JP2020084139A - Rubber composition, tire, and additive - Google Patents

Abstract

To provide a rubber composition that expresses excellent low heat build-up properties and toughness, without using any special mixing method, and has excellent workability for tire production.SOLUTION: A rubber composition contains (a) a rubber component, (b) a hydrazide compound of a specific structure, (c) a pyrazolone compound of a specific structure, and (d) carbon black and/or inorganic filler.SELECTED DRAWING: None

Description

The present invention relates to a rubber composition, a tire, and an additive.

In recent years, from the viewpoint of resource saving, energy saving, and environmental protection, regulations on exhaust gas such as carbon dioxide have become strict, and demands for low fuel consumption of automobiles are increasing. Although the driving system and the transmission system such as an engine greatly contribute to the reduction of fuel consumption of an automobile, the rolling resistance of the tire is also greatly involved. Therefore, not only the drive system and the transmission system, but also the rolling resistance of the tire is required to be improved.

As a method of improving the rolling resistance of a tire, it is known to use a rubber composition such that the amount of heat generated by the tire during running is reduced, as an example of such a rubber composition. A composition to which a hydrazide compound is added is known.

In Patent Document 1, by using a rubber composition in which a hydrazide compound is added to a rubber component, it is possible to reduce the heat generation amount of a tire during traveling while maintaining toughness, and as a result, hysteresis loss (rolling). It is described that a tire having low resistance) can be obtained. In the present specification, when a tire is manufactured from a rubber composition, a small amount of heat generated during running of the tire is referred to as "the rubber composition has low heat buildup".

Since the hydrazide compound has a high reactivity with the functional group on the surface of carbon black, the kneading method of a usual rubber composition cannot sufficiently exert the effect of reducing the heat generation of the hydrazide compound, resulting in a special A kneading method of a rubber composition is required (Patent Document 2), and the rubber composition described in Patent Document 1 cannot sufficiently exhibit the effect of low exothermicity having a hydrazide compound.

Further, as is clear from the results of Patent Document 1, if a hydrazide compound is added to the rubber component, workability deteriorates.

JP-A-2000-190704 Japanese Patent Laid-Open No. 8-27315

An object of the present invention is to provide a rubber composition which exhibits excellent low heat buildup and durability without a special kneading method and has excellent processability during tire production.
Another object of the present invention is to provide a tire exhibiting excellent low heat buildup while maintaining the reinforcing property without performing a special kneading method.
Another object of the present invention is to provide an additive that imparts an excellent low exothermicity while maintaining the reinforcing property without performing a special kneading method, and imparts excellent processability. It is in.

The present inventors have conducted extensive studies to solve the above problems, and by using a hydrazide-based compound and a pyrazolone-based compound in combination, it is possible to manufacture a tire without performing a special kneading method. It was found that the rubber component can be imparted with excellent low heat build-up, toughness, and excellent processability during tire production. The present inventors have completed the present invention as a result of further studies based on such findings.

That is, the present invention provides a rubber composition, a method for producing the rubber composition, a tire, and an additive shown below.
Item 1.
A rubber composition containing the following components (a), (b), (c) and (d):
Component (a) rubber component,
Component (b) at least one compound selected from compounds represented by formulas (1) to (3),
Component (c) Compounds represented by Formulas (4) and (5), and at least one compound selected from salts of the compounds,
Component (d) carbon black and/or an inorganic filler.

（式中、Ｚは芳香族環、置換されているか、置換されていないヒダントイン環、炭素原子数０〜１８の飽和又は不飽和直鎖状炭化水素からなる群より選んだ１種であり、Ｑは芳香族基であり、Ｑの置換基Ｘはヒドロキシ基、アミノ基より選んだ少なくとも１種であり、Ｙはピリジル基、ヒドラジノ基より選んだ１種である。Ｒ^ａ〜Ｒ^ｄは水素及び炭素数１〜１８からなるアルキル基、シクロアルキル基、芳香族環であり、それぞれ同じでも異なっていてもよい。）

(In the formula, Z is one selected from the group consisting of an aromatic ring, a substituted or unsubstituted hydantoin ring, and a saturated or unsaturated linear hydrocarbon having 0 to 18 carbon atoms; Is an aromatic group, the substituent X of Q is at least one selected from a hydroxy group and an amino group, Y is one selected from a pyridyl group and a hydrazino group, and R ^{a to} R ^d are hydrogen and An alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, and an aromatic ring, which may be the same or different.)

（式（４）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 (4), R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. R ³ and R ⁴ are They may be bonded to each other to form an alkylidene group, or any two of R ² , R ³ and R ⁴ may be bonded to each other to form an alkylene group, and each of these groups is substituted with one or more substituents. It may have a group.)

（式（５）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．
前記式（２）で表される化合物において、Ｘはヒドロキシ基であり、Ｒ^ａ及びＲ^ｂは同一又は異なって、炭素数１〜１８からなる直鎖状又は分岐状のアルキル基を示す、項１に記載のゴム組成物。
項３．
前記成分（ｃ）が式（４）で表される化合物である、項１又は２に記載のゴム組成物。
項４．
前記成分（ａ）がジエン系ゴムである、項１〜３のいずれかに記載のゴム組成物。
項５．
前記成分（ｂ）及び成分（ｃ）の合計１００質量％中に、前記成分（ｂ）の配合割合が０．０１〜５０質量％である、項１〜４のいずれかに記載のゴム組成物。
項６．
項１〜５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７．
前記成分（ｂ）及び（ｃ）を含む添加剤。
項８．
前記成分（ａ）、（ｂ）、（ｃ）、及び（ｄ）を含む原料成分を混合する工程（Ａ）、並びに、工程（Ａ）で得られる混合物及び加硫剤を混合する工程（Ｂ）を含む、ゴム組成物の製造方法。
項９．
前記工程（Ａ）が、前記成分（ａ）、（ｂ）及び（ｃ）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（ｄ）を混合する工程である、項８に記載の製造方法。

(In the formula (5), 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 or an aralkyl. A group, an aryl group, or a heterocyclic group, each of which may have one or more substituents.)
Item 2.
In the compound represented by the above formula (2), X is a hydroxy group, R ^a and R ^b are the same or different, and represent a linear or branched alkyl group having 1 to 18 carbon atoms, The rubber composition according to 1.
Item 3.
Item 3. The rubber composition according to Item 1 or 2, wherein the component (c) is a compound represented by the formula (4).
Item 4.
Item 4. The rubber composition according to any one of Items 1 to 3, wherein the component (a) is a diene rubber.
Item 5.
Item 5. The rubber composition according to any one of Items 1 to 4, wherein a blending ratio of the component (b) is 0.01 to 50 mass% in a total of 100 mass% of the component (b) and the component (c). ..
Item 6.
A tire produced using the rubber composition according to any one of Items 1 to 5.
Item 7.
An additive containing the components (b) and (c).
Item 8.
The step (A) of mixing the raw material components containing the components (a), (b), (c), and (d), and the step (B of mixing the mixture and the vulcanizing agent obtained in the step (A). The manufacturing method of the rubber composition containing these.
Item 9.
The step (A) includes the step (A-1) of mixing the components (a), (b) and (c), and the mixture obtained in the step (A-1) and the component (d). Item 9. The manufacturing method according to Item 8, which is the step of:

The present invention provides a rubber composition that exhibits excellent low heat build-up and toughness without a special kneading method and has excellent processability during tire production, and a method for producing the rubber composition. be able to.
INDUSTRIAL APPLICABILITY The present invention can provide a fuel-efficient tire having excellent low heat buildup while maintaining reinforcing properties.
INDUSTRIAL APPLICABILITY The present invention can provide an additive for imparting excellent low exothermicity and processability to a rubber component while maintaining the reinforcing property without performing a special kneading method.

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), (c) and (d).
Component (a) Rubber component Component (b) At least one compound selected from compounds represented by Formulas (1) to (3) (c) Compounds represented by Formulas (4) and (5), and At least one compound component (d) carbon black and/or inorganic filler selected from salt of compound

（式中、Ｚは芳香族環、置換されているか、置換されていないヒダントイン環、炭素原子数０〜１８の飽和又は不飽和直鎖状炭化水素からなる群より選んだ１種であり、Ｑは芳香族基であり、Ｑの置換基Ｘはヒドロキシ基、アミノ基より選んだ少なくとも１種であり、Ｙはピリジル基、ヒドラジノ基より選んだ１種である。Ｒ^ａ〜Ｒ^ｄは水素及び炭素数１〜１８からなるアルキル基、シクロアルキル基、芳香族環であり、それぞれ同じでも異なっていてもよい。）

(In the formula, Z is one selected from the group consisting of an aromatic ring, a substituted or unsubstituted hydantoin ring, and a saturated or unsaturated linear hydrocarbon having 0 to 18 carbon atoms; Is an aromatic group, the substituent X of Q is at least one selected from a hydroxy group and an amino group, Y is one selected from a pyridyl group and a hydrazino group, and R ^{a to} R ^d are hydrogen and An alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, and an aromatic ring, which may be the same or different.)

（式（４）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 (4), R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. R ³ and R ⁴ are They may be bonded to each other to form an alkylidene group, or any two of R ² , R ³ and R ⁴ may be bonded to each other to form an alkylene group, and each of these groups is substituted with one or more substituents. It may have a group.)

（式（５）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 the formula (5), 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. A group, an aryl group, or a heterocyclic group, each of which may have one or more substituents.)

By adding the components (b) and (c) to the component (a), imparting excellent low heat build-up, toughness and processability to the component (a) without performing a special kneading method. You can

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

Examples of the natural rubber include natural rubber latex, technically graded rubber (TSR), smoked sheet (RSS), gutta percha, natural rubber derived from Tonaka, natural rubber derived from guayule and natural rubber derived from dandelion, and further modified natural rubber. Modified natural rubbers such as epoxidized natural rubber, methacrylic acid modified natural rubber, halogen modified natural rubber, deproteinized natural rubber and styrene modified natural rubber are also included in the natural rubber of the present invention.

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. Examples thereof include polymer rubber (EPDM), styrene-isoprene-styrene ternary block copolymer (SIS), styrene-butadiene-styrene ternary block copolymer (SBS), and modified synthetic diene rubbers thereof. The modified synthetic diene rubber includes a diene rubber obtained by a modification method such as main chain modification, one-end modification, and both-end modification. Here, examples of the modified functional group of the modified synthetic diene rubber include various functional groups such as an epoxy group, an amino group, an alkoxysilyl group, and a hydroxyl group, and one or more of these functional groups are modified synthetic diene rubbers. 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. The glass transition point of the synthetic diene rubber is also not particularly limited.

Further, the ratio of cis/trans/vinyl of the double bond portion of the natural rubber and the synthetic diene rubber is not particularly limited, and any ratio can be preferably used. The number average molecular weight and the molecular weight distribution of the diene rubber are not particularly limited, but the number average molecular weight of 500 to 3,000,000 and the molecular weight distribution of 1.5 to 15 are preferable. A wide variety of known non-diene rubbers can be used.

The rubber component may be used singly or as a mixture (blend) of two or more. Among them, the preferred rubber component is natural rubber, IR, SBR, BR or a mixture of two or more selected from these, and more preferably natural rubber, SBR, BR or a mixture of two or more selected from these. ..

(1.2. Component (b): at least one compound selected from compounds represented by formulas (1) to (3))
The rubber composition of the present invention is a compound represented by the following formulas (1) to (3) (compound (1),
It contains at least one compound selected from (2) and (3).

（式中、Ｚは芳香族環、置換されているか、置換されていないヒダントイン環、炭素原子数０〜１８の飽和又は不飽和直鎖状炭化水素からなる群より選んだ１種であり、Ｑは芳香族基であり、Ｑの置換基Ｘはヒドロキシ基、アミノ基より選んだ少なくとも１種であり、Ｙはピリジル基、ヒドラジノ基より選んだ１種である。Ｒ^ａ〜Ｒ^ｄは水素及び炭素数１〜１８からなるアルキル基、シクロアルキル基、芳香族環であり、それぞれ同じでも異なっていてもよい。）

(In the formula, Z is one selected from the group consisting of an aromatic ring, a substituted or unsubstituted hydantoin ring, and a saturated or unsaturated linear hydrocarbon having 0 to 18 carbon atoms; Is an aromatic group, the substituent X of Q is at least one selected from a hydroxy group and an amino group, Y is one selected from a pyridyl group and a hydrazino group, and R ^{a to} R ^d are hydrogen and An alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, and an aromatic ring, which may be the same or different.)

In the present specification, the “aryl group” is not particularly limited, and examples thereof include a phenyl group, a biphenyl group, a naphthyl group, a dihydroindenyl group and a 9H-fluorenyl group.

In the present specification, the “alkyl group” is not particularly limited and includes, for example, a linear, branched or cyclic alkyl group, and specifically, for example, methyl, ethyl, n-propyl, isopropyl. , N-butyl, isobutyl, s-butyl, t-butyl, 1-ethylpropyl, and other linear or branched alkyl groups having 1 to 4 carbon atoms, and further 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, and other linear or branched alkyl groups having 1 to 18 carbon atoms; cyclic alkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc. Is mentioned.

These alkyl group and aryl group may each have one or more substituents at any substitutable position. The "substituent" is not particularly limited, and examples thereof include a halogen atom, amino group, aminoalkyl group, alkoxycarbonyl group, acyl group, acyloxy group, amide group, carboxyl group, carboxyalkyl group, formyl group, nitrile group. , 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 have preferably 1 to 5, more preferably 1 to 3.

In the present specification, examples of the “halogen atom” include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom, a bromine atom and an iodine atom.

In the present specification, examples of the “amino group” include not only an amino group represented by —NH ₂ but also methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, s. Linear or branched monoalkyl such as -butylamino, t-butylamino, 1-ethylpropylamino, n-pentylamino, neopentylamino, n-hexylamino, isohexylamino and 3-methylpentylamino groups. Amino group; a substituted amino group such as a dialkylamino group having two linear or branched alkyl groups such as dimethylamino, ethylmethylamino and diethylamino groups is also included.

In the present specification, 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 and like aminoalkyl groups, monoalkyl-substituted aminoalkyl groups or dialkyl-substituted aminoalkyl. Groups and the like.

In the present specification, the "alkoxycarbonyl group" is not particularly limited, and examples thereof include a methoxycarbonyl group and an ethoxycarbonyl group.

In the present specification, the “acyl group” is not particularly limited and includes, for example, a linear or branched alkylcarbonyl group having 1 to 4 carbon atoms such as acetyl, propionyl, pivaloyl group and the like.

In the present specification, the “acyloxy group” is not particularly limited, and examples thereof include acetyloxy, propionyloxy, n-butyryloxy group 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; and the like.

In the present specification, the “carboxyalkyl group” is not particularly limited, and includes, for example, carboxymethyl, carboxyethyl, carboxy-n-propyl, carboxy-n-butyl, carboxy-n-pentyl, carboxy-n-hexyl groups. And other carboxyalkyl groups.

In the present specification, 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.

In the present specification, the "alkoxy group" is not particularly limited and includes, for example, a linear, branched or cyclic alkoxy group, and specific examples thereof include methoxy, ethoxy, n-propoxy and iso. Linear or branched alkoxy group of propoxy, n-butoxy, t-butoxy, n-pentyloxy, neopentyloxy, n-hexyloxy group; cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclo Examples thereof include cyclic alkoxy groups such as heptyloxy and cyclooctyloxy groups.

In the present specification, the “aryloxy group” is not particularly limited, and examples thereof include a phenoxy group, a biphenyloxy group and a naphthoxy group.

In the present specification, the "heterocyclic group" is not particularly limited, and includes, 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-oxa) 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-isobenzofurnyl, 2-benzothienyl, 3-benzothienyl, 4- Benzothienyl, 5-benzothienyl, 6-benzothienyl, 7-benzothienyl, 2-benzoxazolyl, 4-benzoxazolyl, 5-benzoxazolyl, 6-benzoxazolyl, 7-benzooxa 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 and the like.

In the present specification, the "alkylthio group" is not particularly limited, and examples thereof include a methylthio group, an ethylthio group, and an n-propylthio group.

In the present specification, the "arylthio group" is not particularly limited, and examples thereof include a phenylthio group, a naphthylthio group, a biphenylthio group and the like.

As Z of the compound (1) used in the present invention, an aromatic ring (substituted at the ortho, meta or para position), a substituted or unsubstituted hydantoin ring, a saturated or unsaturated C0-18 ring Examples of the saturated linear hydrocarbon include ethylene group, tetramethylene group, heptamethylene group, octamethylene group, octadecamethylene group, and 7,11-octadecadienylene group. R ^{a to} R ^d are hydrogen and an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, or an aromatic ring (substituted at the ortho, meta, or para positions), and they may be the same or different (hereinafter The same applies to the hydrazide compounds (2) and (3)).

Among the compounds (1), the compounds represented by the following chemical formula (1-1) are preferable.

（式（１−１）中、Ｚは、アリール基、アルキル基、及び又はヒダントイン基であり、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。Ｒ^ａ〜Ｒ^ｄは同一又は異なって、水素原子、アルキル基、又はアリール基でありを示し、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 the formula (1-1), Z is an aryl group, an alkyl group, and or a hydantoin group, each of these groups, which may have one or more substituents each .R ^a to R ^d Are the same or different and represent a hydrogen atom, an alkyl group, or an aryl group, and each of these groups may have one or more substituents.

Among the compounds (1-1), compounds in which Z is an alkyl group or an aryl group are preferable.

Among the compounds (1-1), compounds in which R ^a and R ^b are the same or different and each is a linear or branched alkyl group having 1 to 18 carbon atoms are preferable, and a linear or branched alkyl group having 1 to 4 carbon atoms or More preferred are compounds that are branched alkyl groups.

Among the compounds (1-1), compounds in which Z is an aryl group, R ^a and R ^b are the same or different and are ^a linear or branched alkyl group having 1 to 18 carbon atoms, and Z is phenyl Group or a naphthyl group, R ^a and R ^b are the same or different, and a compound having a linear or branched alkyl group having 1 to 4 carbon atoms is more preferable, Z is a phenyl group, and R ^a and R a ^A compound in which ^b is the same or different and is a linear or branched alkyl group having 1 to 4 carbon atoms is particularly preferable.

Specifically, as the compound (1-1), for example, di(1-methylethylidene)hydrazide isophthalate, di(1-methylethylidene)hydrazide adipic acid, di(1-methylpropylidene)hydrazide isophthalate, adipine Acid di(1-methylpropylidene) hydrazide, isophthalic acid di(1,3-dimethylpropylidene) hydrazide, adipic acid di(1,3-dimethylpropylidene) hydrazide, isophthalic acid di(1-phenylethylidene) hydrazide, Examples include adipic acid di(1-phenylethylidene)hydrazide and the like.

Q of the compound (2) used in the present invention is an aromatic group such as a phenyl group and a naphthyl group, and the substituent X of Q is a hydroxy group or an amino group.

Among the compounds (2), compounds represented by the following chemical formula (2-1) are preferable.

（式（２−１）中、Ｑはアリール基であり、ＸはＱの置換基である。Ｒ^ａ及びＲ^ｂは同一又は異なって、水素原子、アルキル基、又はアリール基でありを示し、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 the formula (2-1), Q is an aryl group, and X is a substituent of Q. R ^a and R ^b are the same or different and represent a hydrogen atom, an alkyl group, or an aryl group, Each of these groups may have one or more substituents.)

Among the compounds (2-1), compounds in which R ^a and R ^b are the same or different and each is a linear or branched alkyl group having 1 to 18 carbon atoms are preferable, and a linear or branched alkyl group having 1 to 4 carbon atoms or More preferred are compounds that are branched alkyl groups.

Among the compounds (2-1), compounds in which Q is an aryl group, R ^a and R ^b are the same or different and are ^a linear or branched alkyl group having 1 to 18 carbon atoms, and Q is phenyl Group or a naphthyl group, R ^a and R ^b are the same or different, and a compound which is a linear or branched alkyl group having 1 to 4 carbon atoms is more preferable, Q is a naphthyl group, and R ^a and R a ^A compound in which ^b is the same or different and is a linear or branched alkyl group having 1 to 4 carbon atoms is particularly preferable.

Specifically, as the compound (2-1), for example, N′-(1,3-dimethylbutylidene)salicylic acid hydrazide, 3-hydroxy-N′-(1,3-dimethylbutylidene)-2-naphthoate Examples thereof include acid hydrazide and 1-hydroxy-N′-(1,3-dimethylbutylidene)-2-naphthoic acid hydrazide.

Among the compounds (3), the compounds represented by the following chemical formula (3-1) are preferable.

（式（３−１）中、Ｙは、ピリジル基、及び又はヒドラジノ基であり、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。Ｒ^ａ及びＲ^ｂは同一又は異なって、水素原子、アルキル基、又はアリール基でありを示し、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 the formula (3-1), Y is a pyridyl group and/or a hydrazino group, and each of these groups may have one or more substituents. R ^a and R ^b are the same or different. And a hydrogen atom, an alkyl group, or an aryl group, each of which may have one or more substituents.)

Among the compounds (3-1), compounds in which R ^a and R ^b are the same or different and each is a linear or branched alkyl group having 1 to 18 carbon atoms are preferable, and a linear or branched alkyl group having 1 to 4 carbon atoms or More preferred are compounds that are branched alkyl groups.

Among the compounds (3-1), compounds in which Y is a hydrazino group, R ^a and R ^b are the same or different, and are linear or branched alkyl groups having 1 to 18 carbon atoms are preferable, and Y is hydrazino. More preferred are compounds in which R ^a and R ^b are the same or different and are ^a linear or branched alkyl group having 1 to 4 carbon atoms.

Specifically, as the compound (3-1), for example, isonicotinic acid (1-methylethylidene) hydrazide, isonicotinic acid (1-methylpropylidene) hydrazide, isonicotinic acid (1,3-dimethylpropylidene) Examples thereof include hydrazide and isonicotinic acid (1-phenylethylidene) hydrazide.

Of the compounds (1-1) to (3-1), the compound (2-1) is preferable, and specifically, N'-(1,3-dimethylbutylidene)salicylic acid hydrazide and 3-hydroxy-N'- are used. (1,3-Dimethylbutylidene)-2-naphthoic acid hydrazide and 1-hydroxy-N′-(1,3-dimethylbutylidene)-2-naphthoic acid hydrazide are preferable, and 3-hydroxy-N′-(1 ,3-Dimethylbutylidene)-2-naphthoic acid hydrazide is particularly preferred.

As the component (b) in the rubber composition of the present invention, one kind of these compounds may be contained alone, or two or more kinds thereof may be mixed and contained.

(1.3. Component (c): compound represented by formula (4) or (5) or salt of the compound)
The rubber composition of the present invention contains a compound represented by the following formula (4) or a salt thereof (compound (4)) or a compound represented by the following formula (5) or a salt thereof (compound (5)).

（式（４）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 (4), R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. R ³ and R ⁴ are They may be bonded to each other to form an alkylidene group, or any two of R ² , R ³ and R ⁴ may be bonded to each other to form an alkylene group, and each of these groups is substituted with one or more substituents. It may have a group.)

（式（５）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 the formula (5), 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. A group, an aryl group, or a heterocyclic group, each of which may have one or more substituents.)

In the present specification, the “aralkyl group” is not particularly limited, and examples thereof include a benzyl, phenethyl, trityl, 1-naphthylmethyl, 2-(1-naphthyl)ethyl, and 2-(2-naphthyl)ethyl group. Can be mentioned.

In the present specification, the “alkylidene group” is not particularly limited, and examples thereof include a methylidene group, an ethylidene group, a propylidene group, an isopropylidene group and a butylidene group.

In the present specification, the “alkylene group” is not particularly limited, and examples thereof include an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group and a heptamethylene group. These alkylene groups may contain a nitrogen atom, an oxygen atom and a sulfur atom, and may be via a phenylene group. Such alkylene groups, for _{example, -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 -, - CH 2 NHCH 2} NHCH 2 -, - CH 2 CH 2 CH 2 NHCH 2 CH 2 CH 2 -, - CH 2 OCH 2 CH 2 -, - CH 2 CH 2 OCH 2 CH 2 -, - CH 2 _{SCH 2 CH 2 -, - CH} 2 CH 2 SCH 2 CH 2 -,

等が挙げられる。

Etc.

Each of these alkyl group, aralkyl group, aryl group, heterocyclic group, alkylidene group, and alkylene group may have one or more substituents at arbitrary substitutable positions. The "substituent" is not particularly limited, and examples thereof include a halogen atom, amino group, aminoalkyl group, alkoxycarbonyl group, acyl group, acyloxy group, amide group, carboxyl group, carboxyalkyl group, formyl group, nitrile group. , 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 have preferably 1 to 5, more preferably 1 to 3.

In compound (4), R ¹ , R ³ and R ⁴ are the same or different and each 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. Are preferred.

Among the compounds (4), compounds in which R ¹ is a hydrogen atom are preferable.

Among the compounds (4), compounds in which 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 are preferable, and a hydrogen atom and a carbon number are included. More preferably, the compound is a linear or branched alkyl group having 1 to 4 groups, a benzyl group, a phenyl group, a naphthyl group, or a furyl group, and a compound having a hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms. Is particularly preferable.

Among compounds (4), compounds in which at least one of R ³ and R ⁴ is a hydrogen atom are preferable, and compounds in which both R ³ and R ⁴ are hydrogen atoms are more preferable.

In the compound (4), 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 ^A compound in which ³ and R ⁴ are both hydrogen atoms, and 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 compound which is a heterocyclic group and in which R ³ and R ⁴ are taken together to form an alkylidene group is more preferable, R ¹ is a hydrogen atom, and R ² is a hydrogen atom or a straight chain having 1 to 4 carbon atoms. A compound which is a chain alkyl group and in which R ³ and R ⁴ are both hydrogen atoms is particularly preferable.

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

Among the compounds (5), compounds in which R ⁶ is a linear alkyl group having 1 to 4 carbon atoms, an aralkyl group, or an aryl group are preferable, and a linear alkyl group having 1 to 4 carbon atoms or an aryl group is preferable. Certain compounds are more preferred.

Among the compounds (5), compounds in which R ⁷ and R ⁸ are the same or different and are a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or an amino group are preferable.

In compound (5), 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, and a hydrogen atom, A compound having a linear alkyl group having 1 to 4 carbon atoms or an amino group is preferable.

Among the compound (4) and the compound (5), the compound (4) is particularly preferable.

Specifically, as the compound (4) or (5), for example, 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-pyrazol-5(4H)-one, 4-(2-hydroxyethyl)-3-methyl-1H-pyrazol-5(4H)-one, 4-benzyl-3-methyl-1H-. Pyrazole-5(4H)one, 4,4'-(phenylmethylene)bis(5-methyl-1H-pyrazol-3(2H)-one), 4-[(dimethylamino)methylidene]-3-methyl-1H -Pyrazol-5(4H)-one, 4-methyl-2,3-diazospiro[4.4]non-3en-1-one, 5-methyl-2-(4-nitrophenyl)-1H-pyrazole- 3(2H)-one, 5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, 1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one, 4,5,6,7-tetrahydro-2H-indazol-3(3aH)-one, 4-{[4-dimethylamino]phenyl}methylidene}-3-methyl-1H-pyrazol-5(4H)-one, 1-phenyl-1H-pyrazol-3(2H)-one, 4,4′-(4-hydroxyphenylmethylene)bis(5-methyl-1H-pyrazol-3(2H)-one), 1,3-diphenyl -1H-pyrazol-5(4H)-one, 4,4'-(4-nitrophenylmethylene)bis(5-methyl-1H-pyrazol-3(2H)-one), and 4-amino-1, 5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one and the like can be mentioned.

Among them, the preferable compound is the compound (4), and among them, 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 preferable.

As the component (c) in the rubber composition of the present invention, one kind of the compounds described above as the compounds (4) and (5) may be contained alone, or two or more kinds thereof may be mixed and contained.

Some of the compounds (4) and (5) produce tautomers. The chemical equilibrium of tautomers may be reached if tautomerization is possible (eg, in solution). The compound (4) or (5) can exist as tautomers represented by the formulas (6) to (12), for example.

In the above formula (4), the compound (compound (4)-A) in which R ¹ and R ³ are hydrogen atoms has tautomers represented by the following formulas (6) to (8). ..

（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 (4), the compound (compound (4)-B) in which R ³ is a hydrogen atom has tautomers represented by the following formulas (9) to (10).

［式中、Ｒ^１、Ｒ^２及びＲ^４は、前記に同じ。］

[Wherein R ¹ , R ² and R ⁴ are the same as defined above. ]

In the above formula (4), the compound (compound (4)-C) in which R ¹ is a hydrogen atom has a tautomer represented by the following formula (11).

（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 formula (5), the compound (compound (5)-A) in which R ⁵ is a hydrogen atom has a tautomer represented by the following formula (12).

（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 formulas (6) to (12) and the compound (4) or (5) have reached an equilibrium state in which both isomers coexist. Thus, unless otherwise stated, all tautomeric forms of compound (4) or (5) herein are within the scope of the invention.

Further, the salt of the compound represented by the formula (4) or (5) 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, calcium Examples thereof include alkaline earth metal salts such as salts; ammonium salts such as dimethylammonium and triethylammonium.

The component (c) in the rubber composition of the present invention may include a mixture containing the compound (4) or the compound (5) in an arbitrary ratio.

(1.4. Component (d): carbon black and/or inorganic filler)
The rubber composition of the present invention contains carbon black and/or an inorganic filler.
Carbon black is usually used to improve the toughness of rubber. In this specification, the inorganic filler does not include carbon black.

The carbon black is not particularly limited, and examples thereof include commercially available carbon black and Carbon-Silica Dual phase filler. By containing carbon black in the rubber component, it is possible to enjoy the effect of reducing the electric resistance of the rubber, suppressing the charging, and further improving the strength of the rubber.

Specifically, examples of the carbon black include high, medium or low structure SAF, ISAF, IISAF, N110, N134, N220, N234, N330, N339, N375, N550, HAF, FEF, GPF, and SRF grade carbon. Examples include black. Among them, preferable carbon black is SAF, ISAF, IISAF, N134, N234, N330, N339, N375, HAF, or FEF grade carbon black.

The DBP absorption amount of carbon black is not particularly limited and is preferably 60 to 200 cm ³ /100 g, more preferably 70 to 180 cm ³ /100 g or more, and particularly preferably 80 to 160 cm ³ /100 g.

The nitrogen adsorption specific surface area of carbon black (N2SA, measured according to JIS K6217-2:2001) is preferably 30 to 200 m ² /g, more preferably 40 to 180 m ² /g, and particularly preferably 50 to It is 160 m ² /g.

In the rubber composition containing carbon black, the compound (1) or the reaction product of the rubber component and the compound (1) may strongly interact with the carbon black. Therefore, according to the rubber composition of the present invention, the dispersibility of carbon black is significantly improved, and the low heat build-up of the rubber composition can be significantly improved.

The inorganic filler is not particularly limited as long as it is an inorganic compound usually used in the rubber industry. Examples of inorganic compounds that can be used include silica; alumina such as γ-alumina and α-alumina (Al ₂ O ₃ ); alumina monohydrate such as boehmite and diaspore (Al ₂ O ₃ .H ₂ O); gibbsite , Aluminum hydroxide [Al(OH) ₃ ], such as bayerite; aluminum carbonate [Al ₂ (CO ₃ ) ₃ ], magnesium hydroxide [Mg(OH) ₂ ], magnesium oxide (MgO), magnesium carbonate (MgCO ₃ ). ), talc _{(3MgO · 4SiO 2 · H 2} O), Ataparujai _{(5MgO · 8SiO 2 · 9H 2} O), titanium white (TiO _2), titanium black _{(TiO 2n-1),} calcium oxide (CaO), hydroxide Calcium [Ca(OH) ₂ ], aluminum magnesium oxide (MgO·Al ₂ O ₃ ), clay (Al ₂ O ₃ ·2SiO ₂ ), kaolin (Al ₂ O ₃ ·2SiO ₂ ·2H ₂ O), pyrophyllite _{(Al 2 O 3 · 4SiO 2} · H 2 O), bentonite _{(Al 2 O 3 · 4SiO 2} · 2H 2 O), aluminum silicate _{(Al 2 SiO 5, Al 4} · 3SiO 4 · 5H 2 O , etc.), Magnesium silicate (Mg ₂ SiO ₄ , MgSiO ₃ etc.), calcium silicate (Ca ₂ ·SiO ₄ etc.), aluminum calcium silicate (Al ₂ O ₃ ·CaO·2SiO ₂ etc.), magnesium calcium silicate (CaMgSiO ₄ etc.) ), calcium carbonate (CaCO ₃ ), zirconium oxide (ZrO ₂ ), zirconium hydroxide [ZrO(OH) ₂ ·nH ₂ O], zirconium carbonate [Zr(CO ₃ ) ₂ ], zinc acrylate, zinc methacrylate, Examples thereof include crystalline aluminosilicate containing hydrogen, an alkali metal, or an alkaline earth metal that corrects electric charges, such as various zeolites. In these inorganic fillers, the surface of the inorganic filler may be organically treated in order to improve the affinity with the rubber component.

As the inorganic filler, silica is preferable from the viewpoint of imparting rubber strength, and more preferably silica alone or in combination with one or more of the inorganic compounds normally used in the rubber industry. When silica and the above-mentioned inorganic compound other than silica are used together as the inorganic filler, the total amount of all components of the inorganic filler may be appropriately adjusted so as to fall within the above range.
Silica is preferably added because it can impart rubber strength.

Any commercially available silica can be used. Among them, preferable silica is wet silica, dry silica, or colloidal silica, more preferably wet silica. The surface of the silica may be organically treated in order to improve the affinity with the rubber component.

The BET specific surface area of silica is not particularly limited, and examples thereof include a range of 40 to 350 m ² /g. Silica having a BET specific surface area within this range has an advantage of achieving both rubber toughness and dispersibility in a rubber component. The BET specific surface area is measured according to ISO5794/1.

From this viewpoint, preferable silica is a silica having a BET specific surface area in the range of 80 to 300 m ² /g, more preferably silica having a BET specific surface area of 100 to 270 m ² /g, and particularly preferably, Silica having a BET specific surface area of 110 to 270 m ² /g.

Commercially available products of such silica include Quechen Silicon Chemical Co. , Ltd. Product name "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 "Nipseal AQ" (BET specific surface area = 205 m ² /g), "Nipseal KQ" (BET specific surface area = 240 m ² /g), Degussa manufactured by Tosoh Silica Corporation The trade name “Ultrasil VN3” (BET specific surface area=175 m ² /g) manufactured by the company can be mentioned.

In a rubber composition containing an inorganic filler, particularly silica, the compound (1) or the compound (2) is added, whereby the dispersibility of silica is significantly improved and the low heat buildup of the rubber composition can be significantly improved. .. That is, the compound (1) or the compound (2) can be used as a dispersant for carbon black and/or an inorganic filler, a low exothermic agent, an exothermic preventive, or an exothermic suppressor, and preferably a dispersant for rubber. It can be used as a low heat generating agent for rubber, a heat generating preventing material for rubber, or a heat generating suppressing agent for rubber.

The blending amount of the component (b) is usually 0.01 to 50 parts by mass, preferably 0.1 to 30 parts by mass, relative to 100 parts by mass of the component (a) in the rubber composition. It is more preferably 0.5 to 10 parts by mass.

The compounding amount of the component (c) is usually 0.01 to 50 parts by mass, preferably 0.1 to 30 parts by mass, relative to 100 parts by mass of the component (a) in the rubber composition. It is more preferably 0.5 to 10 parts by mass.

The compounding amount of the component (d) is usually 0.5 to 300 parts by mass, preferably 1 to 200 parts by mass, and more preferably 100 parts by mass of the component (a) in the rubber composition. Is 5 to 150 parts by mass.

When both the carbon black and the inorganic filler are blended in the component (d), it may be appropriately adjusted so that the total amount of both components is within the above range.

In the component (d), if the compounding amount of carbon black and/or the inorganic filler is 2 parts by mass or more, it is preferable from the viewpoint of improving the toughness of the rubber composition, and if 200 parts by mass or less, the rolling resistance is reduced. From the viewpoint of.

In the component (d), the blending amount of carbon black is usually 20 to 200 parts by mass, preferably 30 to 130 parts by mass, and more preferably 35 to 100 parts by mass with respect to 100 parts by mass of the rubber component. It is a department.

In the component (d), if the amount of carbon black is 2 parts by mass or more, it is preferable from the viewpoint of ensuring antistatic performance and rubber strength performance, and if it is 200 parts by mass or less, it is preferable from the viewpoint of reducing rolling resistance. ..

In the component (d), the compounding amount of the inorganic filler is usually 10 to 200 parts by mass with respect to 100 parts by mass of the rubber component.

In the component (d), the compounding amount of silica is usually 2 to 1200 parts by mass, preferably 30 to 130 parts by mass, and more preferably 35 to 130 parts by mass with respect to 100 parts by mass of the rubber component. Is.

In the above-mentioned component (d), the amount of silica to be blended, in particular, to achieve both good exercise performance and low fuel consumption performance, is usually 20 to 200 parts by mass, preferably 30 to 100 parts by mass with respect to 100 parts by mass of the rubber component. It is 130 parts by mass, more preferably 35 to 130 parts by mass.

The blending ratio of the component (b) is preferably 0.01 to 90% by mass, and 0.1 to 50% by mass, in the total 100% by mass of the component (b) and the component (c). It is more preferable that the amount is 0.5 to 30% by mass.

(1.5. Other compounding agents)
In the rubber composition of the present invention, in addition to the components (a), (b), (c) and (d) described above, compounding agents usually used in the rubber industry, such as an antioxidant and an antiozonant. , Softening agents, processing aids, waxes, resins, foaming agents, oils, fatty acids having 8 to 30 carbon atoms such as stearic acid, zinc oxide (ZnO), vulcanization accelerators, vulcanization retarders, vulcanizing agents (sulfur ) And the like can be appropriately selected and blended within a range that does not impair the object of the present invention. Commercially available products can be preferably used as these compounding agents.

Further, in the rubber composition containing the above component (d), silane is used for the purpose of increasing the toughness of the rubber composition by carbon black and/or silica, or for increasing the tear resistance and abrasion resistance of the rubber composition. You may mix|blend a coupling agent, a titanate coupling agent, an aluminate coupling agent, and a zirconate coupling agent.

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

Examples of the sulfide-based silane coupling agent 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 preferable.

Examples of the thioester-based silane coupling agent include 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 can be mentioned.

Examples of the thiol-based silane coupling agent include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-[ethoxybis(3,6,9,12,15). -Pentaoxaoctacosan-1-yloxy)silyl]-1-propanethiol and the like.
Examples of the olefin-based silane coupling agent include dimethoxymethylvinylsilane, vinyltrimethoxysilane, dimethylethoxyvinylsilane, diethoxymethylvinylsilane, triethoxyvinylsilane, vinyltris(2-methoxyethoxy)silane, allyltrimethoxysilane, and allyltrisilane. Ethoxysilane, p-styryltrimethoxysilane, 3-(methoxydimethoxydimethylsilyl)propyl acrylate, 3-(trimethoxysilyl)propyl acrylate, 3-[dimethoxy(methyl)silyl]propyl methacrylate, 3-(trimethoxysilyl) Examples thereof include propyl methacrylate, 3-[dimethoxy(methyl)silyl]propyl methacrylate, 3-(triethoxysilyl)propyl methacrylate, 3-[tris(trimethylsiloxy)silyl]propyl methacrylate and the like.

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 preferable.

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

Examples of the alkyl silane coupling agent include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, and isobutyltriethoxy. Examples thereof include silane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, and n-decyltrimethoxysilane. 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 carbon black and/or the inorganic filler is not particularly limited, and commercially available products can be preferably used. Examples of such titanate coupling agents include alkoxide-based, chelate-based, and acylate-based titanate coupling agents.

Examples of the alkoxide-based titanate coupling agent include tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetraoctyl titanate, tetratert-butyl titanate, and tetrastearyl titanate. Of these, tetraisopropyl titanate is preferred.

Examples of the chelate-type titanate coupling agent include titanium acetylacetonate, titanium tetraacetylacetonate, titanium ethyl acetoacetate, titanium dodecylbenzenesulfonate compound, titanium phosphate compound, titanium octylene glycolate, titanium ethylacetoacetate. , Titanium lactate ammonium salt, titanium lactate, titanium ethanolaminate, titanium octylene glycolate, titanium aminoethylamino ethanolate and the like. Of these, titanium acetylacetonate is preferred.

Examples of the acylate-based titanate coupling agent include titanium isostearate and the like.

The aluminate coupling agent that can be used in combination with carbon black and/or the inorganic filler is not particularly limited, and commercially available products can be preferably used. Examples of such an aluminate coupling agent include 9-octadecenyl acetoacetate aluminum diisopropylate, aluminum secondary butoxide, aluminum trisacetylacetonate, aluminum bisethylacetoacetate monoacetylacetonate, and aluminum trisethylacetoacetate. Can be mentioned. Of these, 9-octadecenyl acetoacetate aluminum diisopropylate is preferred. The zirconate coupling agent that can be used in combination with carbon black and/or the inorganic filler is not particularly limited, and commercially available products can be preferably used. Examples of such zirconate coupling agents include alkoxide-based, chelate-based, and acylate-based zirconate coupling agents.

Examples of the alkoxide-based zirconium-based coupling agent include normal propyl zirconate and normal butyl zirconate. Of these, normal butyl zirconate is preferable.

Examples of chelate-based zirconate coupling agents include zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium ethylacetoacetate, zirconium lactate ammonium salt, and the like. Of these, zirconium tetraacetylacetonate is preferred.

Examples of the acylate-based zirconate coupling agent include zirconium stearate and zirconium octylate. Of 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 alone or in combination of two or more.

The compounding amount of the silane coupling agent of the rubber composition of the present invention is preferably 0.1 to 20 parts by mass and particularly preferably 3 to 15 parts by mass with respect to 100 parts by mass of the component (d). If it is 0.1 parts by mass or more, the effect of improving the tear strength of the rubber composition can be more suitably expressed, and if it is 20 parts by mass or less, the cost of the rubber composition is reduced and the economical efficiency is improved. Because it does.

(1.6. Masterbatch)
In producing the rubber composition of the present invention, a masterbatch in which the above components (a), (b) and (c) are mixed in advance at an arbitrary ratio may be used.

The compounding amount of the component (b) of the masterbatch of the rubber composition of the present invention is preferably 0.01 to 200 parts by mass, and particularly preferably 0.1 to 100 parts by mass, relative to 100 parts by mass of the component (a). preferable.

The compounding amount of the component (c) of the masterbatch of the rubber composition of the present invention is preferably 0.01 to 200 parts by mass, particularly 0.1 to 100 parts by mass, relative to 100 parts by mass of the component (a). preferable.

(2. Method for producing rubber composition)
In the present invention, as a method for producing a rubber composition, the above components (a), (b), (c), (d), a vulcanizing agent, and other compounding agents may be mixed, and the order of compounding is appropriately set. I hope it is done. For example, a step (A) of mixing raw material components containing the above components (a), (b), (c) and (d), and a step of mixing the mixture and the vulcanizing agent obtained in the step (A) ( B), the step (A) of mixing the raw material components containing the above components (a), (b) and (c), and the mixture, the component (d) and the vulcanizing agent obtained in the step (A). A method including the step (B) of mixing, the step (A) of mixing the raw material components including the components (a), (b) and (d), and the mixture and the component (c) obtained in the step (A). ) And the step (B) of mixing a vulcanizing agent, the step (A) of mixing the raw material components containing the above-mentioned components (a), (c) and (d), and the step (A). Obtained in the method including the step (B) of mixing the mixture, the component (b) and the vulcanizing agent, the step (A) of mixing the raw material components including the above components (a) and (b), and the step (A) Mixture, components (c), (d) and a method including a step (B) of mixing a vulcanizing agent, a step (A) of mixing raw material components including the above components (a) and (c), and a step The method including the step (B) of mixing the mixture obtained in (A), the components (b) and (d), and the vulcanizing agent, and the step of mixing the raw material components including the above components (a) and (d) (A ), and a method including the step (B) of mixing the mixture obtained in the step (A), the components (b) and (c), and the vulcanizing agent. Among them, the preferable production method includes the step (A) of kneading the raw material components containing the above components (a), (b), (c) and (d), and the mixture and vulcanization obtained in the step (A). A method including a step (B) of mixing agents.

(2.1. Process (A))
The step (A) is a step of mixing raw material components including the above components (a), (b), (c) and (d).

In the step (A), the above-mentioned other compounding agents and the like can be further compounded, if necessary. In the present specification, “mixing” includes not only a mode of simply mixing but also a mode of so-called “kneading”.

In the step (A), raw material components including the above components (a), (b), (c) and (d) are mixed. In this mixing method, the entire amount of each component may be mixed at once, or each component may be dividedly added and mixed depending on the purpose such as viscosity adjustment. Further, after mixing the components (a) and (d), the components (b) and (c) are added and mixed, or the components (a), (b) and (c) are mixed. After that, the above component (d) may be added and mixed. The mixing operation may be repeated in order to uniformly disperse each component. Further, a filler masterbatch rubber in which the filler is added to the rubber in advance by a wet method and/or a dry mixing method may be used.

Further, as another mixing method in the step (A), a step (A-1) of mixing the above components (a), (b) and (c), and a mixture obtained in the step (A-1) There can be mentioned a two-stage mixing method including a step (A-2) of mixing the raw material component containing the component (d).

The temperature when mixing the rubber composition in the step (A) is not particularly limited, and for example, the upper limit of the temperature of the rubber composition is preferably 100 to 190°C, and preferably 110 to 175°C. More preferably, it is more preferably 120 to 170°C.

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

The temperature for mixing the components (a), (b) and (c) in the step (A-1) is preferably 60 to 190°C, more preferably 70 to 160°C. It is more preferably 80 to 150°C. This is because if the mixing temperature is lower than 60° C., the reaction does not proceed, and if it is 190° C. or higher, the deterioration of the rubber proceeds.

The mixing time in the step (A-1) is preferably 10 seconds to 20 minutes, more preferably 30 seconds to 10 minutes, and further 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, when the mixing time is within 20 minutes, the productivity is excellent.

The temperature at the time of mixing the mixture obtained in the step (A-1) in the step (A-2) and the component (d) is not particularly limited, and for example, the upper limit of the temperature of the mixture is 100 to 190. C. is preferable, 110 to 175.degree. C. is more preferable, and 130 to 170.degree. C. is further preferable.

The mixing time in the step (A-2) is not particularly limited and is, for example, preferably 10 seconds to 20 minutes, more preferably 30 seconds to 10 minutes, and further preferably 1 minute to 8 minutes. Is more preferable.

In the step (A), the total blending amount of the components (b) and (c) is not particularly limited and is, for example, 0.01 to 50 parts by mass with respect to 100 parts by mass of the component (a). , Preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass.

(2.2. Process (B))
Step (B) is a step of mixing the mixture and the vulcanizing agent obtained in step (A).

In the step (B), a vulcanization accelerator and the like can be further compounded, if necessary.

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

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

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

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

In the method for producing the rubber composition of the present invention, various compounding agents such as stearic acid, zinc oxide, and an antioxidant, which are usually compounded in the rubber composition, are added, if necessary, in the step (A) or the step (B). Can be added at.

The above-mentioned compounding agent may be added in either step (A) or step (B), or may be added separately in step (A) and step (B).

(2.3. Method for molding rubber composition)
The rubber composition in the present invention is mixed using a Banbury mixer, a roll, an intensive mixer, a kneader, a single screw extruder, a twin screw extruder, or the like. Then, it is extruded and processed in an extrusion step, and is formed as, for example, a tread member or a sidewall member. Then, it is pasted and molded by a usual method on a tire molding machine to mold a green tire. The raw tire is heated and pressed 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 tires for passenger cars, tires for heavy loads, tires for motorcycles (motorcycles), studless tires, and the like, and among them, the tires for passenger cars can be preferably used.

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 a tread portion, a sidewall portion, a bead area portion, a belt portion, a carcass portion and a shoulder portion.

Above all, it is preferable to form the tire tread portion or the sidewall portion of the pneumatic tire with the rubber composition, and it is particularly preferable to form the tire tread portion with the rubber composition.

The tread portion has a tread pattern, is a portion that is in direct contact with the road surface, is the outer skin portion of the tire that protects the carcass and prevents abrasion and external damage, and of the cap tread and/or the cap tread that constitutes the ground contact portion of the tire. Refers to the base tread arranged inside.

The sidewall portion is, for example, a portion from the lower side of the shoulder portion of the pneumatic radial tire to the bead portion, which protects the carcass and is the portion which is most bent when traveling.

The bead area part is a part that fixes both ends of the carcass cord and at the same time fixes the tire to the rim. A bead is a structure in which high carbon steel is bundled.

The belt portion is a reinforcing band stretched in the circumferential direction between the tread having a radial structure and the carcass. The carcass is tightened like a trough to increase the rigidity of the tread.

The carcass portion is a portion of the cord layer forming the skeleton of the tire and plays a role of withstanding the load, impact, and filled air pressure of the tire.

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

The tire of the present invention can be manufactured according to a method known so far in the field of tires. Further, as the gas to be filled in the tire, normal air or air whose oxygen partial pressure is adjusted; inert gas such as nitrogen, argon, helium or the like can be used.

The tire of the present invention has excellent low heat build-up, toughness, and processability, and the rolling resistance of the tire is reduced, so that fuel consumption of an automobile can be reduced. Further, a rubber composition highly filled with carbon black and/or an inorganic filler also exhibits high low heat buildup, so that a fuel-efficient tire having high exercise performance can be provided.

(4. Applications other than tires)
The rubber composition of the present invention can be used for belts (conveyor belts), anti-vibration rubbers, seismic isolation rubbers, etc., in addition to the above tire applications.

(5. Additive)
The additive of the present invention is an additive for rubber, more specifically, an additive for a rubber composition for tire, which contains the above-mentioned components (b) and (c).

The component (c) contained in the additive of the present invention includes tautomers of the compound (2) or (3).

The additive amount of the present invention is usually 0.01 to 50 parts by mass, preferably 0.1 to 30 parts by mass, relative to 100 parts by mass of the component (a) in the rubber composition. It is more preferably 0.5 to 20 parts by mass. When the content of the additive of the present invention is 0.01 parts by mass or more with respect to 100 parts by mass of the component (a), it is expected that low heat buildup, toughness and workability can be sufficiently exhibited. It is economically preferable that the content of the additive is 50 parts by mass or less with respect to 100 parts by mass of the component (a).

In the additive of the present invention, the components (b) and (c) may be used separately, or the components (b) and (c) may be used in a mixed state. When used in a mixed state, the above-mentioned components (b) and (c) may be weighed in predetermined or appropriate amounts and mixed by a known method. Mixing can be carried out by using a rotary ball mill, a vibrating ball mill, a planetary mill, a paint shaker, a rocking mill, a rocking mixer, a bead mill, a fluid mixer, a stirrer or the like, both wet and dry.

By adding the additive of the present invention to the rubber component, it is possible to impart excellent low heat build-up, toughness, and processability to the rubber component without performing a special kneading method.

Although the embodiments of the present invention have been described above, the present invention is not limited to such examples, and it goes without saying that the present invention can be implemented in various forms without departing from the scope of the present invention.

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

Production Example 1: Production of 3-hydroxy-N'-(1,3-dimethylbutylidene)-2-naphthoic acid hydrazide (Compound (b)-1) Dean Stark type reactor equipped with reflux condenser and stirrer Then, 500 ml of methyl isobutyl ketone and 50.5 g (0.25 mol) of 3-hydroxy-2-naphthoic acid hydrazide were charged, and then heated and refluxed for 5 hours while removing distilled water. After cooling the reaction solution to 20° C., the precipitated crystals were separated by filtration and dried under reduced pressure to give slightly hydroxy crystalline 3-hydroxy-N′-(1,3-dimethylbutylidene)-2-naphthoic acid hydrazide 67. 0.6 g was obtained.
Melting point: 146°C
¹ H-NMR (300 MHz, d ₆ -DMSO, δppm):
0.90 (m, 6H), 1.93 (s, 3H), 2.00 (m, 1H), 2.17 (m, 2H), 7.38 (m, 2H), 7.46 (m , 1H), 7.75 (m, 1H), 7.95 (m, 1H), 8.58 (m, 1H), 11.15 (b, 1H), 11.65 (b, 1H)
IR (KBR): 3400 to 2400, 1650, 1550, 1510, 1470, 1360, 1230, 1170, 1140, 1120, 1050, 950, 900, 880, 770, 740, 670, 600, 550, 480 cm ^-1.

Production Example 2: Production of 3-(naphthalen-2-yl)-1H-pyrazol-5(4H)-one (Compound (c)-2) 8.5 g (52.1 mmol) of carbonyldiimidazole in a 100 mL eggplant flask. And 60 mL of dehydrated tetrahydrofuran were added, and the mixture was stirred at room temperature. Next, 7.5 g (43.6 mmol) of 2-naphthoic acid was added to this mixture, and the mixture was stirred at room temperature overnight. 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 the mixture was stirred under ice cooling. Next, 10.4 g (109.2 mmol) of magnesium chloride was added to this mixture, and the mixture was 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 at room temperature overnight.

The reaction solution was concentrated, 125 mL of toluene was added to the obtained residue, 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. 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 white solid 3-(naphthalen-2-yl)-1H-pyrazol-5(4H)-one. It was
Melting point: 204°C
¹ H-NMR (300 MHz, d ₆ -DMSO, δppm):
11.94 (1H, br), 8.20 to 8.21 (1H, J=1.2Hz, d), 7.82 to 7.96 (4H, m), 7.47 to 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 3: Production of 3-(furan-2-yl)-1H-pyrazol-5(4H)-one (Compound (c)-3) 8.7 g (53.5 mmol) of carbonyldiimidazole in a 100 mL eggplant flask. And 60 mL of dehydrated tetrahydrofuran were added, and the mixture was stirred at room temperature. Next, 5.0 g (45.0 mmol) of 2-furancarboxylic acid was added to this mixture, and the mixture was stirred at room temperature overnight. 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 the mixture was stirred under ice cooling. Next, 10.4 g (109.2 mmol) of magnesium chloride was added to this mixture, and the mixture was stirred at room temperature for 4 hours. The above reaction solution 2 was added dropwise to this reaction solution, and the mixture was stirred at room temperature overnight.
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, 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 obtained liquid, 2.0 mL (35.0 mmol) of acetic acid was added dropwise, and the mixture was refluxed for 4 hours. The obtained reaction solution was returned to room temperature, 30 mL of diisopropyl ether was added, and the precipitated crystals were filtered to obtain white solid 3-(furan-2-yl)-1H-pyrazol-5(4H)-one. 47 g was obtained.
Melting point: 231°C
¹ H-NMR (300 MHz, d ₆ -DMSO, δppm):
11.79 (2H, br), 7.68 to 7.69 (1H, m), 6.69 (1H, J=3.3Hz, 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 4: Production of 3-phenyl-1H-pyrazol-5(4H)-one (Compound (c)-4) 25 g (0.13 mol) ethyl benzoylacetate and 25 mL ethanol were added to a 100 mL four-necked flask and stirred. did. While cooling this with a water bath, 6.5 mL (0.13 mol) of hydrazine monohydrate was added dropwise. After stirring at room temperature for 4 hours, the generated white solid was filtered off, washed with 50 mL of a mixed solution of water:methanol=1:1 (volume ratio), and dried to give white solid 3-phenyl-1H-pyrazole. 18.8 g of -5(4H)-one were obtained.
Melting point: 236°C
¹ H-NMR (500 MHz, d ₆ -DMSO, δ ppm):
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 5: Production of 3-propyl-1H-pyrazol-5(4H)-one (compound (c)-5) 24.8 g (0.16 mol) of methyl 3-oxohexanoate in a 500 mL four-necked flask, and 260 mL of ethanol was added and stirred. While cooling this in an ice bath, 8.6 mL (0.18 mol) of hydrazine monohydrate was added dropwise, and the mixture was stirred under ice cooling for 2 hours, then heated under reflux for 2 hours, and the reaction solution was cooled to room temperature. The produced white solid was filtered off, washed with 50 mL of a mixed solution of water:methanol=1:1 (volume ratio), and dried to give a white solid of 3-propyl-1H-pyrazol-5(4H)-one. 13.2 g was obtained.
Melting point: 205-206°C
¹ H-NMR (500 MHz, d ₆ -DMSO, δ ppm):
11.11 (1H, br), 9.42 (1H, br), 5.23 (1H, s), 2.41 (2H, J=7.5Hz, t), 1.54 (2H, m) , 0.88 (3H, J=7.3Hz, t)
¹³ C-NMR (500 MHz, d ₆ -DMSO, δppm):
160.87, 144.04, 87.93, 27.67, 21.93, 13.57

Production Example 6: Production of 4,4'-(phenylmethylene)bis(5-methyl-1H-pyrazol-3(2H)-one) (Compound (c)-6) In a 2L four-necked flask, 1L 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 dodecyl sulfate were added and stirred at room temperature for 30 minutes, and then refluxed for 1 hour. did. The reaction solution was stirred for 30 minutes while cooling in an ice bath, filtered off, washed with 500 mL of water, and dried to give 4,4′-(phenylmethylene)bis(5-methyl-) as a pale yellow solid. 1H-pyrazol-3(2H)-one) 12.1 g was obtained.
Melting point: 230-232°C
¹ H-NMR (500 MHz, d ₆ -DMSO, δ ppm):
11.31 (4H, br), 7.20 (2H, m), 7.12 (3H, m), 4.81 (1H, 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 7: Production of 4,4′-(4-hydroxyphenylmethylene)bis(5-methyl-1H-pyrazol-3(2H)-one) (Compound (c)-7) In a 3L 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 dodecyl sulfate were added at room temperature. After stirring for 30 minutes, the mixture was refluxed for 1 hour. The reaction mixture was stirred for 30 minutes while cooling in an ice bath, filtered off, washed with 2.5 L of water, and dried to give a pale yellow solid 4,4′-(4-hydroxyphenylmethylene)bis. 33.5 g of (5-methyl-1H-pyrazol-3(2H)-one) was obtained.
Melting point: 262-264°C
¹ H-NMR (500 MHz, d ₆ -DMSO, δ ppm):
11.22 (4H, br), 9.03 (1H, s), 6.91 (2H, J = 8.5Hz, d), 6.59 (2H, J = 8.5Hz, 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 8: Production of 4,4′-(4-nitrophenylmethylene)bis(5-methyl-1H-pyrazol-3(2H)-one) (Compound (c)-8) In a 3L 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 dodecyl sulfate were added at room temperature. After stirring for 30 minutes, the mixture was refluxed for 1 hour. The reaction solution was stirred for 30 minutes while being cooled in an ice bath, filtered off, washed with 500 mL of methanol, and dried to give a pale yellow solid 4,4′-(4-nitrophenylmethylene)bis(5. 37.8 g of -methyl-1H-pyrazol-3(2H)-one) was obtained.
Melting point: 300-302°C
¹ H-NMR (500 MHz, d ₆ -DMSO, δ ppm):
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

Preparation Example 9: Preparation of 4-[(dimethylamino)methylidene]-3-methyl-1H-pyrazol-5(4H)-one (Compound (c)-9) In a 500 mL four-necked flask, 300 mL of xylene, 3- Methyl-5-pyrazolone (14.7 g, 0.15 mol) and N,N-dimethylformamide dimethyl acetal (21.6 g, 0.18 mol) were added, and the mixture was stirred at 110°C overnight. After cooling the reaction solution to room temperature, the resulting solid was filtered off, washed with 300 mL of toluene and dried to give 4-[(dimethylamino)methylidene]-3-methyl-1H-pyrazole-5( as a yellow solid. 4H)-one (20.3 g) was obtained.
Melting point: 158-159°C
¹ H-NMR (500 MHz, d ₆ -DMSO, δ ppm):
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 10: Production of 4-{[4-dimethylamino]phenyl}methylidene}-3-methyl-1H-pyrazol-5(4H)-one (Compound (c)-10) In a 3 L four-necked flask, ethanol was added. 2.7 L, 3-methyl-5-pyrazolone 27.0 g (0.28 mol), 4-dimethylaminobenzaldehyde 44.4 g (0.30 mol), and piperidine 4.7 g (55 mmol) were added, and the mixture was refluxed for 3 hours. .. The reaction solution was stirred overnight at room temperature, filtered off and dried to give 4-{[4-dimethylamino]phenyl}methylidene}-3-methyl-1H-pyrazole-5(4H) as a pale yellow solid. 46.3 g of -one were obtained.
Melting point: 164°C
¹ H-NMR (500 MHz, d ₇ -DMF, δ ppm):
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 ₇ -DMF, δppm):
166.74, 153.84, 150.55, 146.23, 136.92, 122.49, 120.74, 111.43, 39.58, 12.98.

Production Example 11: Production of 3-undecyl-1H-pyrazol-5(4H)-one (compound (c)-11) To a 50 mL eggplant flask, 2.8 g (17.4 mmol) of carbonyldiimidazole and 20 mL of chloroform were added. , Stirred at room temperature. Then, 2.9 g (14.5 mmol) of lauric acid was added to this mixture, and the mixture was stirred at room temperature overnight. Hereinafter, the obtained reaction liquid is referred to as "reaction liquid 3".
To a 200 mL four-necked flask, 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, and the mixture was stirred under ice cooling. Then, 3.5 g (36.4 mmol) of magnesium chloride was added to the obtained mixture, and the mixture was stirred at room temperature for 4 hours. The above reaction solution 3 was added dropwise to this reaction solution, and the mixture was stirred at room temperature overnight. The obtained reaction solution was concentrated, 42 mL of chloroform was added, washed with 48 mL of 2M hydrochloric acid and 48 mL of water, the organic layer was dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure.

To this, 20 mL of ethanol and 0.7 mL (14.9 mmol) of hydrazine monohydrate were added, 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 separated by filtration to give 3-undecyl-1H-pyrazol-5(4H)-one (2.83 g) 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 to 2.44 (2H, J=7.5Hz, t), 1.48 to 1.53 (2H,m), 1.30 (16H,s), 0.83 to 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 12: Production of 4-(2-hydroxyethyl)-3-methyl-1H-pyrazol-5(4H)-one (Compound (c)-12) In a 100 mL four-necked flask, α-acetyl-γ- Butyrolactone 24.3 g (0.19 mol) and ethanol 24 mL 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 separated by filtration, washed with 50 mL of isopropanol, and dried to obtain 23.8 g of white solid 4-(2-hydroxyethyl)-3-methyl-1H-pyrazol-5(4H)-one. It was
Melting point: 182°C
¹ H-NMR (500 MHz, d ₇ -DMF, δ ppm):
10.62 (2H, br), 3.78 (2H, J = 7.0Hz, t), 3.66 (1H, br), 2.69 (2H, J = 7.0Hz, t), 2. 31 (3H,s)
¹³ C-NMR (500 MHz, d ₇ -DMF, δppm):
160.88, 137.87, 98.61, 62.29, 26.18, 9.66

Production Example 13: Production of 4-benzyl-3-methyl-1H-pyrazol-5(4H)one (Compound (c)-13) In a 100 mL four-necked flask, 24.5 g of ethyl 2-benzylacetoacetate (0. 11 mol) and 25 mL of ethanol were added and stirred. While cooling this with an ice bath, 5.7 mL (0.12 mol) of hydrazine monohydrate was added dropwise, followed by stirring at room temperature for 3 hours. The precipitated solid was separated by filtration, washed with 50 mL of a mixed solution of water:methanol=1:1 (volume ratio), and dried to give white solid 4-benzyl-3-methyl-1H-pyrazole-5(4H ) On, 15.6 g was obtained.
Melting point: 228-229°C
¹ H-NMR (500 MHz, d ₆ -DMSO, δ ppm):
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

Production Example 14: Production of 1-phenyl-1H-pyrazol-3(2H)-one (Compound (c)-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. To this, 317 mg (3.2 mmol) of copper (I) chloride was added and stirred overnight in an open system. Water (750 mL) was added to the reaction solution, and the mixture was stirred for 30 minutes while cooling in an ice bath, filtered, washed with water (750 mL), and dried to give 1-phenyl-1H-pyrazole-3 (2H) as a light brown solid. -6.1 g of on were obtained.
Melting point: 152°C
¹ H-NMR (500 MHz, d ₆ -DMSO, δ ppm):
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 15: Production of 4-methyl-2,3-diazospiro[4.4]non-3en-1-one (Compound (c)-15) 7.2 g (62 g ) of methyl acetoacetate in a 500 mL four-necked flask. 0.0mmol), 23.1 g (75 mmol) of 1,4-diiodobutane, 42.9 g (310 mmol) of potassium carbonate, and 220 mL of dimethyl sulfoxide were added, and the mixture was stirred at room temperature overnight. 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. The organic layer was dried over sodium sulfate, concentrated, and purified by column (hexane:ethyl acetate=50:1 (volume ratio)) to obtain 6.5 g (36 mmol) of an intermediate.
The resulting intermediate was mixed with 6 mL of ethanol, 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 was obtained.
Melting point: 83-84°C
¹ H-NMR (500 MHz, d ₆ -DMSO, δ ppm):
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

Production Example 16: Production of 4,5,6,7-tetrahydro-2H-indazol-3(3aH)-one (Compound (c)-16) Ethyl 2-oxocyclohexanecarboxylate in a 100 mL four-necked flask. 5 g (0.14 mol) and 24 mL of ethanol were added and mixed. 7.3 mL (0.15 mol) of hydrazine monohydrate was added dropwise thereto while cooling with an ice bath, and the mixture was stirred at 80° C. for 3 hours, and then stirred for 30 minutes while cooling with an ice bath. Then, the reaction solution is filtered off, washed with 50 mL of a mixed solution of water:methanol=1:1 (volume ratio), and dried to give 4,5,6,7-tetrahydro-2H-indazole-3 as a white solid. 17.3 g of (3aH)-one was obtained.
Melting point: 286-288°C
¹ H-NMR (500 MHz, d ₆ -DMSO, δ ppm):
10.50 (1H, br), 9.66 (1H, br), 2.43 (2H, J = 5.7Hz, t), 2.22 (2H, J = 5.7Hz, 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

Production Example 17: Production of 1,3-diphenyl-1H-pyrazol-5(4H)-one (Compound (c)-17) In a 1 L four-necked flask, 50.0 g (0.26 mol) of benzoyl ethyl acetate and phenyl were used. 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 this at 100° C. for 1 hour, the mixture was stirred for 30 minutes while cooling in an ice bath, filtered, washed with 1 L of a mixed solution of water:methanol=1:1 (volume ratio), and dried to give a pale orange color. 58.0 g of solid 1,3-diphenyl-1H-pyrazol-5(4H)-one was obtained.
Melting point: 137-138°C
¹ H-NMR (500 MHz, d ₆ -DMSO, δ ppm):
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 12 and Comparative Examples 1 to 9: Production of Rubber Composition The components described in the step (A) of Tables 1 to 4 below were mixed in the ratio (parts by mass), and mixed with a Banbury mixer. After curing until the temperature of the mixture becomes 60°C or lower, the respective components described in step (B) of Tables 1 to 4 are added in the proportion (parts by mass), and the maximum temperature of the mixture becomes 70°C or lower. The rubber composition was manufactured by mixing while adjusting as described above.

The details of each component in Tables 1 to 3 are as follows.
*1: Component (a): NR (natural rubber); GUANGKEN RUBBER, TSR-20
*2: Component (b): Compound (b-1); 3-hydroxy-N'-(1,3-dimethylbutylidene)-2-naphthoic acid hydrazide produced in Production Example 1 *3: Component (c) : Compound (c-1); Otsuka Chemical Co., Ltd., 3-methyl-5-pyrazolone *4: Component (d): Carbon black; Cabot, N234
*5: Zinc oxide; Darian Zinc Oxide Co. , Ltd. *6: stearic acid; Sichuan Tianyu Grease, Inc. *7: anti-aging agent (N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine); Kemai Chemical Co. , Ltd. *8: Wax; Rhein Chemie Rheinau, Antilux 111
*9: Vulcanization accelerator N-(tert-butyl)-2-benzothiazolesulfenamide; Sanshin Chemical Co., Ltd., Sansera NS-G
*10: Sulfur; Changhai Jinghai Chemical Co. , Ltd. *11: Component (a): SBR (styrene butadiene rubber); Asahi Kasei, Tuffden 2000R

Examples 1 to 12 and Comparative Examples 1 to 9: Low heat buildup (Tan δ value) test For the rubber compositions of the following Examples 1 to 12 and Comparative Examples 1 to 9, a viscoelasticity measuring device (manufactured by Metravib) was used. The Tan δ value was measured at a temperature of 40° C., a dynamic strain of 5% and a frequency of 15 Hz. For comparison, rubber compositions (Comparative Examples 1, 3, 5, 7 to 9) were prepared with the same formulation content and the same production method as those in Examples, except that the above components (b) and (c) were not added. The Tan δ value was set to 100. The low exothermic index was calculated based on the following formula. The smaller the value of the low heat buildup index, the lower the heat buildup and the smaller the hysteresis loss.

Formula: Low exothermicity index=(Tan δ value of rubber compositions of Examples 1 to 3)/(Tan δ value of Comparative Example 1)×100

Formula: Low heat buildup index=(Tan δ value of rubber compositions of Examples 4 to 6)/(Tan δ value of Comparative Example 3)×100

Formula: Low heat buildup index=(Tan δ value of rubber compositions of Examples 7 to 9)/(Tan δ value of Comparative Example 5)×100

Formula: Low exothermicity index=(Tan δ value of rubber composition of each Example 10)/(Tan δ value of Comparative Example 7)×100

Formula: Low heat buildup index=(Tan δ value of rubber composition of each Example 11)/(Tan δ value of Comparative Example 8)×100

Formula: Low exothermicity index=(Tan δ value of rubber composition of each Example 12)/(Tan δ value of Comparative Example 9)×100

Examples 1 to 12 and Comparative Examples 1 to 9: Toughness (elongation rate at break) test Each elongation index at break of the rubber compositions obtained in the following Examples 1 to 12 and Comparative Examples 1 to 9. Was measured for elongation at break according to ASTM-D412. For comparison, rubber compositions (Comparative Examples 1, 3, 5, 7 to 9) were prepared with the same formulation content and the same production method as those in Examples, except that the above components (b) and (c) were not added. The elongation rate was set to 100. The elongation at break index was calculated based on the following formula. It should be noted that the larger the value of the elongation rate at break is, the higher the elongation rate at break is and the more excellent the toughness is.

Formula: elongation at break index=(elongation at break of rubber compositions of Examples 1 to 3)/(elongation at break of Comparative Example 1)×100

Formula: elongation at break index=(elongation at break of rubber compositions of Examples 4 to 6)/(elongation at break of Comparative Example 3)×100

Formula: elongation at break index=(elongation at break of rubber compositions of Examples 7 to 9)/(elongation at break of Comparative Example 5)×100

Formula: elongation at break index=(elongation at break of rubber composition of each Example 10)/(elongation at break of Comparative Example 7)×100

Formula: elongation at break index=(elongation at break of rubber composition of each Example 11)/(elongation at break of Comparative Example 8)×100

Formula: elongation at break index=(elongation at break of rubber composition of each Example 12)/(elongation at break of Comparative Example 9)×100

Examples 1 to 12 and Comparative Examples 1 to 9: Workability (Scorch Time) Test Each scorch time index of the unvulcanized rubber compositions obtained in the following Examples 1 to 12 and Comparative Examples 1 to 9 is JIS. The scorch time was measured according to K 6300. For comparison, rubber compositions (Comparative Examples 1, 3, 5, 7 to 9) were prepared with the same formulation content and the same production method as those in Examples, except that the above components (b) and (c) were not added. The scorch time was set to 100. The scorch time index was calculated based on the following formula. The larger the value of the scorch time index, the longer the scorch time and the better the workability.

Formula: Scorch time index=(Scorch time value of the rubber compositions of Examples 1 to 3)/(Scorch time value of Comparative Example 1)×100

Formula: Scorch time index=(Scorch time value of the rubber compositions of Examples 4 to 6)/(Scorch time value of Comparative Example 3)×100

Formula: Scorch time index=(Scorch time value of the rubber compositions of Examples 7 to 9)/(Scorch time value of Comparative Example 5)×100

Formula: scorch time index=(scorch time value of rubber composition of each Example 10)/(scorch time value of Comparative Example 7)×100

Formula: scorch time index=(scorch time value of rubber composition of each Example 11)/(scorch time value of Comparative Example 8)×100

Formula: scorch time index=(scorch time value of rubber composition of each Example 12)/(scorch time value of Comparative Example 9)×100

The rubber composition of the present invention can impart excellent low heat build-up, toughness, and processability to a rubber component without performing a special kneading method. Therefore, it can be used as each member of various pneumatic tires of various automobiles, particularly as a tread member of a pneumatic radial tire, a sidewall member, a bead area member, a belt member, a carcass member, and a shoulder member. it can.

Claims (9)

A rubber composition containing the following components (a), (b), (c) and (d):
Component (a) rubber component,
Component (b) at least one compound selected from compounds represented by formulas (1) to (3),
Component (c) Compounds represented by Formulas (4) and (5), and at least one compound selected from salts of the compounds,
Component (d) carbon black and/or an inorganic filler.

(In the formula, Z is one selected from the group consisting of an aromatic ring, a substituted or unsubstituted hydantoin ring, and a saturated or unsaturated linear hydrocarbon having 0 to 18 carbon atoms; Is an aromatic group, the substituent X of Q is at least one selected from a hydroxy group and an amino group, Y is one selected from a pyridyl group and a hydrazino group, and R ^{a to} R ^d are hydrogen and An alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, and an aromatic ring, which may be the same or different.)

(In formula (4), R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. R ³ and R ⁴ are They may be bonded to each other to form an alkylidene group, or any two of R ² , R ³ and R ⁴ may be bonded to each other to form an alkylene group, and each of these groups is substituted with one or more substituents. It may have a group.)

(In the formula (5), 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. A group, an aryl group, or a heterocyclic group, each of which may have one or more substituents.) In the compound represented by the above formula (2), X is a hydroxy group, R ^a and R ^b are the same or different and each represents a linear or branched alkyl group having 1 to 18 carbon atoms. Item 2. The rubber composition according to item 1. The rubber composition according to claim 1 or 2, wherein the component (c) is a compound represented by the formula (4). The rubber composition according to claim 1, wherein the component (a) is a diene rubber. The blending ratio of the component (b) is 0.01 to 50 parts by mass in 100% by mass of the total of the component (b) and the component (c). Rubber composition.
A tire produced using the rubber composition according to any one of claims 1 to 5. An additive containing the components (b) and (c). The step (A) of mixing the raw material components containing the components (a), (b), (c), and (d), and the step (B of mixing the mixture and the vulcanizing agent obtained in the step (A). The manufacturing method of the rubber composition containing these. In the step (A), the step (A-1) of mixing the components (a), (b) and (c), and the mixture (d) obtained in the step (A-1) are mixed. The manufacturing method according to claim 8, which is a step of performing.