

In formula (1), R ¹ , R ³ and R ⁴ are the same or different and represent a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, an aralkyl group, an aryl group, or a heterocyclic group is preferably

In formula (1), R ¹ is preferably a hydrogen atom.

In formula (1), R ² is preferably a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, an aralkyl group, an aryl group, or a heterocyclic group; It is more preferably a linear or branched alkyl group of 1 to 4, benzyl, phenyl, naphthyl, or furyl group, and is a hydrogen atom or a linear alkyl group of 1 to 4 carbon atoms. is more preferred.

In formula (1), at least one of R ³ and R ⁴ is preferably a hydrogen atom, more preferably both R ³ and R ⁴ are hydrogen atoms.

In formula (1), R ¹ is a hydrogen atom, R ² is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, an aralkyl group, an aryl group, or a heterocyclic group, and R ³ and R ⁴ are ^both hydrogen atoms; R ¹ is hydrogen atom; or a heterocyclic group, more preferably R ³ and R ⁴ together form an alkylidene group, R ¹ is a hydrogen atom, R ² is a hydrogen atom or a C 1-4 It is particularly preferred that it is a linear alkyl group and that both R ³ and R ⁴ are hydrogen atoms.

In formula (2), R ⁵ is a hydrogen atom, R ⁶ is a linear or branched alkyl group, aralkyl group, or aryl group having 1 to 4 carbon atoms, and R ⁷ and R ⁸ are the same or Differently, it is preferably a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, an aralkyl group, an aryl group, an amino group or a heterocyclic group.

In formula (2), R ⁶ is preferably a linear alkyl group having 1 to 4 carbon atoms, an aralkyl group or an aryl group, and a linear alkyl group having 1 to 4 carbon atoms or an aryl group. It is more preferable to have

In formula (2), R ⁷ and R ⁸ are the same or different and are preferably a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or an amino group.

In formula (2), R ⁵ is a hydrogen atom, R ⁶ is a linear alkyl group having 1 to 4 carbon atoms or an aryl group, R ⁷ and R ⁸ are the same or different, a hydrogen atom, A linear alkyl group having 1 to 4 carbon atoms or an amino group is preferred.

Among compound (1) and compound (2), compound (1) is particularly preferred.

Examples of compound (1) include 5-pyrazolone, 3-methyl-5-pyrazolone, 3-(naphthalen-2-yl)-1H-pyrazol-5(4H)-one, 3-(furan-2-yl )-1H-pyrazol-5(4H)-one, 3-phenyl-1H-pyrazol-5(4H)-one, 3-propyl-1H-pyrazol-5(4H)-one, 3-undecyl-1H-pyrazole -5(4H)-one, 4-(2-hydroxyethyl)-3-methyl-1H-pyrazol-5(4H)-one, 4-benzyl-3-methyl-1H-pyrazol-5(4H)-one, 4,4′-(phenylmethylene)bis(5-methyl-1H-pyrazol-3(2H)-one), 4-[(dimethylamino)methylidene]-3-methyl-1H-pyrazole-5(4H)- one, 4-methyl-2,3-diazospiro[4.4]non-3en-1-one, 5-methyl-2-(4-nitrophenyl)-1H-pyrazol-3(2H)-one, 5 -methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, 4,5,6,7-tetrahydro-2H-indazol-3(3aH)-one, 4-{[4-dimethylamino ] Phenyl}methylidene}-3-methyl-1H-pyrazol-5(4H)-one, 4,4′-(4-hydroxyphenylmethylene)bis(5-methyl-1H-pyrazol-3(2H)-one) , and 1,3-diphenyl-1H-pyrazol-5(4H)-one, 4,4′-(4-nitrophenylmethylene)bis(5-methyl-1H-pyrazol-3(2H)-one) and the like mentioned.

Examples of compound (2) include 1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one, 1-phenyl-1H-pyrazol-3(2H)-one, 4-amino-1 ,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one and the like.

Among them, preferred compounds are compounds (1), among which 5-pyrazolone, 3-methyl-5-pyrazolone, 3-(naphthalen-2-yl)-1H-pyrazol-5(4H)-one, 3 -(furan-2-yl)-1H-pyrazol-5(4H)-one, 3-phenyl-1H-pyrazol-5(4H)-one, and 3-propyl-1H-pyrazol-5(4H)-one is more preferred.

The component (b) in the rubber composition of the present invention may contain only one of the compounds (1) and (2) described above, or may contain two or more of them in combination.

Some compounds (1) or (2) give rise to tautomers. A chemical equilibrium of tautomers can be reached when tautomerization is allowed (eg, in solution). Compounds (1) or (2) can exist as tautomers, eg as represented by formulas (3)-(9).

In the above formula (1), the compound in which R ¹ and R ³ are hydrogen atoms (compound (1)-A) has tautomers represented by the following formulas (3) to (5). .

（式中、Ｒ^２及びＲ^４は、前記に同じ。）

(In the formula, R ² and R ⁴ are the same as above.)

In the above formula (1), the compound in which R ³ is a hydrogen atom (compound (1)-B) has tautomers represented by the following formulas (6) and (7).

（式中、Ｒ^１、Ｒ^２及びＲ^４は、前記に同じ。）

(In the formula, R ¹ , R ² and R ⁴ are the same as above.)

In the above formula (1), the compound in which R ¹ is a hydrogen atom (compound (1)-C) has a tautomer represented by the following formula (8).

（式中、Ｒ^２、Ｒ^３及びＲ^４は、前記に同じ。）

(In the formula, R ² , R ³ and R ⁴ are the same as above.)

In the above formula (2), the compound in which R ⁵ is a hydrogen atom (compound (2)-A) has a tautomer represented by the following formula (9).

（式中、Ｒ^６、Ｒ^７及びＲ^８は、前記に同じ。）

(In the formula, R ⁶ , R ⁷ and R ⁸ are the same as above.)

The tautomers represented by the above formulas (3) to (9) and the compound (1) or (2) have reached an equilibrium state in which both isomers coexist. Thus, unless otherwise stated, all tautomeric forms of compound (1) or (2) are intended herein to be within the scope of the invention.

Moreover, the salt of the compound represented by formula (1) or (2) is not particularly limited and includes all kinds of salts. Examples of such salts include inorganic acid salts such as hydrochlorides, sulfates and nitrates; organic acid salts such as acetates and methanesulfonates; alkali metal salts such as sodium salts and potassium salts; magnesium salts and calcium salts; alkaline earth metal salts such as salts; and ammonium salts such as dimethylammonium and triethylammonium.

Component (b) in the rubber composition of the present invention may include a mixture containing compound (1) and/or compound (2) in any proportion.

The amount of component (b) compounded is preferably 0.01 to 50 parts by mass, more preferably 0.05 to 30 parts by mass, with respect to 100 parts by mass of component (a) in the rubber composition. is more preferable, and 0.1 to 10 parts by mass is even more preferable.

The content of component (b) in the total 100% by mass of components (a), (b), (c), and (d) in the rubber composition for tires is 0.001 to 40% by mass. is preferred, and 0.005 to 30% by mass is more preferred. By containing 0.001% by mass or more of component (b), wet grip performance can be improved. On the other hand, when the component (b) contained in the tire rubber composition is 40% by mass or less, the durability of the rubber composition can be maintained without deteriorating.

As used herein, the "alkyl group" is not particularly limited, and examples thereof include linear, branched or cyclic alkyl groups, and specific examples include methyl, ethyl, n-propyl, Linear or branched alkyl groups having 1 to 4 carbon atoms such as isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, further 1-ethylpropyl, n-pentyl, isopentyl, neopentyl, n -hexyl, isohexyl, 3-methylpentyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, 5-propylnonyl, n-tridecyl, n-tetradecyl, n-pentadecyl , hexadecyl, heptadecyl, octadecyl, etc., linear or branched C5-18 alkyl groups; C3-8 cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like.

In the present specification, the "aralkyl group" is not particularly limited, and examples thereof include benzyl, phenethyl, trityl, 1-naphthylmethyl, 2-(1-naphthyl)ethyl, 2-(2-naphthyl)ethyl groups and the like. mentioned.

As used herein, the "aryl group" is not particularly limited and includes, for example, phenyl, biphenyl, naphthyl, dihydroindenyl, 9H-fluorenyl groups and the like.

In the present specification, the "heterocyclic group" is not particularly limited, for example, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrazinyl, 2-pyrimidyl, 4-pyrimidyl, 5-pyrimidyl, 3- pyridazyl, 4-pyridazyl, 4-(1,2,3-triazyl), 5-(1,2,3-triazyl), 2-(1,3,5-triazyl), 3-(1,2,4 -triazyl), 5-(1,2,4-triazyl), 6-(1,2,4-triazyl), 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7- quinolyl, 8-quinolyl, 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 8-isoquinolyl, 2-quinoxalyl, 3-quinoxalyl, 5-quinoxalyl, 6-quinoxalyl, 7-quinoxalyl, 8-quinoxalyl, 3-cinnolyl, 4-cinnolyl, 5-cinnolyl, 6-cinnolyl, 7-cinnolyl, 8-cinnolyl, 2-quinazolyl, 4-quinazolyl, 5-quinazolyl, 6-quinazolyl, 7- quinazolyl, 8-quinazolyl, 1-phthalazyl, 4-phthalazyl, 5-phthalazyl, 6-phthalazyl, 7-phthalazyl, 8-phthalazyl, 1-tetrahydroquinolyl, 2-tetrahydroquinolyl, 3-tetrahydroquinolyl, 4- Tetrahydroquinolyl, 5-tetrahydroquinolyl, 6-tetrahydroquinolyl, 7-tetrahydroquinolyl, 8-tetrahydroquinolyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 2-furyl, 3-furyl, 2- thienyl, 3-thienyl, 1-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 4-(1,2,3-thiadiazolyl), 5- (1,2,3-thiadiazolyl), 3-(1,2,5-thiadiazolyl), 2-(1,3,4-thiadiazolyl), 4-(1,2,3-oxadiazolyl), 5-(1 ,2,3-oxadiazolyl), 3-(1,2,4-oxadiazolyl), 5-(1,2,4-oxadiazolyl), 3-(1,2,5-oxadiazolyl) diazolyl), 2-(1,3,4-oxadiazolyl), 1-(1,2,3-triazolyl), 4-(1,2,3-triazolyl), 5-(1,2,3-triazolyl) , 1-(1,2,4-triazolyl), 3-(1,2,4-triazolyl), 5-(1,2,4-triazolyl), 1-tetrazolyl, 5-tetrazolyl, 1-indolyl, 2 - indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl, 1-isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5-isoindolyl, 6-isoindolyl, 7-isoindolyl , 1-benzimidazolyl, 2-benzimidazolyl, 4-benzimidazolyl, 5-benzimidazolyl, 6-benzimidazolyl, 7-benzimidazolyl, 2-benzofuranyl, 3-benzofuranyl, 4-benzofuranyl, 5-benzofuranyl, 6-benzofuranyl, 7-benzofuranyl, 1 -isobenzofuranyl, 3-isobenzofuranyl, 4-isobenzofuranyl, 5-isobenzofuranyl, 6-isobenzofuranyl, 7-isobenzofuranyl, 2-benzothienyl, 3-benzothienyl, 4- benzothienyl, 5-benzothienyl, 6-benzothienyl, 7-benzothienyl, 2-benzoxazolyl, 4-benzoxazolyl, 5-benzoxazolyl, 6-benzoxazolyl, 7-benzoxa zolyl, 2-benzothiazolyl, 4-benzothiazolyl, 5-benzothiazolyl, 6-benzothiazolyl, 7-benzothiazolyl, 1-indazolyl, 3-indazolyl, 4-indazolyl, 5-indazolyl, 6-indazolyl, 7-indazolyl, 2-morpholyl , 3-morpholyl, 4-morpholyl, 1-piperazyl, 2-piperazyl, 1-piperidyl, 2-piperidyl, 3-piperidyl, 4-piperidyl, 2-tetrahydropyranyl, 3-tetrahydropyranyl, 4-tetrahydropyranyl , 2-tetrahydrothiopyranyl, 3-tetrahydrothiopyranyl, 4-tetrahydrothiopyranyl, 1-pyrrolidyl, 2-pyrrolidyl, 3-pyrrolidyl, furanyl, 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl , 3-tetrahydrothienyl, 5-methyl-3-oxo-2,3-dihydro-1H-pyrazol-4-yl group, morpholino group and the like.

In the present specification, the "alkylene group" is not particularly limited, and examples thereof include ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group and the like. These alkylene groups may contain a nitrogen atom, an oxygen atom, or a sulfur atom, and may be via a phenylene group. Examples of such alkylene groups include -CH ₂ NHCH ₂ -, -CH ₂ NHCH ₂ CH ₂ -, -CH ₂ NHNHCH ₂ -, -CH ₂ CH ₂ NHCH ₂ CH ₂ -, -CH ₂ NHNHCH ₂ CH _{2- , -CH2NHCH2NHCH2- , -CH2CH2CH2NHCH2CH2CH2- , -CH2OCH2CH2- , -CH2CH2OCH2CH2- , -CH2 _ _ _ _ _ _ _} SCH ₂ CH ₂ -, -CH ₂ CH ₂ SCH ₂ CH ₂ -,

等が挙げられる。

etc.

As used herein, the "alkylidene group" is not particularly limited, and examples thereof include methylidene, ethylidene, propylidene, isopropylidene, and butylidene groups.

Each of these alkyl groups, aralkyl groups, aryl groups, heterocyclic groups and alkylene groups may have one or more substituents at any substitutable position. The "substituent" is not particularly limited, and examples thereof include halogen atoms, amino groups, aminoalkyl groups, alkoxycarbonyl groups, acyl groups, acyloxy groups, amide groups, carboxyl groups, carboxyalkyl groups, formyl groups, and nitrile groups. , nitro group, alkyl group, hydroxyalkyl group, hydroxyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, thiol group, alkylthio group, arylthio group and the like. The substituent may preferably have 1 to 5, more preferably 1 to 3.

As used herein, "halogen atom" includes fluorine, chlorine, bromine and iodine atoms, preferably chlorine, bromine and iodine atoms.

As used herein, the term “amino group” includes not only the amino group represented by —NH ₂ but also, for example, methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, s -butylamino, t-butylamino, 1-ethylpropylamino, n-pentylamino, neopentylamino, n-hexylamino, isohexylamino, 3-methylpentylamino and other linear or branched mono Alkylamino group: Substituted amino groups such as dialkylamino groups having two linear or branched alkyl groups such as dimethylamino, ethylmethylamino and diethylamino groups are also included.

As used herein, the "aminoalkyl group" is not particularly limited, and examples thereof include aminomethyl, methylaminomethyl, ethylaminomethyl, dimethylaminomethyl, ethylmethylaminomethyl, diethylaminomethyl, 2-aminoethyl, 2- (methylamino) ethyl, 2-(ethylamino) ethyl, 2-(dimethylamino) ethyl, 2-(ethylmethylamino) ethyl, 2-(diethylamino) ethyl, 3-aminopropyl, 3-(methylamino) propyl , 3-(ethylamino)propyl, 3-(dimethylamino)propyl, 3-(ethylmethylamino)propyl, 3-(diethylamino)propyl groups and other aminoalkyl groups, monoalkyl-substituted aminoalkyl groups or dialkyl-substituted aminoalkyl groups and the like.

As used herein, the "alkoxycarbonyl group" is not particularly limited, and examples thereof include methoxycarbonyl and ethoxycarbonyl groups.

As used herein, the "acyl group" is not particularly limited, and examples thereof include linear or branched alkylcarbonyl groups having 1 to 4 carbon atoms such as acetyl, propionyl and pivaloyl groups.

As used herein, the "acyloxy group" is not particularly limited, and examples thereof include acetyloxy, propionyloxy, n-butyryloxy groups and the like.

In the present specification, the "amide group" is not particularly limited, and examples thereof include carboxylic acid amide groups such as acetamide and benzamide groups; thioamide groups such as thioacetamide and thiobenzamide groups; N-methylacetamide and N-benzylacetamide. N-substituted amide groups such as groups;

As used herein, the "carboxyalkyl group" is not particularly limited, and examples thereof include carboxymethyl, carboxyethyl, carboxy-n-propyl, carboxy-n-butyl, carboxy-n-pentyl, and carboxy-n-hexyl groups. and other carboxyalkyl groups.

As used herein, the "hydroxyalkyl group" is not particularly limited, and examples thereof include hydroxyalkyl groups such as hydroxymethyl, hydroxyethyl, hydroxy-n-propyl and hydroxy-n-butyl groups.

As used herein, the "alkoxy group" is not particularly limited, and examples thereof include linear, branched or cyclic alkoxy groups, and specific examples include methoxy, ethoxy, n-propoxy, Linear or branched alkoxy groups of isopropoxy, n-butoxy, t-butoxy, n-pentyloxy, neopentyloxy and n-hexyloxy groups; cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy , cycloheptyloxy, and cyclic alkoxy groups such as cyclooctyloxy groups.

In the present specification, the "aryloxy group" is not particularly limited, and examples thereof include phenoxy, biphenyloxy, naphthoxy and the like.

As used herein, the "alkylthio group" is not particularly limited, and examples thereof include methylthio, ethylthio, n-propylthio and the like.

As used herein, the "arylthio group" is not particularly limited, and examples thereof include a phenylthio group, a naphthylthio group, a biphenylthio group and the like.

(1.3. Component (c): Silica)
The rubber composition of the present invention contains silica.

Silica to be used is not particularly limited, and for example, commercially available products can be preferably used. Among them, preferred silica is wet silica, dry silica, or colloidal silica, and more preferred is wet silica. The surface of these silicas may be organically treated in order to improve the affinity with the rubber component. Such organic treatment is not particularly limited, and for example, treatment with a silane coupling agent can be exemplified.

The BET specific surface area of silica is not particularly limited, and is preferably 40 to 350 m ² /g, for example. When the BET specific surface area of silica is within such a range, there is an advantage that both rubber toughness and dispersibility in the rubber component can be achieved. The BET specific surface area shall be measured according to ISO5794/1.

From this point of view, preferred silica is silica having a BET specific surface area of 80 to 300 m ² /g, more preferably silica having a BET specific surface area of 100 to 270 m ² /g, further preferably Silica having a BET specific surface area in the range of 110 to 270 m ² /g.

Commercially available products of such silica are available from Quechen Silicon Chemical Co.; , Ltd. product names "HD165MP" (BET specific surface area = 165 m ² /g), "HD115MP" (BET specific surface area = 115 m ² /g), "HD200MP" (BET specific surface area = 200 m ² /g), "HD250MP" ( BET specific surface area = 250 m ² /g), trade name “Nip Seal AQ” (BET specific surface area = 205 m ² /g) manufactured by Tosoh Silica Co., Ltd., “Nip Seal KQ” (BET specific surface area = 240 m ² /g), Degussa trade name "Ultrasil VN3" (BET specific surface area = 175 m ² /g) manufactured by Co., Ltd., and the like.

By blending compound (1) and/or compound (2) in the rubber composition of the present invention, the dispersibility of silica can be greatly improved, and the wet grip performance of the rubber composition can be significantly improved. That is, the compound (1) and/or compound (2) can be used as a silica dispersant, preferably as a rubber dispersant.

The amount of component (c) compounded is preferably 10 to 100 parts by mass, more preferably 20 to 80 parts by mass, with respect to 100 parts by mass of component (a) in the rubber composition. More preferably 40 to 60 parts by mass.

Similarly, the amount of component (b) is preferably 0.2 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, with respect to 100 parts by mass of component (c) in the rubber composition. is more preferable, and 1 to 3 parts by mass is even more preferable. When component (b) is 0.2 parts by mass or more per 100 parts by mass of component (c), wet grip properties are improved. On the other hand, when component (b) is 10 parts by mass or less per 100 parts by mass of component (c), hardness can be maintained.

The content of component (c) in the total 100% by mass of components (a), (b), (c), and (d) in the tire rubber composition is preferably 1 to 70% by mass. , more preferably 1.5 to 60% by mass. When the component (c) is contained in an amount of 1% by mass or more, the abrasion resistance of the rubber composition can be maintained without deteriorating. On the other hand, when the component (c) contained in the rubber composition for tires is 70% by mass or less, there is an advantage that elasticity can be imparted to the rubber composition.

(1.4. Component (d): Hydrocarbon Polymer)
The rubber composition of the present invention preferably further contains a hydrocarbon polymer as component (d).

As used herein, the term "hydrocarbon-based polymer" refers to a polar group containing a heteroatom (e.g., a hydroxy group, an amino group, a carboxyl group, a nitro group, a cyano group, a mercapto group, a ketone group, etc.) in the structure. is defined as a polymer that does not have

Examples of hydrocarbon-based polymers include dicyclopentadiene resins, styrene polymers, coumarone-indene resins, and hydrogenated dicyclopentadiene resins. is preferred.

The amount of component (d) compounded is preferably 5 to 40 parts by mass, more preferably 10 to 30 parts by mass, with respect to 100 parts by mass of component (a) in the rubber composition. More preferably 15 to 25 parts by mass.

The content of component (d) in the total 100% by mass of components (a), (b), (c) and (d) in the tire rubber composition is preferably 1 to 20% by mass. , more preferably 1.5 to 10% by mass. Wet grip performance can be improved by containing 1% by mass or more of component (d). On the other hand, when the component (d) contained in the rubber composition for tires is 20% by mass or less, there is an advantage that the wear resistance of the rubber composition can be maintained without deteriorating.

(1.5. Other compounds)
In addition to the above components, the rubber composition of the present invention may contain compounding agents commonly used in the rubber industry, such as antioxidants, antiozonants, softeners, processing aids, waxes, liquid rubbers, and foaming agents. , oil, fatty acids with 8 to 30 carbon atoms such as stearic acid, zinc oxide (ZnO), vulcanization accelerators, vulcanization retarders, and vulcanizing agents (sulfur), etc., within a range that does not impair the purpose of the present invention. can be appropriately selected and blended. As these compounding agents, it is possible to employ a wide range of known compounding agents used in rubber compositions for tires, and for example, commercially available products can be preferably used.

In addition, in the rubber composition containing the above component (c), a silane coupling agent, titanate, etc. may be added for the purpose of increasing the toughness of the rubber composition by silica, or for the purpose of increasing the abrasion resistance as well as the tear strength of the rubber composition. A coupling agent, an aluminate coupling agent, and a zirconate coupling agent may be blended.

The silane coupling agent that can be used in combination with component (c) is not particularly limited, and commercially available products can be suitably used. Examples of such silane coupling agents include sulfide, polysulfide, thioester, thiol, olefin, epoxy, amino and alkyl silane coupling agents.

Examples of sulfide-based silane coupling agents include bis(3-triethoxysilylpropyl) tetrasulfide, bis(3-trimethoxysilylpropyl) tetrasulfide, bis(3-methyldimethoxysilylpropyl) tetrasulfide, bis( 2-triethoxysilylethyl) tetrasulfide, bis(3-triethoxysilylpropyl) disulfide, bis(3-trimethoxysilylpropyl) disulfide, bis(3-methyldimethoxysilylpropyl) disulfide, bis(2-triethoxysilyl) ethyl) disulfide, bis(3-triethoxysilylpropyl) trisulfide, bis(3-trimethoxysilylpropyl) trisulfide, bis(3-methyldimethoxysilylpropyl) trisulfide, bis(2-triethoxysilylethyl) trisulfide Sulfide, bis(3-monoethoxydimethylsilylpropyl) tetrasulfide, bis(3-monoethoxydimethylsilylpropyl) trisulfide, bis(3-monoethoxydimethylsilylpropyl) disulfide, bis(3-monomethoxydimethylsilylpropyl) Tetrasulfide, bis(3-monomethoxydimethylsilylpropyl)trisulfide, bis(3-monomethoxydimethylsilylpropyl)disulfide, bis(2-monoethoxydimethylsilylethyl)tetrasulfide, bis(2-monoethoxydimethylsilylethyl) ) trisulfide, bis(2-monoethoxydimethylsilylethyl)disulfide and the like. Of these, bis(3-triethoxysilylpropyl)tetrasulfide is particularly preferred.

Thioester-based silane coupling agents include, for example, 3-hexanoylthiopropyltriethoxysilane, 3-octanoylthiopropyltriethoxysilane, 3-decanoylthiopropyltriethoxysilane, and 3-lauroylthiopropyltriethoxysilane. , 2-hexanoylthioethyltriethoxysilane, 2-octanoylthioethyltriethoxysilane, 2-decanoylthioethyltriethoxysilane, 2-lauroylthioethyltriethoxysilane, 3-hexanoylthiopropyltrimethoxysilane, 3-octanoylthiopropyltrimethoxysilane, 3-decanoylthiopropyltrimethoxysilane, 3-lauroylthiopropyltrimethoxysilane, 2-hexanoylthioethyltrimethoxysilane, 2-octanoylthioethyltrimethoxysilane, 2 -decanoylthioethyltrimethoxysilane, 2-lauroylthioethyltrimethoxysilane and the like.

Thiol-based silane coupling agents include, for example, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-[ethoxybis(3,6,9,12,15 -Pentaoxaoctacosan-1-yloxy)silyl]-1-propanethiol and the like.

Examples of olefin-based silane coupling agents include dimethoxymethylvinylsilane, vinyltrimethoxysilane, dimethylethoxyvinylsilane, diethoxymethylvinylsilane, triethoxyvinylsilane, vinyltris(2-methoxyethoxy)silane, allyltrimethoxysilane, and allyltrimethoxysilane. Ethoxysilane, p-styryltrimethoxysilane, 3-(methoxydimethoxydimethylsilyl)propyl acrylate, 3-(trimethoxysilyl)propyl acrylate, 3-[dimethoxy(methyl)silyl]propyl methacrylate, 3-(trimethoxysilyl) Propyl methacrylate, 3-[dimethoxy(methyl)silyl]propyl methacrylate, 3-(triethoxysilyl)propyl methacrylate, 3-[tris(trimethylsiloxy)silyl]propyl methacrylate and the like can be mentioned.

Examples of epoxy-based silane coupling agents include 3-glycidyloxypropyl(dimethoxy)methylsilane, 3-glycidyloxypropyltrimethoxysilane, diethoxy(3-glycidyloxypropyl)methylsilane, and triethoxy(3-glycidyloxypropyl)silane. , 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and the like. Of these, 3-glycidyloxypropyltrimethoxysilane is preferred.

Examples of amino-based silane coupling agents include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyltriethoxysilane, 3-ethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)- 2-aminoethyl-3-aminopropyltrimethoxysilane and the like can be mentioned. Of these, 3-aminopropyltriethoxysilane is preferred.

Examples of alkyl-based silane coupling agents include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane. silane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane and the like. Of these, methyltriethoxysilane is preferred.

Among these silane coupling agents, bis(3-triethoxysilylpropyl)tetrasulfide can be particularly preferably used.

The titanate coupling agent that can be used in combination with component (c) is not particularly limited, and commercially available products can be suitably used. Examples of such titanate coupling agents include alkoxide, chelate and acylate titanate coupling agents.

Examples of alkoxide titanate coupling agents include tetraisopropyl titanate, tetra-normal butyl titanate, butyl titanate dimer, tetraoctyl titanate, tetra-tert-butyl titanate, tetra-stearyl titanate and the like. Of these, tetraisopropyl titanate is preferred.

Examples of chelate titanate coupling agents include titanium acetylacetonate, titanium tetraacetylacetonate, titanium ethylacetoacetate, titanium dodecylbenzenesulfonic acid compounds, titanium phosphate compounds, titanium octylene glycolate, and titanium ethylacetoacetate. , titanium lactate ammonium salt, titanium lactate, titanium ethanolamine, titanium octylene glycolate, titanium aminoethylaminoethanolate, and the like. Among these, titanium acetylacetonate is preferred.

Examples of the acylate titanate coupling agent include titanium isostearate.

The aluminate coupling agent that can be used in combination with component (c) is not particularly limited, and commercially available products can be suitably used. Examples of such aluminate coupling agents include 9-octadecenylacetoacetate aluminum diisopropylate, aluminum secondary butoxide, aluminum trisacetylacetonate, aluminum bisethylacetoacetate monoacetylacetonate, aluminum trisethylacetoacetate and the like. can be mentioned. Of these, 9-octadecenylacetoacetate aluminum diisopropylate is preferred.

The zirconate coupling agent that can be used in combination with component (c) is not particularly limited, and commercially available products can be suitably used. Examples of such zirconate coupling agents include alkoxide, chelate, and acylate zirconate coupling agents.

Examples of alkoxide-based zirconium-based coupling agents include normal propyl zirconate and normal butyl zirconate. Among these, normal butyl zirconate is preferred.

Chelate-based zirconate coupling agents include, for example, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium ethylacetoacetate, zirconium lactate ammonium salt, and the like. Among these, zirconium tetraacetylacetonate is preferred.

Examples of the acylate zirconate coupling agent include zirconium stearate and zirconium octylate. Among these, zirconium stearate is preferred.

In the present invention, the silane coupling agent, titanate coupling agent, aluminate coupling agent, and zirconate coupling agent may be used singly or in combination of two or more.

The amount of the silane coupling agent compounded in the rubber composition of the present invention is preferably 0.1 to 20 parts by mass, more preferably 3 to 15 parts by mass, per 100 parts by mass of component (c). By making it 0.1 parts by mass or more, the effect of improving the tear strength of the rubber composition can be more suitably expressed, and by making it 20 parts by mass or less, the cost of the rubber composition can be reduced, and as a result , it is possible to improve the economy.

(2. Method for producing rubber composition)
As a method for producing the rubber composition of the present invention, the above components (a), (b), and (c) and, if necessary, (d) may be mixed, and the order of blending may be appropriately set. . For example, a method including the step (A) of mixing raw material components containing the components (a), (b), and (c), and a step of mixing the raw material components containing the components (a) and (b) ( A), and a method comprising a step (B) of mixing the mixture obtained in step (A) and the component (c), and a step of mixing the raw material components including the components (a) and (c) (A ), and a method comprising a step (B) of mixing the mixture obtained in the step (A) and the component (b), and a step (A) of mixing the raw material components containing the components (a) and (b) and a method comprising a step (B) of mixing the mixture obtained in the step (A) and the component (c), a step (A) of mixing the raw material components including the components (a) and (c), and a method including step (B) of mixing the mixture obtained in step (A) and component (b).

When the above component (d) is added, it may be added in either step (A) or step (B) of the above method.

Among them, a preferable production method is a method including the step (A) of kneading the raw material components including the components (a), (b) and (c).

A preferable manufacturing method when adding the above component (d) is a method including the step (A) of kneading the raw material components including the above components (a), (b), (c) and (d).

(2.1. Step (A))
In the production method of the present invention, the preferred step (A) is the step of mixing raw material components including the above components (a), (b), and (c), and optionally (d).

In this specification, "mixing" includes not only the mode of simply mixing, but also the mode of so-called "kneading".

In step (A), raw material components including components (a), (b), and (c), and optionally (d) are mixed. In this mixing method, the total amount of each component may be mixed at once, or each component may be divided and mixed according to the purpose such as viscosity adjustment. Further, after mixing the components (a) and (b), the component (c) is added, or after the components (a) and (c) are mixed, the component (b) is added. When the component (d) is mixed, the component (d) is added after the components (a), (b) and (c) are mixed, or the component (a) , (b), and (d) are mixed and then the component (c) is added, or after the components (a), (c) and (d) are mixed, the component (b) is added. Or, after mixing the components (a) and (b), the components (c) and (d) are added, or after mixing the components (a) and (c), the components (b) and (d) may be added, or after the components (a) and (d) are mixed, the components (b) and (c) may be added and mixed. The mixing operation may be repeated to evenly disperse the components. Also, a filler masterbatch rubber in which a filler is previously added to the rubber by a wet method and/or a dry mixing method may be used.

In addition, another mixing method in step (A) includes step (A-1) of mixing the above components (a) and (b) and, if necessary, (d), and the A two-step mixing method including a step (A-2) of mixing the obtained mixture with raw material components including the component (c) can be mentioned.

The temperature at which the rubber composition is mixed in step (A) is not particularly limited. For example, the temperature of the rubber composition is preferably 100 to 190°C, more preferably 110 to 175°C. , 120 to 170°C.

The mixing time in step (A) is not particularly limited. For example, it is preferably 10 seconds to 20 minutes, more preferably 30 seconds to 10 minutes, and further preferably 1 minute to 8 minutes. preferable.

Also, a masterbatch in which the above components (a) and (b) are mixed in an arbitrary ratio in advance may be used.

The amount of component (b) in the masterbatch is preferably 0.01 to 200 parts by mass, particularly preferably 0.1 to 100 parts by mass, per 100 parts by mass of component (a).

The temperature at which the components (a) and (b), and optionally (d) are mixed in step (A-1) is preferably 60 to 190°C, more preferably 70 to 160°C. is more preferred, and 80 to 150°C is even more preferred. By setting the mixing temperature to 60°C or higher, the reaction can proceed smoothly, and by setting the mixing temperature to 190°C or lower, deterioration of the rubber can be suppressed.

The mixing time in step (A-1) is desirably 10 seconds to 20 minutes, more preferably 30 seconds to 10 minutes, even more preferably 60 seconds to 7 minutes. By setting the mixing time to 10 seconds or more, the reaction can be sufficiently advanced. On the other hand, by setting the mixing time within 20 minutes, it is excellent in terms of productivity.

The temperature at which the mixture obtained in step (A-1) and the component (c) in step (A-2) are mixed is not particularly limited. It is preferably 110 to 175°C, even more preferably 130 to 170°C.

The mixing time in step (A-2) is not particularly limited. For example, it is preferably 10 seconds to 20 minutes, more preferably 30 seconds to 10 minutes, and 1 minute to 8 minutes. is more preferred.

(2.2. Step (B))
In the production method of the present invention, a preferred step (B) is a step of mixing the mixture obtained in step (A) and, if necessary, other compounding agents.

Step (B) can be performed under heating conditions. The heating temperature in this step is not particularly limited, and is preferably 60 to 140°C, more preferably 80 to 120°C, and even more preferably 90 to 120°C.

The mixing time is not particularly limited, and is preferably 10 seconds to 20 minutes, more preferably 30 seconds to 10 minutes, even more preferably 60 seconds to 5 minutes.

When proceeding from step (A) to step (B), it is preferable to lower the temperature after completion of the previous step by 30° C. or more before proceeding to the next step (B).

In step (A), mixing is performed using a Banbury mixer, rolls, intensive mixer, kneader, single-screw extruder, twin-screw extruder, or the like. After that, it is extruded and processed in an extrusion process, and formed into, for example, a tread member or a sidewall member. Subsequently, it is pasted and molded by a normal method on a tire molding machine to mold a green tire. The raw tire is heated and pressurized in a vulcanizer to obtain a tire.

In the method for producing the rubber composition of the present invention, other compounding agents such as stearic acid, zinc oxide, anti-aging agents, vulcanizing agents, etc., which are usually blended in the rubber composition, are optionally added to the step (A) or It can be added in step (B).

Other compounding agents may be added in either step (A) or step (B), or may be added separately in step (A) and step (B). Among other compounding agents, the vulcanizing agent or vulcanization accelerator is preferably added in the step (B).

(2.3. Molding method of rubber composition)
The rubber composition in the present invention is mixed using a Banbury mixer, rolls, intensive mixer, kneader, single-screw extruder, twin-screw extruder, or the like. After that, it is extruded and processed in an extrusion process, and formed into, for example, a tread member or a sidewall member. Subsequently, it is pasted and molded by a normal method on a tire molding machine to mold a green tire. The raw tire is heated and pressurized in a vulcanizer to obtain a tire.

(3. Tire)
The tire of the present invention is a tire produced using the rubber composition of the present invention.

Examples of the tire of the present invention include pneumatic tires (radial tires, bias tires, etc.), solid tires, and the like.

The use of the tire is not particularly limited, and examples thereof include passenger car tires, high-load tires, motorcycle (motorcycle) tires, studless tires, etc. Among them, it can be suitably used for passenger car tires.

The shape, structure, size and material of the tire of the present invention are not particularly limited and can be appropriately selected according to the purpose.

In the tire of the present invention, the rubber composition is used for at least one member selected from the tread portion, sidewall portion, bead area portion, belt portion, carcass portion and shoulder portion.

Among them, it is preferable to form the tire tread portion or the sidewall portion of the pneumatic tire from the rubber composition, and forming the tire tread portion from the rubber composition is a particularly preferable embodiment.

The tread part is the part that has a tread pattern and is in direct contact with the road surface, and is the outer skin part of the tire that protects the carcass and prevents wear and damage. Refers to the base tread on the inside.

The sidewall portion is, for example, the portion from the lower side of the shoulder portion to the bead portion in the pneumatic radial tire, which protects the carcass and is the portion that bends the most during running.

The bead area portion is a portion that has the role of fixing both ends of the carcass cord and fixing the tire to the rim at the same time. A bead is a bundled structure of high carbon steel.

The belt portion is a reinforcing band stretched in the circumferential direction between the radial structure tread and the carcass. The carcass is strongly tightened like a hoop on a bucket, increasing the rigidity of the tread.

The carcass portion is a portion of the cord layer that forms the skeleton of the tire, and plays a role in withstanding the load, impact, and filling air pressure that the tire receives.

The shoulder portion is the shoulder portion of the tire and serves to protect the carcass.

The tire of the invention can be manufactured according to methods hitherto known in the field of tires. As the gas to be filled in the tire, normal air or air with adjusted oxygen partial pressure; inert gas such as nitrogen, argon, helium, etc. can be used.

The tire of the present invention can provide a tire having excellent wet grip performance.

Although the embodiments of the present invention have been described above, the present invention is by no means limited to such examples, and can of course be embodied in various forms without departing from the gist of the present invention.

EXAMPLES Hereinafter, embodiments of the present invention will be described more specifically based on Examples, but the present invention is not limited to these.

Production Example 1: Production of 3-(naphthalen-2-yl)-1H-pyrazol-5(4H)-one (Compound (b)-2) 8.5 g (52.1 mmol) of carbonyldiimidazole was placed in a 100 mL eggplant-shaped flask, and 60 mL of dehydrated tetrahydrofuran were added and stirred at room temperature. Then 7.5 g (43.6 mmol) of 2-naphthoic acid was added to the mixture and stirred overnight at room temperature. Hereinafter, the obtained reaction liquid is referred to as "reaction liquid 1".

14.8 g (87.0 mmol) of potassium monoethylmalonate, 210 mL of dehydrated acetonitrile, and 18.3 mL (132.4 mmol) of triethylamine were added to a 500 mL four-necked flask and stirred under ice cooling. Then, 10.4 g (109.2 mmol) of magnesium chloride was added to this mixture and stirred at room temperature for 4 hours. The above reaction solution 1 was added dropwise to the obtained reaction solution, and the mixture was stirred overnight at room temperature.

The reaction mixture was concentrated, 125 mL of toluene was added to the resulting residue, and the mixture was washed with 70 mL of 4M hydrochloric acid and 70 mL of water, and the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. This was purified by silica gel column chromatography (n-hexane:ethyl acetate=4:1 (volume ratio)) to obtain a colorless transparent liquid.

2.2 mL (44.8 mmol) of hydrazine monohydrate was added to this liquid, 2.0 mL (35.0 mmol) of acetic acid was added dropwise, and the mixture was refluxed for 4 hours. The reaction solution was returned to room temperature, 30 mL of diisopropyl ether was added, and the precipitated crystals were filtered to obtain 8.22 g of 3-(naphthalen-2-yl)-1H-pyrazol-5(4H)-one as a white solid. rice field.
Melting point: 204°C
¹ H-NMR (300 MHz, d ₆ -DMSO, δppm):
11.94 (1H, br), 8.20-8.21 (1H, J=1.2Hz, d), 7.82-7.96 (4H, m), 7.47-7.56 (2H , m), 6.02 (1H, s)
¹³ C-NMR (500 MHz, d ₆ -DMSO, δppm):
168.13, 160.95, 143.83, 133.06, 132.39, 128.30, 127.90, 127.62, 126.55, 126.06, 123.28, 123.14, 87. 10

Production Example 2: Production of 3-(furan-2-yl)-1H-pyrazol-5(4H)-one (Compound (b)-3) 8.7 g (53.5 mmol) of carbonyldiimidazole was placed in a 100 mL eggplant-shaped flask, and 60 mL of dehydrated tetrahydrofuran were added and stirred at room temperature. Then, 5.0 g (45.0 mmol) of 2-furancarboxylic acid was added to this mixture and stirred overnight at room temperature. Hereinafter, the obtained reaction liquid is referred to as "reaction liquid 2".

14.8 g (87.0 mmol) of potassium monoethylmalonate, 200 mL of dehydrated acetonitrile, and 18.3 mL (132.4 mmol) of triethylamine were added to a 500 mL four-necked flask and stirred under ice cooling. Then, 10.4 g (109.2 mmol) of magnesium chloride was added to this mixture and stirred at room temperature for 4 hours. The above reaction liquid 2 was added dropwise to this reaction liquid, and the mixture was stirred overnight at room temperature.

The obtained reaction solution was concentrated, 120 mL of chloroform was added, washed with 70 mL of 4M hydrochloric acid and 70 mL of water, and the organic layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain a colorless transparent liquid.

2.5 mL (50.7 mmol) of hydrazine monohydrate was added to the resulting liquid, 2.0 mL (35.0 mmol) of acetic acid was added dropwise, and the mixture was refluxed for 4 hours. The resulting reaction solution is returned to room temperature, 30 mL of diisopropyl ether is added, and the precipitated crystals are filtered to obtain 3-(furan-2-yl)-1H-pyrazol-5(4H)-one as a white solid.5. 47 g was obtained.
Melting point: 231°C
¹ H-NMR (300 MHz, d ₆ -DMSO, δppm):
11.79 (2H, br), 7.68-7.69 (1H, m), 6.69 (1H, J = 3.3 Hz, d), 6.55 (1H, J = 1.8, 1 .5, 1.8 Hz, dd), 5.69 (1 H, s)
¹³ C-NMR (500 MHz, d ₆ -DMSO, δppm):
160.23, 146.16, 142.24, 135.84, 111.50, 105.77, 85.88

Production Example 3: Production of 3-phenyl-1H-pyrazol-5(4H)-one (Compound (b)-4) 25 g (0.13 mol) of ethyl benzoylacetate and 25 mL of ethanol are added to a 100 mL four-necked flask and stirred. did. While cooling this in a water bath, 6.5 mL (0.13 mol) of hydrazine monohydrate was added dropwise. After stirring at room temperature for 4 hours, the precipitated solid was filtered, washed with 50 mL of a mixture of water:methanol=1:1 (volume ratio), and dried to give 3-phenyl-1H-pyrazole-5 as a white solid. 18.8 g of (4H)-one were obtained.
Melting point: 236°C
¹ H-NMR (500 MHz, d ₆ -DMSO, δppm):
12.03 (1H, br), 9.69 (1H, br), 7.66 (2H, m), 7.39 (2H, m), 7.30 (1H, m), 5.88 (1H , s)
¹³ C-NMR (500 MHz, d ₆ -DMSO, δppm):
161.00, 143.48, 130.48, 128.73, 127.71, 124.73, 86.87

Production Example 4: Production of 3-propyl-1H-pyrazol-5(4H)-one (Compound (b)-5) In a 500 mL four-necked flask, 24.8 g (0.16 mol) of methyl 3-oxohexanoate, and 260 mL of ethanol was added and stirred. While cooling in an ice bath, 8.6 mL (0.18 mol) of hydrazine monohydrate was added dropwise, and after stirring for 2 hours under ice cooling, the reaction solution was heated under reflux for 2 hours, and the reaction solution was cooled to room temperature. The precipitated solid was filtered, washed with 50 mL of a mixed solution of water:methanol=1:1 (volume ratio), and dried to give 3-propyl-1H-pyrazol-5(4H)-one as a white solid13. 2 g was obtained.
Melting point: 205-206°C
¹ H-NMR (500 MHz, d ₆ -DMSO, δppm):
11.11 (1H, br), 9.42 (1H, br), 5.23 (1H, s), 2.41 (2H, J = 7.5 Hz, t), 1.54 (2H, m) , 0.88 (3H, J=7.3 Hz, t)
¹³ C-NMR (500 MHz, d ₆ -DMSO, δppm):
160.87, 144.04, 87.93, 27.67, 21.93, 13.57

Production Example 5: Production of 4,4′-(phenylmethylene)bis(5-methyl-1H-pyrazol-3(2H)-one) (Compound (b)-6) In a 2 L four-necked flask, 1 L of water, 10 g (0.10 mol) of 3-methyl-5-pyrazolone, 5.4 g (0.05 mol) of benzaldehyde, and 0.73 g (2.5 mmol) of sodium dodecylsulfate were added, stirred at room temperature for 30 minutes, and then refluxed for 1 hour. did. After stirring the reaction mixture for 30 minutes while cooling it in an ice bath, the precipitated solid was filtered, washed with 500 mL of water, and dried to obtain 4,4′-(phenylmethylene)bis(5) as a pale yellow solid. -methyl-1H-pyrazol-3(2H)-one) were obtained.
Melting point: 230-232°C
¹ H-NMR (500 MHz, d ₆ -DMSO, δppm):
11.31 (4H, br), 7.20 (2H, m), 7.12 (3H, m), 4.81 (1 H, s), 2.07 (6H, s)
¹³ C-NMR (500 MHz, d ₆ -DMSO, δppm):
161.24, 143.33, 139.73, 127.67, 127.47, 125.35, 104.21, 32.72, 10.34

Production Example 6: Production of 4,4′-(4-hydroxyphenylmethylene)bis(5-methyl-1H-pyrazol-3(2H)-one) (compound (b)-7) In a 3 L four-necked flask, 2.5 L of water, 25.0 g (0.26 mol) of 3-methyl-5-pyrazolone, 15.6 g (0.13 mol) of 4-hydroxybenzaldehyde, and 1.84 g (6.4 mmol) of sodium dodecylsulfate were added to room temperature. After stirring at rt for 30 minutes, it was refluxed for 1 hour. After stirring the reaction mixture for 30 minutes while cooling it in an ice bath, the precipitated solid was filtered, washed with 2.5 L of water, and dried to give a pale yellow solid of 4,4'-(4-hydroxyphenyl). 33.5 g of methylene)bis(5-methyl-1H-pyrazol-3(2H)-one) are obtained.
Melting point: 262-264°C
¹ H-NMR (500 MHz, d ₆ -DMSO, δppm):
11.22 (4H, br), 9.03 (1H, s), 6.91 (2H, J = 8.5 Hz, d), 6.59 (2H, J = 8.5 Hz, d), 4. 71 (1H, s), 2.06 (6H, s)
¹³ C-NMR (500 MHz, d ₆ -DMSO, δppm):
161.12, 155.03, 139.67, 133.44, 128.27, 114.42, 104.84, 31.91, 10.35

Production Example 7: Production of 4,4′-(4-nitrophenylmethylene)bis(5-methyl-1H-pyrazol-3(2H)-one) (compound (b)-8) In a 3 L four-necked flask, 2.5 L of water, 25.0 g (0.26 mol) of 3-methyl-5-pyrazolone, 19.3 g (0.13 mol) of 4-nitrobenzaldehyde, and 1.84 g (6.4 mmol) of sodium dodecylsulfate were added and the mixture was stirred at room temperature. After stirring at rt for 30 minutes, it was refluxed for 1 hour. After stirring the reaction mixture for 30 minutes while cooling it in an ice bath, the precipitated solid was filtered, washed with 500 mL of methanol, and dried to give a pale yellow solid of 4,4′-(4-nitrophenylmethylene). 37.8 g of bis(5-methyl-1H-pyrazol-3(2H)-one) are obtained.
Melting point: 300-302°C
¹ H-NMR (500 MHz, d ₆ -DMSO, δppm):
11.40 (4H, br), 8.12 (2H, J=8.8Hz, d), 7.38 (2H, J=8.8Hz, d), 4.98 (1H, s), 2. 10 (6H, s)
¹³ C-NMR (500 MHz, d ₆ -DMSO, δppm):
160.82, 151.71, 145.56, 139.71, 128.76, 122.94, 103.24, 32.95, 10.28

Production Example 8: Production of 4-[(dimethylamino)methylidene)-3-methyl-1H-pyrazol-5(4H)-one (Compound (b)-9) In a 500 mL four-necked flask, 300 mL of xylene, 3- 14.7 g (0.15 mol) of methyl-5-pyrazolone and 21.6 g (0.18 mol) of N,N-dimethylformamide dimethylacetal were added and stirred at 110° C. overnight. After cooling the reaction solution to room temperature, the precipitated solid was filtered, washed with 300 mL of toluene, and dried to give a yellow solid of 4-[(dimethylamino)methylidene]-3-methyl-1H-pyrazole-5(4H). )-one 20.3 g were obtained.
Melting point: 158-159°C
¹ H-NMR (500 MHz, d ₆ -DMSO, δppm):
10.30 (1H, br), 7.27 (1H, s), 3.75 (3H, s), 3.26 (3H, s), 1.97 (3H, s)
¹³ C-NMR (500 MHz, d ₆ -DMSO, δppm):
164.77, 152.66, 149.66, 97.13, 46.74, 42.44, 13.35

Production Example 9: Production of 4-{[4-dimethylamino]phenyl}methylidene}-3-methyl-1H-pyrazol-5(4H)-one (Compound (b)-10) Ethanol was added to a 3 L four-necked flask. 2.7 L, 27.0 g (0.28 mol) of 3-methyl-5-pyrazolone, 44.4 g (0.30 mol) of 4-dimethylaminobenzaldehyde, and 4.7 g (55 mmol) of piperidine were added and refluxed for 3 hours. . After stirring the reaction mixture overnight at room temperature, the precipitated solid is filtered and dried to give 4-{[4-dimethylamino]phenyl}methylidene}-3-methyl-1H-pyrazole-5 as a pale yellow solid. 46.3 g of (4H)-one were obtained.
Melting point: 164°C
¹ H-NMR (500 MHz, d _-DMF , δppm):
10.91 (1H, br), 8.70 (2H, J=9.3Hz, d), 7.45 (1H, s), 6.83 (2H, J=9.3Hz, d), 3. 15 (6H, s), 2.18 (3H, s)
¹³ C-NMR (500 MHz, d _-DMF , δppm):
166.74, 153.84, 150.55, 146.23, 136.92, 122.49, 120.74, 111.43, 39.58, 12.98

Production Example 10: Production of 3-undecyl-1H-pyrazol-5(4H)-one (Compound (b)-11) 2.8 g (17.4 mmol) of carbonyldiimidazole and 20 mL of chloroform were added to a 50 mL eggplant flask. , and stirred at room temperature. To this mixture was then added 2.9 g (14.5 mmol) of lauric acid and stirred overnight at room temperature. Hereinafter, the obtained reaction liquid is referred to as "reaction liquid 3".

4.9 g (30.0 mmol) of potassium monoethylmalonate, 70 mL of dehydrated acetonitrile, and 6.1 mL (44.1 mmol) of triethylamine were added to a 200 mL four-necked flask and stirred under ice-cooling. Then, 3.5 g (36.4 mmol) of magnesium chloride was added to the resulting mixture and stirred at room temperature for 4 hours. The above reaction solution 3 was added dropwise to this reaction solution, and the mixture was stirred overnight at room temperature. The resulting reaction solution was concentrated, 42 mL of chloroform was added, washed with 48 mL of 2M hydrochloric acid and 48 mL of water, and the organic layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain the desired product.

20 mL of ethanol and 0.7 mL (14.9 mmol) of hydrazine monohydrate were added to the resulting desired product, 0.7 mL (11.7 mmol) of acetic acid was added dropwise, and the mixture was refluxed for 4 hours. The reaction solution was returned to room temperature, 10 mL of diisopropyl ether was added, and the precipitated crystals were filtered to obtain 2.83 g of 3-undecyl-1H-pyrazol-5(4H)-one as a white solid.
Melting point: 188°C
¹ H-NMR (300 MHz, d ₆ -DMSO, δppm):
11.05 (1H, br), 9.45 (1H, br), 5.21 (1H, s), 2.39-2.44 (2H, J=7.5Hz, t), 1.48- 1.53 (2H, m), 1.30 (16H, s), 0.83-0.88 (3H, m)
¹³ C-NMR (500 MHz, d ₆ -DMSO, δppm):
160.85, 144.20, 87.84, 31.27, 29.01, 28.98, 28.95, 28.71, 28.68, 28.62, 28.57, 25.60, 22. 06, 13.90

Production Example 11: Production of 4-(2-hydroxyethyl)-3-methyl-1H-pyrazol-5(4H)-one (Compound (b)-12) In a 100 mL four-necked flask, α-acetyl-γ- 24.3 g (0.19 mol) of butyrolactone and 24 mL of ethanol were added and stirred. While cooling this with an ice bath, 9.7 mL (0.20 mol) of hydrazine monohydrate was added dropwise, and the mixture was stirred at room temperature for 3 hours. The precipitated solid was filtered, washed with 50 mL of isopropanol, and dried to obtain 23.8 g of 4-(2-hydroxyethyl)-3-methyl-1H-pyrazol-5(4H)-one as a white solid. .
Melting point: 182°C
¹ H-NMR (500 MHz, d _-DMF , δppm):
10.62 (2H, br), 3.78 (2H, J = 7.0 Hz, t), 3.66 (1 H, br), 2.69 (2H, J = 7.0 Hz, t), 2. 31 (3H, s)
¹³ C-NMR (500 MHz, d _-DMF , δppm):
160.88, 137.87, 98.61, 62.29, 26.18, 9.66

Production Example 12: Production of 4-benzyl-3-methyl-1H-pyrazol-5(4H)one (Compound (b)-13) Into a 100 mL four-necked flask, 24.5 g of ethyl 2-benzylacetoacetate (0.5 g) was added. 11 mol), and 25 mL of ethanol were added and stirred. After 5.7 mL (0.12 mol) of hydrazine monohydrate was added dropwise while cooling this in an ice bath, the mixture was stirred at room temperature for 3 hours. The precipitated solid was filtered, washed with 50 mL of a mixture of water:methanol=1:1 (volume ratio), and dried to give 4-benzyl-3-methyl-1H-pyrazole-5(4H) as a white solid. 15.6 g of on were obtained.
Melting point: 228-229°C
¹ H-NMR (500 MHz, d ₆ -DMSO, δppm):
11.08 (1H, br), 9.46 (1H, br), 7.24 (2H, m), 7.14 (3H, m), 3.55 (2H, s), 2.01 (3H , s)
¹³ C-NMR (500 MHz, d ₆ -DMSO, δppm):
159.58, 141.90, 136.82, 128.06, 127.96, 125.37, 99.94, 27.28, 9.94

Preparation Example 13: Preparation of 1-phenyl-1H-pyrazol-3(2H)-one (Compound (b)-14) In a 1 L four-necked flask, 10 g (62 mmol) of 1-phenyl-3-pyrazolidone and N, 150 mL of N-dimethylformamide was added and stirred. 317 mg (3.2 mmol) of copper (I) chloride was added thereto, and the mixture was stirred overnight in an open system. 750 mL of water was added to the reaction mixture, and the mixture was stirred for 30 minutes while cooling in an ice bath. The precipitated solid was filtered, washed with 750 mL of water, and dried to obtain 1-phenyl-1H-pyrazole-3 as a pale brown solid. 6.1 g of (2H)-one were obtained.
Melting point: 152°C
¹ H-NMR (500 MHz, d ₆ -DMSO, δppm):
10.22 (1H, br), 8.22 (1H, s), 7.68 (2H, m), 7.42 (2H, m), 7.18 (1H, m), 5.80 (1H , s)
¹³ C-NMR (500 MHz, d ₆ -DMSO, δppm):
162.64, 139.79, 129.29, 128.37, 124.59, 116.76, 94.47

Production Example 14: Production of 4-methyl-2,3-diazospiro[4.4]non-3en-1-one (Compound (b)-15) 7.2 g of methyl acetoacetate (62 .0 mmol), 23.1 g (75 mmol) of 1,4-diiodobutane, 42.9 g (310 mmol) of potassium carbonate, and 220 mL of dimethylsulfoxide were added and stirred overnight at room temperature. After adding 220 mL of water to the reaction solution and stirring for 10 minutes, the organic layer obtained by extraction with 300 mL of isopropyl ether was washed twice with 200 mL of water. After the organic layer was dried over sodium sulfate, it was concentrated and subjected to column purification (hexane:ethyl acetate=50:1 (volume ratio)) to obtain 6.5 g (36 mmol) of the intermediate.

The obtained intermediate and 6 mL of ethanol were mixed, 1.8 mL (39 mmol) of hydrazine monohydrate was added while cooling on an ice bath, and the mixture was stirred at 60° C. overnight. The solid obtained by concentrating the reaction solution was washed with 40 mL of a mixed solution of hexane:ethyl acetate=5:1 (volume ratio) to give 4-methyl-2,3-diazospiro[4.4] as a white solid. 3.8 g of non-3en-1-one were obtained.
Melting point: 83-84°C
¹ H-NMR (500 MHz, d ₆ -DMSO, δppm):
10.77 (1H, s), 1.92 (3H, s), 1.86-1.66 (8H, m)
¹³ C-NMR (500 MHz, d ₆ -DMSO, δppm):
181.64, 163.37, 55.78, 33.53, 26.48, 13.34

Preparation 15: Preparation of 4,5,6,7-tetrahydro-2H-indazol-3(3aH)-one (Compound (b)-16) Ethyl 2-oxocyclohexanecarboxylate was added to a 100 mL four-necked flask. 5 g (0.14 mol) and 24 mL of ethanol were added and mixed. While cooling with an ice bath, 7.3 mL (0.15 mol) of hydrazine monohydrate was added dropwise thereto, and after stirring at 80° C. for 3 hours, the mixture was stirred for 30 minutes while cooling with an ice bath. After that, the precipitated solid was filtered, washed with 50 mL of a mixture of water:methanol=1:1 (volume ratio), and dried to obtain 4,5,6,7-tetrahydro-2H-indazole-3 as a white solid. 17.3 g of (3aH)-one were obtained.
Melting point: 286-288°C
¹ H-NMR (500 MHz, d ₆ -DMSO, δppm):
10.50 (1H, br), 9.66 (1H, br), 2.43 (2H, J = 5.7 Hz, t), 2.22 (2H, J = 5.7 Hz, t), 1. 67-1.62 (4H, m)
¹³ C-NMR (500 MHz, d ₆ -DMSO, δppm):
158.30, 139.62, 98.41, 22.86, 22.27, 21.26, 18.88

Preparation Example 16: Preparation of 1,3-diphenyl-1H-pyrazol-5(4H)-one (Compound (b)-17) In a 1 L four-necked flask, 50.0 g (0.26 mol) of ethyl benzoylacetate, phenyl 28.1 g (0.26 mol) of hydrazine, 4.5 mL (0.08 mol) of acetic acid, and 500 mL of water were added and mixed. After stirring at 100° C. for 1 hour, stirring was continued for 30 minutes while cooling in an ice bath, the precipitated solid was filtered, washed with 1 L of a mixed liquid of water:methanol=1:1 (volume ratio), and dried. As a result, 58.0 g of pale orange solid 1,3-diphenyl-1H-pyrazol-5(4H)-one was obtained.
Melting point: 137-138°C
¹ H-NMR (500 MHz, d ₆ -DMSO, δppm):
11.81 (1H, br), 7.83 (4H, m), 7.49 (2H, m), 7.42 (2H, m), 7.35-7.28 (2H, m), 6 .02 (1H, s)
¹³ C-NMR (500 MHz, d ₆ -DMSO, δppm):
153.73, 149.52, 138.85, 133.41, 128.87, 128.51, 127.78, 125.65, 125.04, 121.11, 85.05

Examples 1 to 2 and Comparative Examples 1 to 3: Production of rubber composition Each component shown in step (A) in Table 1 below was mixed in its ratio (parts by weight) and mixed in a Banbury mixer. After curing until the temperature of the mixture reaches 60 ° C. or lower, each component described in step (B) in Table 1 is added in the proportion (parts by mass), and the maximum temperature of the mixture is adjusted to 70 ° C. or lower. A rubber composition was produced by mixing while stirring.

尚、表１における各成分の詳細は、下記の通りである。
※１：成分（ａ）：ＮＲ（天然ゴム）；ＧＵＡＮＧＫＥＮ ＲＵＢＢＥＲ社製、ＴＳＲ－２０
※２：成分（ａ）：ＳＢＲ（スチレンブタジエンゴム）；ＪＳＲ社製、ＳＬ５６３
※３：成分（ａ）：ＢＲ（ブタジエンゴム）；宇部興産社製、ＢＲ１５０Ｂ
※４：カーボンブラック；Ｃａｂｏｔ社製、Ｎ２３４
※５：成分（ｃ）：シリカ；東ソー・シリカ社製、Ｎｉｐｓｉｌ ＡＱ
※６：シランカップリング剤：エボニック社製、Ｓｉ６９
※７：老化防止剤（Ｎ－フェニル－Ｎ'－（１,３－ジメチルブチル）－ｐ－フェニレンジアミン）；Ｋｅｍａｉ Ｃｈｅｍｉｃａｌ Ｃｏ．，Ｌｔｄ社製
※８：ワックス；Ｒｈｅｉｎ Ｃｈｅｍｉｅ Ｒｈｅｉｎａｕ社製、Ａｎｔｉｌｕｘ １１１
※９：酸化亜鉛；Ｄａｌｉａｎ Ｚｉｎｃ Ｏｘｉｄｅ Ｃｏ．，Ｌｔｄ社製
※１０：ステアリン酸；Ｓｉｃｈｕａｎ Ｔｉａｎｙｕ Ｇｒｅａｓｅ社製
※１１：成分（ｄ）：ジシクロペンタジエン樹脂：丸善石油社製、マルカレッツＭ－８９０Ａ
※１２：フェノール樹脂：旭有機材社製、ＳＰ１００６Ｎ
※１３：成分（ｂ）：化合物（ｂ）－１；大塚化学株式会社製、３－メチル－５－ピラゾロン
※１４：加硫促進剤：Ｎ－シクロヘキシル－２－ベンゾチアゾリルスルフェンアミド；大内新興社製、ノクセラーＣＺ－Ｇ
※１５：加硫促進剤：１,３-ジフェニルグアニジン；大内新興社製、ノクセラーＤ
※１６：硫黄 ；Ｓｈａｎｇｈａｉ Ｊｉｎｇｈａｉ Ｃｈｅｍｉｃａｌ Ｃｏ．，Ｌｔｄ社製

The details of each component in Table 1 are as follows.
*1: Component (a): NR (natural rubber); TSR-20 manufactured by GUANGKEN RUBBER
*2: Component (a): SBR (styrene-butadiene rubber); manufactured by JSR, SL563
*3: Component (a): BR (butadiene rubber); BR150B manufactured by Ube Industries, Ltd.
*4: Carbon black; manufactured by Cabot, N234
* 5: Component (c): Silica; manufactured by Tosoh Silica, Nipsil AQ
*6: Silane coupling agent: Si69 manufactured by Evonik
*7: Anti-aging agent (N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine); Kemai Chemical Co.; , Ltd. * 8: Wax; Rhein Chemie Rheinau, Antilux 111
*9: Zinc oxide; Dalian Zinc Oxide Co.; , Ltd. * 10: Stearic acid; Sichuan Tianyu Grease * 11: Component (d): Dicyclopentadiene resin: Maruzen Oil Co., Ltd., Markarets M-890A
* 12: Phenolic resin: SP1006N manufactured by Asahi Organic Chemicals Co., Ltd.
*13: Component (b): Compound (b)-1; Otsuka Chemical Co., Ltd., 3-methyl-5-pyrazolone *14: Vulcanization accelerator: N-cyclohexyl-2-benzothiazolylsulfenamide; large Noxcellar CZ-G manufactured by Naisho Shinko Co., Ltd.
*15: Vulcanization accelerator: 1,3-diphenylguanidine; manufactured by Ouchi Shinko Co., Ltd., Noxcellar D
*16: Sulfur; Shanghai Jinghai Chemical Co.; , Ltd.

Examples 1-2 and Comparative Examples 1-3: Wet Grip Performance Test For the rubber compositions of Examples 1-2 and Comparative Examples 1-3 below, a BPST friction tester was used, and abrasive paper soaked with water was used as a road surface. Frictional resistance was measured under room temperature conditions using #A200. Expressed as an index with the value of Comparative Example 1 obtained here as 100, the wet grip performance index was calculated based on the following formula. It should be noted that the higher the wet grip performance index, the better the wet grip performance.
Formula: Wet grip performance index = (frictional force value of rubber compositions of Examples 1 and 2 and Comparative Examples 2 and 3)/(frictional resistance value of Comparative Example 1) × 100

The rubber composition of the present invention can impart excellent wet grip properties to the rubber component. Therefore, it can be used as each member of various pneumatic tires of various automobiles, especially as tread member, sidewall member, bead area member, belt member, carcass member and shoulder member of pneumatic radial tire. can.

Claims (9)

comprising the following components (a), (b) and (c),
A rubber composition for a tire , wherein the amount of the component (b) is 0.2 to 10 parts by mass relative to 100 parts by mass of the component (c):
Component (a) a rubber component,
Component (b) at least one compound selected from the group consisting of compounds represented by formula (1), compounds represented by formula (2), and salts of the compounds;
Component (c) Silica.

(In formula (1), R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group. R ³ and R ⁴ are Any two of R ² , R ³ and R ⁴ may combine with each other to form an alkylene group, and each of these groups may be combined with one or more substituents. You may have a group.)

(In Formula (2), R ⁵ , R ⁷ and R ⁸ are the same or different and represent a hydrogen atom, an amino group, an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group, and R ⁶ is an alkyl group, an aralkyl group, aryl group, or heterocyclic group, each of which may have one or more substituents.) 2. The rubber composition for a tire according to claim 1, wherein said component (b) is a compound represented by formula (1). The rubber composition for tires according to claim 1 or 2, comprising 5 to 120 parts by mass of component (c) with respect to 100 parts by mass of component (a). The rubber composition for tires according to any one of claims 1 to 3, further comprising a component (d) a hydrocarbon polymer. A tire produced using the tire rubber composition according to any one of claims 1 to 4. The method for producing a rubber composition for tires according to any one of claims 1 to 4, comprising a step (A) of mixing raw material components including the components (a), (b) and (c). 7. The method for producing a rubber composition for tires according to claim 6, wherein said component (d) is further mixed in said step (A). The step (A) includes a step (A-1) of mixing the components (a) and (b), and a step (A-1) of mixing the mixture obtained in the step (A-1) and the component (c). -2), the method for producing a rubber composition for tires according to claim 6. The method for producing a rubber composition for tires according to claim 8, wherein said component (d) is further mixed in said step (A-1).