JP7312024B2 - Rubber composition and tire - Google Patents

Description

The present invention relates to rubber compositions and tires.

Rubber moldings are widely used in applications such as machinery, home appliances, civil engineering and construction materials, automobiles, and vehicles. Among them, rubber compositions used for tires, conveyor belts, anti-vibration rubbers and the like are subjected to impacts under severe conditions, and therefore require high durability, particularly tear strength.

Moreover, from the viewpoint of production efficiency of rubber moldings, there is also a demand for a rubber composition having excellent processability.

The following rubber compositions have been proposed in order to improve both tear strength and processability of rubber compositions (for example, Patent Documents 1 and 2).

In Patent Document 1, a rubber composition containing silica and a liquid acrylic polymer having a modifying group that interacts with a silanol group on the silica surface in a rubber component containing a modified diene rubber into which a functional group containing a hetero atom is introduced. things are described.

Patent Document 2 describes a rubber composition containing a disulfide compound and a benzimidazole antioxidant in a rubber component containing natural rubber and/or isoprene rubber and butadiene rubber having a specific structure.

However, since Patent Documents 1 and 2 require the use of specific rubber components, it is difficult to adjust the compounding because the rubber components cannot be changed according to various uses.

JP 2015-28113 A JP 2015-17160 A

An object of the present invention is to provide a rubber composition with excellent processability and to provide a tire produced from the rubber composition with excellent tear strength performance.

As a result of intensive studies to solve the above problems, the present inventors have found that 0 to The tear strength performance of the tire obtained from the second rubber composition obtained by further adding a vulcanizing agent to the first rubber composition containing 1 part by mass is improved, and the processability of the rubber composition is improved. I found

That is, the present invention provides the following first rubber composition, method for producing the first rubber composition, second rubber composition, method for producing the second rubber composition, and tire.
Section 1.
A first rubber composition comprising the following components (a), (b), and (c), and containing 0 to 1 part by mass of a vulcanizing agent per 100 parts by mass of the following component (a).
(a) a rubber component;
(b) at least one compound selected from the group consisting of compounds represented by formula (1), compounds represented by formula (2), and salts of the compounds;
(c) an anti-aging agent;

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

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

（式（２）中、Ｒ^５、Ｒ^７及びＲ^８は同一又は異なって、水素原子、アミノ基、アルキル基、アラルキル基、アリール基、又は複素環基を示し、Ｒ^６はアルキル基、アラルキル基、アリール基、又は複素環基を示す。これら各基は、それぞれ１個以上の置換基を有していてもよい。）
項２．
前記成分（ｂ）が式（１）で表される化合物である、項１に記載の第一ゴム組成物。
項３．
前記成分（ａ）１００質量部に対して、前記成分（ｃ）を０．１～１０質量部含む、項１又は２に記載の第一ゴム組成物。
項４．
項１～３のいずれかに記載の第一ゴム組成物に、加硫剤を添加してなる、第二ゴム組成物。
項５．
項４に記載の第二ゴム組成物を用いて作製されたタイヤ。
項６．
前記成分（ａ）、（ｂ）及び（ｃ）を混合する工程（Ａ）を有する、項１～３のいずれかに記載の第一ゴム組成物の製造方法。
項７．
項６に記載の方法で作製された第一ゴム組成物に、加硫剤を混合する工程（Ｂ）を有する、第二ゴム組成物の製造方法。
項８．
前記成分（ａ）、（ｂ）及び（ｃ）を混合する工程（Ａ）、並びに工程（Ａ）から得られる第一ゴム組成物、及び加硫剤を混合する工程（Ｂ）を有する、第二ゴム組成物の製造方法。

(In formula (2), R ⁵ , R ⁷ and R ⁸ are the same or different and represent a hydrogen atom, an amino group, an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group, and R ⁶ is an alkyl group, an aralkyl group, aryl group, or heterocyclic group, each of which may have one or more substituents.)
Section 2.
Item 1. The first rubber composition according to item 1, wherein the component (b) is a compound represented by formula (1).
Item 3.
Item 3. The first rubber composition according to item 1 or 2, containing 0.1 to 10 parts by mass of component (c) with respect to 100 parts by mass of component (a).
Section 4.
A second rubber composition obtained by adding a vulcanizing agent to the first rubber composition according to any one of Items 1 to 3.
Item 5.
Item 5. A tire produced using the second rubber composition according to Item 4.
Item 6.
Item 4. The method for producing the first rubber composition according to any one of Items 1 to 3, comprising the step (A) of mixing the components (a), (b) and (c).
Item 7.
Item 7. A method for producing a second rubber composition, comprising a step (B) of mixing a vulcanizing agent with the first rubber composition produced by the method according to Item 6.
Item 8.
a step (A) of mixing the components (a), (b) and (c), and a step (B) of mixing the first rubber composition obtained from the step (A) and a vulcanizing agent; A method for producing a two-rubber composition.

INDUSTRIAL APPLICABILITY The present invention can provide a rubber composition excellent in processability and a tire produced from the rubber composition excellent in tear strength performance.

The present invention will be described in detail below.

(1. First rubber composition)
The first rubber composition of the present invention contains the following components (a), (b), and (c), and contains 0 to 1 part by mass of a vulcanizing agent with respect to 100 parts by mass of the following component (a). It is a rubber composition.
(a) a rubber component;
(b) at least one compound selected from the group consisting of compounds represented by formula (1), compounds represented by formula (2), and salts of the compounds;
(c) anti-aging agent

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

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

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

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

The first rubber composition of the present invention uses the above components (b) and (c) in combination with respect to 100 parts by mass of the above component (a), and contains 0 to 1 part by mass of a vulcanizing agent. Since the first rubber composition of the present invention has excellent processability, and a tire produced from the first rubber composition of the present invention has excellent tear strength, it is preferably used for tire production.

(1.1. Component (a): rubber component)
Component (a) is a rubber component. Such rubber components are not particularly limited, and examples include natural rubber (NR), synthetic diene rubber, synthetic non-diene rubber, a mixture of natural rubber and synthetic diene rubber, and natural rubber and synthetic non-diene rubber. and a mixture of a synthetic diene rubber and a synthetic non-diene rubber.

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

Synthetic diene rubbers include styrene-butadiene copolymer rubber (SBR), butadiene rubber (BR), isoprene rubber (IR), nitrile rubber (NBR), chloroprene rubber (CR), ethylene-propylene-diene ternary copolymer Polymer rubbers (EPDM), styrene-isoprene-styrene triblock copolymers (SIS), styrene-butadiene-styrene triblock copolymers (SBS), etc., and modified synthetic diene-based rubbers thereof can be mentioned.

Modified synthetic diene-based rubbers include diene-based rubbers obtained by modification techniques such as main chain modification, single-end modification, and both-end modification. Here, the modified functional group of the modified synthetic diene rubber includes various functional groups such as an epoxy group, an amino group, an alkoxysilyl group, and a hydroxyl group. It may be contained in rubber.

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

Synthetic non-diene rubbers include butyl rubber (IIR), ethylene-propylene rubber (EPM), ethylene-propylene-diene terpolymer rubber (EPDM), urethane rubber (U), propylene hexafluoride-vinylidene fluoride. Copolymer (FKM), tetrafluoroethylene-propylene copolymer (FEPM), tetrafluoroethylene-perfluorovinyl ether copolymer (FFKM), methyl silicone rubber (MQ), vinyl-methyl silicone rubber (VMQ), phenyl • Methylsilicone rubber (PMQ), etc., and their modified synthetic non-diene rubbers.

The modified synthetic non-diene rubber includes non-diene rubber obtained by modification techniques such as main chain modification, single end modification, and both end modification. Here, the modified functional group of the modified synthetic non-diene rubber includes various functional groups such as epoxy group, amino group, alkoxysilyl group, and hydroxyl group. It may be contained in the diene rubber.

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

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

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

The content of component (a) in the total 100% by mass of components (a), (b), and (c) in the first rubber composition is preferably 10 to 99% by mass, and 20 to 98% by mass. % by mass is more preferred. By containing 10% by mass or more of component (a), elasticity can be imparted to the first rubber composition. On the other hand, since the component (a) contained in the first rubber composition is 99% by mass or less, the cost of the first rubber composition can be reduced, and as a result, it is possible to improve the economic efficiency. There are advantages.

Natural rubber is preferably contained in an amount of 65 to 100% by mass, more preferably 75 to 100% by mass, and even more preferably 80 to 100% by mass in 100% by mass of component (a).

(1.2. Component (b): Compound Represented by Formula (1), Compound Represented by Formula (2), or Salt of the Compound)
Component (b) is a compound represented by the following formula (1) or a salt thereof (hereinafter, the compound and its salt are collectively referred to as compound (1)) or represented by the following formula (2): or a salt thereof (hereinafter, the compound and a salt thereof may be collectively referred to simply as compound (2)).

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

（式中、Ｒ^２及びＲ^４は、前記に同じ。）

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

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

（式中、Ｒ^１、Ｒ^２及びＲ^４は、前記に同じ。）

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

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

（式中、Ｒ^２、Ｒ^３及びＲ^４は、前記に同じ。）

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

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

（式中、Ｒ^６、Ｒ^７及びＲ^８は、前記に同じ。）

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

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

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

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

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

The content of component (b) in the total 100% by mass of components (a), (b), and (c) in the first rubber composition is preferably 0.001 to 30% by mass, and 0 It is more preferably 0.005 to 20% by mass. By containing 0.001% by mass or more of component (b), the tear strength can be improved. On the other hand, when the component (b) contained in the first rubber composition is 30% by mass or less, the cost of the first rubber composition can be reduced and the economic efficiency can be improved.

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

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

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

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

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

等が挙げられる。

etc.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In the compound (1), R ¹ , R ³ and R ⁴ are the same or different and each represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, an aralkyl group, an aryl group, or a heterocyclic ring. Compounds that are radicals are preferred.

(1.3. Component (c): anti-aging agent)
Component (c) is an anti-aging agent. Such anti-aging agents are not particularly limited, and examples thereof include aromatic secondary amine-based anti-aging agents, amine-ketone-based anti-aging agents, monophenol-based anti-aging agents, bisphenol-based anti-aging agents, polyphenol-based anti-aging agents. agent, benzimidazole anti-aging agent, dithiocarbamate anti-aging agent, thiourea anti-aging agent, phosphorous acid anti-aging agent, organic thioacid anti-aging agent, sulfide anti-aging agent, special wax anti-aging agent Among them, at least one selected from aromatic secondary amine-based antioxidants, benzimidazole-based antioxidants, and special wax-based antioxidants is preferable. Commercially available products can be suitably used as these anti-aging agents.

Aromatic secondary amine antioxidants include N-phenyl-1-naphthylamine, alkylated diphenylamine, octylated diphenylamine, 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, p-(p-toluene sulfonylamido)diphenylamine, N,N'-di-2-naphthyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N-phenyl -N'-(1,3-dimethylbutyl)-p-phenylenediamine, N-phenyl-N'-(3-methacryloyloxy-2-hydroxypropyl)-p-phenylenediamine and the like, among which N -Phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine is preferred.

Amine-ketone antioxidants include 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline, reaction of diphenylamine and acetone Among them, 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline is preferred.

Monophenol anti-aging agents include 2,6-di-tert-butyl-4-methylphenol, mono(α-methylbenzyl)phenol, di(α-methylbenzyl)phenol, tri(α-methylbenzyl)phenol and the like. Among them, 2,6-di-tert-butyl-4-methylphenol is preferred.

Bisphenol-based antioxidants include 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-butylidenebis ( 3-methyl-6-tert-butylphenol), 4,4′-thiobis(3-methyl-6-tert-butylphenol), butylated reaction products of p-cresol and dicyclopentadiene, among others, 2,2'-methylenebis(4-ethyl-6-tert-butylphenol) is preferred.

Polyphenol-based antioxidants include 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, etc. Among them, 2,5-di-tert-butylhydroquinone is preferred.

The benzimidazole anti-aging agent includes 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, zinc salts of 2-mercaptobenzimidazole, etc. Among them, 2-mercaptobenzimidazole is preferred.

Examples of the dithiocarbamate anti-aging agent include nickel dibutyldithiocarbamate.

Thiourea-based antioxidants include 1,3-bis(dimethylaminopropyl)-2-thiourea, tributylthiourea, etc. Among them, 1,3-bis(dimethylaminopropyl)-2-thiourea preferable.

Phosphite-based anti-aging agents include tris(nonylphenyl) phosphite and the like.

Examples of organic thioacid anti-aging agents include dilauryl thiodipropionate.

Examples of sulfide anti-aging agents include bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide.

Among the above anti-aging agents, N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine, which is an aromatic secondary amine-based anti-aging agent, and 2,2, which is an amine-ketone-based anti-aging agent ,4-trimethyl-1,2-dihydroquinoline polymer, 2,6-di-tert-butyl-4-methylphenol as a monophenol anti-aging agent, and 2-mercaptobenzimidazole as a benzimidazole anti-aging agent are preferable. , aromatic secondary amine anti-aging agent N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine, and benzimidazole anti-aging agent 2-mercaptobenzimidazole are more preferable, and aromatic N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine, a group secondary amine antioxidant, is particularly preferred.

The amount of component (c) compounded is preferably 0.5 to 10 parts by mass, more preferably 0.7 to 7 parts by mass, with respect to 100 parts by mass of component (a) in the first rubber composition. more preferably 1 to 5 parts by mass.

The content of component (c) in the total 100% by mass of components (a), (b), and (c) in the first rubber composition is preferably 0.1 to 10% by mass, and 0 0.5 to 5% by mass is more preferable. When the component (c) is contained in an amount of 0.1% by mass or more, scission of the rubber main chain due to aging can be suppressed, and low heat build-up can be improved. On the other hand, when the component (c) contained in the first rubber composition is 11% by mass or less, contamination of the rubber composition due to bleeding out can be suppressed.

(1.4. Vulcanizing agent)
The first rubber composition of the present invention contains 0 to 1 part by mass, preferably 0 to 0.5 parts by mass, of a vulcanizing agent with respect to 100 parts by mass of the component (a). It is particularly preferred not to contain any As described above, the vulcanizing agent is particularly preferably contained in an amount of 0 parts by weight (not contained at all) with respect to 100 parts by weight of component (a), but may be contained in an amount of 1 part by weight or less, for example , 0.001 to 1 part by mass per 100 parts by mass of component (a). The vulcanizing agent will be described in detail in (2. Second rubber composition) below.

If the first rubber composition contains more than 1 part by mass of the vulcanizing agent with respect to 100 parts by mass of component (a), the tear strength of the tire, which is the final product, will not be sufficient, and , the workability during tire production is also deteriorated.

(1.5. Other compounds)
In addition to the above components (a), (b), (c) and the vulcanizing agent, the first rubber composition of the present invention contains compounding agents commonly used in the rubber industry, such as carbon black, inorganic Fillers, antiozonants, softeners, processing aids, waxes, resins, liquid rubbers, foaming agents, oils, fatty acids with 8 to 30 carbon atoms such as stearic acid, zinc oxide (ZnO), vulcanization accelerators, vulcanization accelerators, A sulfur retardant or 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 suitably used as these compounding agents.

Carbon black is generally used to improve the reinforcing properties of rubber. In this specification, the inorganic filler does not include carbon black.

Carbon black is not particularly limited, and examples thereof include commercially available carbon black, Carbon-Silica Dual phase filler, and the like. By including carbon black in the rubber component, it is possible to enjoy the effect of reducing the electrical resistance of the rubber to suppress electrification and the effect of improving the strength of the rubber.

Specifically, carbon black includes, for example, high-, medium-, or low-structure SAF, ISAF, IISAF, N110, N134, N220, N234, N330, N339, N375, N550, HAF, FEF, GPF, and SRF grade carbon. black and the like. Among them, preferred carbon blacks are SAF, ISAF, IISAF, N134, N234, N330, N339, N375, HAF, or FEF grade carbon blacks.

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.

In addition, the nitrogen adsorption specific surface area (N2SA, measured according to JISK6217-2:2001) of carbon black is preferably 30 to 200 m ² /g, more preferably 40 to 180 m ² /g, particularly preferably 50 to 200 m 2 /g. 160 m ² /g.

The inorganic filler is not particularly limited as long as it is an inorganic compound commonly used in the rubber industry. Examples of usable inorganic compounds include silica; alumina (Al ₂ O ₃ ) such as γ-alumina and α-alumina; alumina monohydrate (Al ₂ O ₃ ·H ₂ O) such as boehmite and diaspore; , bayerite and other aluminum hydroxide [Al(OH) ₃ ]; aluminum carbonate [ _Al2 ( _CO3 ) ₃ ], magnesium hydroxide [Mg(OH) ₂ ], magnesium oxide (MgO), magnesium carbonate ( _MgCO3 ), talc ( _{3MgO.4SiO.sub.2.H.sub.2O} ), attapulgye _{( 5MgO.8SiO.sub.2.9H.sub.2O} ), titanium white ( _TiO.sub.2 ), titanium black ( _{TiO.sub.2n -1} ), calcium oxide (CaO), hydroxide _Calcium [Ca(OH _{) 2 ]} , _magnesium aluminum oxide _{( MgO.Al2O3} ), clay ( _Al2O3.2SiO2 ), kaolin ( _{Al2O3.2SiO2.2H2O} ), _pyrophyllite ( _{Al2O3.4SiO2.H2O ) , bentonite ( Al2O3.4SiO2.2H2O )} , _aluminum silicate _{( Al2SiO5} , _{Al4.3SiO4.5H2O , etc.} ), magnesium silicate ( _Mg2SiO4 , _MgSiO3 , _etc. ), calcium silicate (Ca2.SiO4 _, etc. ₎ , aluminum calcium silicate (Al2O3.CaO.2SiO2 _{, etc.} ), magnesium calcium silicate _{( CaMgSiO4} ), 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 include crystalline aluminosilicates containing hydrogen, alkali metals, or alkaline earth metals that correct charge such as various zeolites. The surface of these inorganic fillers may be organically treated in order to improve the affinity with the rubber component.

The inorganic filler is preferably silica from the viewpoint of imparting rubber strength, more preferably silica alone, or silica and one or more inorganic compounds commonly used in the rubber industry in combination. When silica and the 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, preferred silica is wet silica, dry silica, or colloidal silica, and more preferred is wet silica. The surface of these silicas may be organically treated in order to improve the affinity with the rubber component.

The BET specific surface area of silica is not particularly limited, and is, for example, in the range of 40 to 350 m ² /g. Silica having a BET specific surface area within this range has the advantage of being able to achieve both rubber reinforcing properties and dispersibility in the rubber component. The BET specific surface area is measured according to ISO5794/1.

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

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

When carbon black is blended into the first rubber composition of the present invention, the amount of carbon black to be blended is not particularly limited. , preferably 30 to 130 parts by mass, more preferably 35 to 110 parts by mass.

When an inorganic filler is blended into the first rubber composition of the present invention, the amount of the inorganic filler to be blended is not particularly limited. parts by mass, preferably 20 to 150 parts by mass, more preferably 30 to 100 parts by mass.

When both the carbon black and the inorganic filler are blended in the first rubber composition of the present invention, the total amount of both components may be appropriately adjusted so as to fall within the above range.

Further, when carbon black or an inorganic filler is blended into the first rubber composition of the present invention, the purpose of increasing the toughness of the rubber composition by the carbon black or the inorganic filler, or the tear strength and abrasion resistance of the rubber composition A silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a zirconate coupling agent, or the like may be blended for the purpose of enhancing the properties.

A silane coupling agent that can be used in combination with carbon black or an inorganic filler is not particularly limited, and commercially available products can be suitably 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 sulfide-based silane coupling agents include bis(3-triethoxysilylpropyl) tetrasulfide, bis(3-trimethoxysilylpropyl) tetrasulfide, bis(3-methyldimethoxysilylpropyl) tetrasulfide, bis( 2-triethoxysilylethyl)tetrasulfide, bis(3-triethoxysilylpropyl)disulfide, bis(3-trimethoxysilylpropyl)disulfide, bis(3-methyldimethoxysilylpropyl)disulfide, bis(2-triethoxysilyl) ethyl)disulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-trimethoxysilylpropyl)trisulfide, bis(3-methyldimethoxysilylpropyl)trisulfide, bis(2-triethoxysilylethyl)trisulfide Sulfide, bis(3-monoethoxydimethylsilylpropyl)tetrasulfide, bis(3-monoethoxydimethylsilylpropyl)trisulfide, bis(3-monoethoxydimethylsilylpropyl)disulfide, bis(3-monomethoxydimethylsilylpropyl) Tetrasulfide, bis(3-monomethoxydimethylsilylpropyl)trisulfide, bis(3-monomethoxydimethylsilylpropyl)disulfide, bis(2-monoethoxydimethylsilylethyl)tetrasulfide, bis(2-monoethoxydimethylsilylethyl) ) trisulfide, bis(2-monoethoxydimethylsilylethyl)disulfide and the like. Of these, bis(3-triethoxysilylpropyl)tetrasulfide is particularly preferred.

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

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

Examples of olefinic silane coupling agents include dimethoxymethylvinylsilane, vinyltrimethoxysilane, dimethylethoxyvinylsilane, diethoxymethylvinylsilane, triethoxyvinylsilane, vinyltris(2-methoxyethoxy)silane, allyltrimethoxysilane, allyltri Ethoxysilane, p-styryltrimethoxysilane, 3-(methoxydimethoxydimethylsilyl)propyl acrylate, 3-(trimethoxysilyl)propyl acrylate, 3-[dimethoxy(methyl)silyl]propyl methacrylate, 3-(trimethoxysilyl) Propyl methacrylate, 3-[dimethoxy(methyl)silyl]propyl methacrylate, 3-(triethoxysilyl)propyl methacrylate, 3-[tris(trimethylsiloxy)silyl]propyl methacrylate and the like can be mentioned.
Examples of epoxy-based silane coupling agents include 3-glycidyloxypropyl(dimethoxy)methylsilane, 3-glycidyloxypropyltrimethoxysilane, diethoxy(3-glycidyloxypropyl)methylsilane, and triethoxy(3-glycidyloxypropyl)silane. , 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and the like. Of these, 3-glycidyloxypropyltrimethoxysilane is preferred.

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

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

Among these silane coupling agents, it is particularly preferable to use bis(3-triethoxysilylpropyl)tetrasulfide.

Titanate coupling agents that can be used in combination with carbon black or inorganic fillers are not particularly limited, and commercially available products can be suitably used. Examples of such titanate coupling agents include alkoxide, chelate, and acylate titanate coupling agents.

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

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

Examples of the acylate titanate coupling agent include titanium isostearate.

Aluminate coupling agents that can be used in combination with carbon black or inorganic fillers are not particularly limited, and commercially available products can be suitably used. Examples of such aluminate coupling agents include 9-octadecenylacetoacetate aluminum diisopropylate, aluminum secondary butoxide, aluminum trisacetylacetonate, aluminum bisethylacetoacetate monoacetylacetonate, aluminum trisethylacetoacetate and the like. can be mentioned. Of these, 9-octadecenylacetoacetate aluminum diisopropylate is preferred.

A zirconate coupling agent that can be used in combination with carbon black or an inorganic filler is not particularly limited, and commercially available products can be suitably used. Examples of such zirconate coupling agents include alkoxide, chelate, and acylate zirconate coupling agents.

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

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

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

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

The amount of the coupling agent in the first rubber composition of the present invention is preferably 0.1 to 20 parts by mass, particularly 3 to 15 parts by mass, with respect to 100 parts by mass of the total amount of carbon black and inorganic filler. preferable. 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 exhibited, and if it is 20 parts by mass or less, the cost of the rubber composition is reduced and economic efficiency is improved. Because it does.

(2. Second rubber composition)
The second rubber composition of the present invention is a rubber composition obtained by adding a vulcanizing agent to the first rubber composition, and can be suitably used as a rubber composition for manufacturing tires.

The vulcanizing agent added to the second rubber composition of the present invention is not particularly limited, and examples thereof include sulfur, peroxides, quinonedioxime compounds, nitrosobenzene compounds, thio compounds, bismaleimide compounds, and the like. , among these, sulfur and peroxides are preferred. Commercially available products can be suitably used as these vulcanizing agents.

Sulfur may be an oil-processed product obtained by adding 2 to 10% by mass of oil generally used in the rubber industry, such as naphthenic oil, to sulfur.

Peroxides include dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butyl-peroxy)hexane and the like, with dicumyl peroxide being preferred.

Examples of the quinonedioxime compound include p-quinonedioxime, o,o'-dibenzoyl-p-quinonedioxime, etc. Among them, p-quinonedioxime is preferred.

Nitrobenzene compounds include poly-p-dinitrosobenzene and the like.

Thio compounds include 4,4'-dithiomorpholine and the like.

Examples of the bismaleimide compound include N,N'-m-phenylenebismaleimide, N,N'-m-phenylenebiscitraconimide, etc. Among them, N,N'-m-phenylenebismaleimide is preferred.

The amount of the vulcanizing agent compounded is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 7 parts by mass, with respect to 100 parts by mass of the component (a) in the first rubber composition. is more preferable, and 0.1 to 5 parts by mass is even more preferable.

The content of the vulcanizing agent in the total 100% by mass of the first rubber composition and the vulcanizing agent in the second rubber composition is preferably 0.01 to 10% by mass, and 0.1 to It is more preferably 5% by mass. By containing 0.01% by mass or more of the vulcanizing agent, low heat build-up can be improved. On the other hand, when the vulcanizing agent is 10% by mass or less, it is possible to reduce the cost of the second rubber composition and, as a result, improve the economic efficiency.

In addition to the first rubber composition and the vulcanizing agent, the second rubber composition of the present invention contains compounding agents that are usually used by the Rubber Industry Association described in (1.5. Other compounding agents) above. , can be appropriately selected and blended within a range that does not impair the object of the present invention. Commercially available products can be suitably used as these compounding agents.

An antioxidant may be newly added to the second rubber composition of the present invention. The anti-aging agent is the same as the above (1.3. Anti-aging agent). The same type of component (c) added in the first rubber composition of the present invention may be further added to the second rubber composition, or a different type may be newly added to the second rubber composition. good.

As described above, after producing the first rubber composition containing the rubber component, the specific pyrazolone-based compound, and the anti-aging agent, the vulcanizing agent is blended to form the second rubber composition. It is possible to achieve the improvement of workability and the improvement of tear strength, which are the targets.

(3. Manufacturing method of first rubber composition: step (A))
The method for producing the first rubber composition of the present invention has a step (A) of mixing the components (a), (b), and (c).

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

In this mixing method, the total amount of each component may be mixed at once, or each component may be divided and mixed according to the purpose such as viscosity adjustment. Alternatively, after mixing the components (a) and (b), the component (c) is added, or after the components (a) and (c) are mixed, the component (b) is added and mixed. You can In order to uniformly disperse each component, the mixing operation may be repeated. Also, a filler masterbatch rubber in which a filler is added in advance to rubber by a wet method and/or a dry mixing method may be used.

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

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

In the method for producing the first rubber composition of the present invention, other compounding agents such as carbon black, inorganic filler, stearic acid, and zinc oxide, which are usually blended in the rubber composition, are optionally added to the step (A) can be added in

Among them, when carbon black and/or an inorganic filler are added to the first rubber composition of the present invention and mixed together, the above components (a), (b), and (c) are mixed together. Alternatively, each component may be separately added and mixed depending on the purpose such as viscosity adjustment.

When carbon black and/or an inorganic filler are added to and mixed with the first rubber composition of the present invention, another kneading method other than the above includes the components (a), (b), and ( A step (A-1) of kneading c), and a step of kneading the first rubber composition of the present invention obtained in step (A-1) with carbon black and/or a raw material component containing an inorganic filler ( A two-stage kneading method including A-2) can be mentioned.

The temperature at which the first rubber composition is mixed in step (A-1) is not particularly limited. and more preferably 120 to 170°C.

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

The temperature at which the first rubber composition of the present invention obtained in step (A-1) in step (A-2) is mixed with carbon black and/or an inorganic filler is not particularly limited. For example, the temperature of the mixture is preferably 100 to 190°C, more preferably 130 to 175°C, even more preferably 110 to 170°C.

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

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

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

When the first rubber composition contains 1 part by mass or less of vulcanizing agent per 100 parts by mass of component (a), the mixing method is not particularly limited.

(3.1. Mixing method of the first rubber composition)
The first rubber composition in the present invention is preferably mixed using a Banbury mixer, roll, intensive mixer, kneader, single-screw extruder, twin-screw extruder, or the like.

(4. Method for producing second rubber composition: step (B))
The method for producing the second rubber composition of the present invention has a step (B) of mixing a vulcanizing agent with the first rubber composition produced in the step (A). It is particularly preferable to add a vulcanizing agent in the step (B) after producing a first rubber composition containing a rubber component, a specific pyrazolone-based compound, and an anti-aging agent and not containing a vulcanizing agent.

Therefore, the method for producing the second rubber composition of the present invention includes the step (A) of mixing the components (a), (b) and (c), and the first rubber composition obtained from the step (A), and a step (B) of mixing a vulcanizing agent.

In the method for producing the second rubber composition of the present invention, an antioxidant may be newly added in step (B).

In the method for producing the second rubber composition of the present invention, other compounding agents such as a vulcanization accelerator, stearic acid, and zinc oxide, which are usually blended in the rubber composition, are added in step (B) as necessary. can do.

The above other compounding agents may be added in either step (A) or step (B),
Alternatively, they may be added separately in step (A) and step (B).

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

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

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

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

(5. Tire)
The tire of the present invention is a tire produced using the second 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 include passenger car tires, high-load tires, motorcycle (motorcycle) tires, studless tires, etc. Among them, it can be suitably used for passenger car tires.

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

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

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

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

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

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

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

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

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

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

The tire of the present invention can provide a tire with excellent tear strength performance.

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

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

Production Example 1: Production of 3-(naphthalen-2-yl)-1H-pyrazol-5(4H)-one (Compound (b)-2) 8.5 g (52.1 mmol) of carbonyldiimidazole was placed in a 100 mL eggplant-shaped flask, and 60 mL of dehydrated tetrahydrofuran were added and stirred at room temperature. Then 7.5 g (43.6 mmol) of 2-naphthoic acid was added to the mixture and stirred overnight at room temperature. Hereinafter, the obtained reaction liquid is referred to as "reaction liquid 1".
14.8 g (87.0 mmol) of potassium monoethylmalonate, 210 mL of dehydrated acetonitrile, and 18.3 mL (132.4 mmol) of triethylamine were added to a 500 mL four-necked flask and stirred under ice cooling. Then, 10.4 g (109.2 mmol) of magnesium chloride was added to this mixture and stirred at room temperature for 4 hours. The above reaction solution 1 was added dropwise to the obtained reaction solution, and the mixture was stirred overnight at room temperature.

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

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

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

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

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

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

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

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

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

Production Example 6: Production of 4,4′-(4-hydroxyphenylmethylene)bis(5-methyl-1H-pyrazol-3(2H)-one) (compound (b)-7) In a 3 L four-necked flask, 2.5 L of water, 25.0 g (0.26 mol) of 3-methyl-5-pyrazolone, 15.6 g (0.13 mol) of 4-hydroxybenzaldehyde, and 1.84 g (6.4 mmol) of sodium dodecylsulfate were added to room temperature. After stirring at rt for 30 minutes, it was refluxed for 1 hour. After stirring the reaction mixture for 30 minutes while cooling it in an ice bath, the precipitated solid was filtered, washed with 2.5 L of water, and dried to give a pale yellow solid of 4,4'-(4-hydroxyphenyl). 33.5 g of methylene)bis(5-methyl-1H-pyrazol-3(2H)-one) are obtained.
Melting point: 262-264°C
¹ H-NMR (500 MHz, d ₆ -DMSO, δppm):
11.22 (4H, br), 9.03 (1H, s), 6.91 (2H, J=8.5Hz, 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 7: Production of 4,4′-(4-nitrophenylmethylene)bis(5-methyl-1H-pyrazol-3(2H)-one) (compound (b)-8) In a 3 L four-necked flask, 2.5 L of water, 25.0 g (0.26 mol) of 3-methyl-5-pyrazolone, 19.3 g (0.13 mol) of 4-nitrobenzaldehyde, and 1.84 g (6.4 mmol) of sodium dodecylsulfate were added and the mixture was stirred at room temperature. After stirring at rt for 30 minutes, it was refluxed for 1 hour. After stirring this reaction solution for 30 minutes while cooling it in an ice bath, the precipitated solid was filtered, washed with 500 mL of methanol, and dried to give a pale yellow solid of 4,4′-(4-nitrophenylmethylene). 37.8 g of bis(5-methyl-1H-pyrazol-3(2H)-one) are obtained.
Melting point: 300-302°C
¹ H-NMR (500 MHz, d ₆ -DMSO, δppm):
11.40 (4H, br), 8.12 (2H, J=8.8Hz, d), 7.38 (2H, J=8.8Hz, d), 4.98 (1H, s), 2. 10 (6H, s)
¹³ C-NMR (500 MHz, d ₆ -DMSO, δppm):
160.82, 151.71, 145.56, 139.71, 128.76, 122.94, 103.24, 32.95, 10.28

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

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

Production Example 10: Production of 3-undecyl-1H-pyrazol-5(4H)-one (Compound (b)-11) 2.8 g (17.4 mmol) of carbonyldiimidazole and 20 mL of chloroform were added to a 50 mL eggplant flask. , and stirred at room temperature. To this mixture was then added 2.9 g (14.5 mmol) of lauric acid and stirred overnight at room temperature. Hereinafter, the obtained reaction liquid is referred to as "reaction liquid 3".
4.9 g (30.0 mmol) of potassium monoethylmalonate, 70 mL of dehydrated acetonitrile, and 6.1 mL (44.1 mmol) of triethylamine were added to a 200 mL four-necked flask and stirred under ice-cooling. Then, 3.5 g (36.4 mmol) of magnesium chloride was added to the resulting mixture and stirred at room temperature for 4 hours. The above reaction solution 3 was added dropwise to this reaction solution, and the mixture was stirred overnight at room temperature. The resulting reaction solution was concentrated, 42 mL of chloroform was added, washed with 48 mL of 2M hydrochloric acid and 48 mL of water, and the organic layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain the desired product.
20 mL of ethanol and 0.7 mL (14.9 mmol) of hydrazine monohydrate were added to the resulting desired product, 0.7 mL (11.7 mmol) of acetic acid was added dropwise, and the mixture was refluxed for 4 hours. The reaction solution was returned to room temperature, 10 mL of diisopropyl ether was added, and the precipitated crystals were filtered to obtain 2.83 g of 3-undecyl-1H-pyrazol-5(4H)-one as a white solid.
Melting point: 188°C
¹ H-NMR (300 MHz, d ₆ -DMSO, δppm):
11.05 (1H, br), 9.45 (1H, br), 5.21 (1H, s), 2.39-2.44 (2H, J=7.5Hz, t), 1.48- 1.53 (2H, m), 1.30 (16H, s), 0.83-0.88 (3H, m)
¹³ C-NMR (500 MHz, d ₆ -DMSO, δppm):
160.85, 144.20, 87.84, 31.27, 29.01, 28.98, 28.95, 28.71, 28.68, 28.62, 28.57, 25.60, 22. 06, 13.90

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

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

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

Production Example 14: Production of 4-methyl-2,3-diazospiro[4.4]non-3en-1-one (Compound (b)-15) 7.2 g of methyl acetoacetate (62 .0 mmol), 23.1 g (75 mmol) of 1,4-diiodobutane, 42.9 g (310 mmol) of potassium carbonate, and 220 mL of dimethylsulfoxide were added and stirred overnight at room temperature. After adding 220 mL of water to the reaction solution and stirring for 10 minutes, the organic layer obtained by extraction with 300 mL of isopropyl ether was washed twice with 200 mL of water. After the organic layer was dried over sodium sulfate, it was concentrated and subjected to column purification (hexane:ethyl acetate=50:1 (volume ratio)) to obtain 6.5 g (36 mmol) of the intermediate.
The obtained intermediate and 6 mL of ethanol were mixed, 1.8 mL (39 mmol) of hydrazine monohydrate was added while cooling on an ice bath, and the mixture was stirred at 60° C. overnight. The solid obtained by concentrating the reaction solution was washed with 40 mL of a mixed solution of hexane:ethyl acetate=5:1 (volume ratio) to give 4-methyl-2,3-diazospiro[4.4] as a white solid. 3.8 g of non-3en-1-one were obtained.
Melting point: 83-84°C
¹ H-NMR (500 MHz, d ₆ -DMSO, δppm):
10.77 (1H, s), 1.92 (3H, s), 1.86-1.66 (8H, m)
¹³ C-NMR (500 MHz, d ₆ -DMSO, δppm):
181.64, 163.37, 55.78, 33.53, 26.48, 13.34

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

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

Example 1 and Comparative Examples 1 to 5: Production of first rubber composition and second rubber composition Each component described in step (A) in Table 1 below was mixed in its proportion (parts by mass) and mixed in a Banbury mixer. A first rubber composition was produced by mixing at After curing until the temperature of the first rubber composition reaches 60 ° C. or less, each component described in step (B) in Table 1 containing a vulcanizing agent is added to the first rubber composition in its proportion (parts by mass) The second rubber composition was produced by throwing in and mixing. Furthermore, they were mixed while adjusting the maximum temperature of the second rubber composition to 70° C. or lower.

尚、表１における各成分の詳細は、下記の通りである。
※１：成分（ａ）天然ゴム；ＧＵＡＮＧＫＥＮ ＲＵＢＢＥＲ社製、ＴＳＲ－２０
※２：成分（ｂ）化合物（ｂ）－１；大塚化学株式会社製、３－メチル－５－ピラゾロン
※３：成分（ｃ）老化防止剤；Ｎ－フェニル－Ｎ’－（１，３－ジメチルブチル）－ｐ－フェニレンジアミン、大内新興化学社製、ノクラック６Ｃ
※４：カーボンブラック；Ｃａｂｏｔ社製、Ｎ２３４
※５：ワックス；大口新興化学社製、サンノック
※６：ステアリン酸；Ｓｉｃｈｕａｎ Ｔｉａｎｙｕ Ｇｒｅａｓｅ社製
※７：酸化亜鉛；Ｄａｌｉａｎ Ｚｉｎｃ Ｏｘｉｄｅ Ｃｏ．，Ｌｔｄ社製
※８：加硫促進剤；Ｎ－（ｔｅｒｔ－ブチル）－２－ベンゾチアゾールスルフェンアミド三新化学工業社製、サンセラーＮＳ－Ｇ
※９：加硫剤（硫黄）；Ｓｈａｎｇｈａｉ Ｊｉｍｇｈａｉ Ｃｈｅｍｉｃａｌ Ｃｏ．，Ｌｔｄ社製

The details of each component in Table 1 are as follows.
*1: Component (a) natural rubber; TSR-20 manufactured by GUANGKEN RUBBER
*2: Component (b) compound (b)-1; manufactured by Otsuka Chemical Co., Ltd., 3-methyl-5-pyrazolone *3: Component (c) anti-aging agent; N-phenyl-N'-(1,3- Dimethylbutyl)-p-phenylenediamine, manufactured by Ouchi Shinko Chemical Co., Ltd., Nocrac 6C
*4: Carbon black; manufactured by Cabot, N234
*5: Wax; manufactured by Oguchi Shinko Chemical Co., Ltd., Sannok *6: Stearic acid; manufactured by Sichuan Tianyu Grease *7: Zinc oxide; manufactured by Dalian Zinc Oxide Co.; , Ltd. *8: Vulcanization accelerator; N-(tert-butyl)-2-benzothiazolesulfenamide Sanshin Chemical Industry Co., Ltd., Suncellar NS-G
*9: Vulcanizing agent (sulfur); Shanghai Jimghai Chemical Co.; , Ltd.

Example 1 and Comparative Examples 1 to 5: Tearing Strength Performance Test The rubber compositions of Example 1 and Comparative Examples 1 to 5 below were tested using a crescent type test piece according to JIS K 6252 at room temperature at a tensile rate of 500 mm/min. The tear strength was calculated under the conditions of The value of Comparative Example 1 obtained here was expressed as an index with 100, and the tear strength index was calculated based on the following formula. It should be noted that the higher the tear strength index, the better the tear strength performance.
Formula: tear strength figure of merit = (tear strength of rubber compositions of Examples 1 and Comparative Examples 2 to 5)/(tear strength of Comparative Example 1) x 100

Example 1 and Comparative Examples 1 to 5: Scorch Time Test The scorch time of the rubber compositions of Example 1 and Comparative Examples 1 to 5 below was measured according to JIS K 6300. The value of Comparative Example 1 obtained here was expressed as an index with 100, and the scorch time index was calculated based on the following formula. In addition, it shows that it is excellent in workability, so that the numerical value of a scorch time index is high.
Formula: Scorch time index = (scorch time of rubber compositions of Examples 1 and Comparative Examples 2 to 5)/(scorch time of Comparative Example 1) x 100

The second rubber composition obtained by adding a vulcanizing agent to the first rubber composition of the present invention can impart excellent tear strength and workability to the rubber component. Therefore, it can be used as each member of various pneumatic tires of various automobiles, especially as tread member, sidewall member, bead area member, belt member, carcass member and shoulder member of pneumatic radial tire. can.

Claims (8)

For producing a second rubber composition containing the following components (a), (b), and (c), and containing 0 to 1 part by mass of a vulcanizing agent with respect to 100 parts by mass of the following component (a) A first rubber composition.
(a) a rubber component;
(b) at least one compound selected from the group consisting of compounds represented by formula (1), compounds represented by formula (2), and salts of the compounds;
(c) an anti-aging agent;

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

(In Formula (2), R ⁵ , R ⁷ and R ⁸ are the same or different and represent a hydrogen atom, an amino group, an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group, and R ⁶ is an alkyl group, an aralkyl group, aryl group, or heterocyclic group, each of which may have one or more substituents.) The first rubber composition according to claim 1, wherein said component (b) is a compound represented by formula (1). The first rubber composition according to claim 1 or 2, comprising 0.1 to 10 parts by mass of component (c) with respect to 100 parts by mass of component (a). A second rubber composition obtained by adding a vulcanizing agent to the first rubber composition according to any one of claims 1 to 3. A tire produced using the second rubber composition according to claim 4 . The method for producing the first rubber composition according to any one of claims 1 to 3, comprising a step (A) of mixing the components (a), (b) and (c). A method for producing a second rubber composition, comprising the step (B) of mixing a vulcanizing agent with the first rubber composition produced by the method according to claim 6. The step (A) of mixing 0 to 1 part by mass of the following components (a), (b), (c) and a vulcanizing agent , and the first rubber composition obtained from the step (A) and the vulcanizing agent A method for producing a second rubber composition, comprising a mixing step (B).
(a) a rubber component;
(b) at least one compound selected from the group consisting of compounds represented by formula (1), compounds represented by formula (2), and salts of the compounds;
(c) an anti-aging agent;

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

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