JP6921596B2 - Additives for rubber, rubber compositions, and tires using them - Google Patents

Description

The present invention relates to a rubber additive, a rubber composition, and a tire using the same.

In recent years, due to consideration for the environment, carbon dioxide emission regulations have become stricter worldwide, and the demand for fuel efficiency of automobiles has increased significantly. The efficiency of the drive system such as the engine and the transmission system contributes greatly to the fuel efficiency, but the rolling resistance of the tire is also greatly involved, and it is important to reduce the rolling resistance to reduce the fuel efficiency of the tire. ..

As a method for reducing the rolling resistance of a tire, it is known to apply a rubber composition having low heat generation to the tire. Examples of such a low heat-generating rubber composition include (1) a rubber composition containing a functionalized polymer having an enhanced affinity with carbon black as a filler and silica (Patent Document 1); (2). ) A rubber composition containing a diene elastomer, an inorganic filler as a reinforcing filler, an alkoxysilane polysulfide as a coupling agent, 1,2-dihydropyridine, and a guanidine derivative (Patent Document 2); (3) Rubber component, aminopyridine derivative. And a rubber composition containing an inorganic filler (Patent Document 3); (4) a rubber composition containing a terminal-modified polymer and an inorganic filler (Patent Documents 4 and 5) and the like.

According to the inventions described in Patent Documents 1 to 5, the heat generation of the rubber composition can be lowered by increasing the affinity between the filler and the rubber component, and as a result, hysteresis loss (rolling) can be achieved. A tire with low resistance) can be obtained.

However, even if the rubber compositions of Patent Documents 1 to 5 are used, the effect of reducing heat generation is insufficient, and a tire having satisfactory fuel efficiency cannot be obtained.

The demand for fuel efficiency of automobiles is increasing, and the development of tires with extremely low heat generation is eagerly desired.

Japanese Unexamined Patent Publication No. 2003-514079 Japanese Patent Application Laid-Open No. 2003-523472 Japanese Unexamined Patent Publication No. 2013-108004 Japanese Unexamined Patent Publication No. 2000-169631 Japanese Unexamined Patent Publication No. 2005-220323

An object of the present invention is to provide an additive for imparting low heat generation to a rubber component.

One of the other objects of the present invention is to provide a rubber composition capable of exhibiting low heat generation.

One of the other objects of the present invention is to provide a modified polymer capable of imparting low heat buildup.

One of the other objects of the present invention is to provide a tire having excellent low heat generation.

As a result of diligent studies to solve the above problems, the present inventors have discovered that an azomethine imine-based compound can impart low heat generation to a rubber component. The present inventors have completed the present invention as a result of further studies based on such findings.

That is, the present invention provides the following additives, modified polymers, rubber compositions, methods for producing the rubber compositions, and tires for imparting low heat generation to the rubber components.
Item 1.
It is an additive for imparting low heat generation to the rubber component.
An additive containing an azomethine imine compound represented by the following general formula (1) or a salt thereof.

[In the formula, R ¹ and R ² represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, which are the same or different, and each of these groups may have one or more substituents. .. R ³ , R ⁴ , R ⁵ and R ⁶ represent the same or different hydrogen atoms, alkyl or aryl groups, each of which may have one or more substituents. n represents an integer of 0 to 2. ]
Item 2.
Item 2. The additive according to Item 1, wherein R ^{1 is an aryl group or a heterocyclic group.}
Item 3.
Item 2. The additive according to Item 1 or 2, wherein the rubber component is a diene-based rubber.
Item 4.
A modified polymer prepared by using a rubber mixture containing a rubber component and the additive according to any one of Items 1 to 3.
Item 5.
Item 2. The modified polymer according to Item 4, wherein the rubber component is a diene-based rubber.
Item 6.
A modified polymer having at least one selected from the compound structures represented by the following general formulas (2-1) to (2-7).

[In the formula, R ¹ and R ² represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, which are the same or different, and each of these groups may have one or more substituents. .. R ³ , R ⁴ , R ⁵ and R ⁶ represent the same or different hydrogen atoms, alkyl or aryl groups, each of which may have one or more substituents. X represents a halogen atom or an alkyl group. n represents an integer of 0 to 2. ]
Item 7.
A rubber composition containing a rubber component, the additive according to any one of Items 1 to 3, an inorganic filler and / or carbon black.
Item 8.
Item 2. The rubber composition according to Item 7, wherein the rubber component is a diene-based rubber.
Item 9.
A rubber composition containing the modified polymer according to any one of Items 4 to 6 and an inorganic filler and / or carbon black.
Item 10.
Item 6. The rubber composition according to any one of Items 7 to 9, which 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.
Item 11.
A tire produced by using the rubber composition according to any one of Items 7 to 10.
Item 12.
The step (I) of mixing the rubber component, the additive according to any one of claims 1 to 3, and the raw material component containing the inorganic filler and / or carbon black, and the mixture obtained in the step (I). A method for producing a rubber composition, which comprises the step (II) of mixing the vulcanizing agent and the vulcanizing agent.
Item 13.
Step (I) is a step (I-1) of mixing the rubber component and the additive according to any one of Items 1 to 3, and the mixture obtained in Step (I-1), and inorganic filling. Item 12. The production method according to Item 12, which is a step (I-2) of mixing the material and / or carbon black.
Item 14.
A modified polymer produced by using a rubber mixture containing 0.1 to 10 parts by mass of the additive according to any one of Items 1 to 3 with respect to 100 parts by mass of the rubber component.
Item 15.
Item 2. The modified polymer according to Item 14, wherein the rubber component is a diene-based rubber.
Item 16.
A rubber composition containing 0.1 to 10 parts by mass of the additive according to any one of Items 1 to 3 with respect to 100 parts by mass of the rubber component.
Item 17.
For 100 parts by mass of the rubber component, 0.1 to 10 parts by mass of the additive according to any one of Items 1 to 3, and 20 to 150 parts by mass of the total amount of the inorganic filler and / or carbon black. Part-containing rubber composition.
Item 18.
Item 2. The rubber composition according to any one of Items 7 to 10 and 17, wherein the blending amount of the inorganic filler is 20 to 150 parts by mass with respect to 100 parts by mass of the rubber component.
Item 19.
Item 8. The rubber composition according to Item 18, wherein the inorganic filler is silica.
Item 20.
Item 2. The rubber composition according to any one of Items 7 to 10 and 17, wherein the amount of carbon black blended is 1 to 150 parts by mass with respect to 100 parts by mass of the rubber composition.
Item 21.
A rubber composition containing 100 parts by mass of the modified polymer according to any one of Items 4 to 6, 14 and 15 and 20 to 150 parts by mass in total of an inorganic filler and / or carbon black.
Item 22.
Item 2. The rubber composition according to any one of Items 7 to 10 and 21, wherein the blending amount of the inorganic filler is 20 to 150 parts by mass with respect to 100 parts by mass of the modified polymer.
Item 23.
Item 22. The rubber composition according to Item 22, wherein the inorganic filler is silica.
Item 24.
Item 2. The rubber composition according to any one of Items 7 to 10 and 21, wherein the amount of carbon black blended is 1 to 150 parts by mass with respect to 100 parts by mass of the modified polymer.
Item 25.
A dispersant containing an azomethine imine compound represented by the following general formula (1) or a salt thereof.

[In the formula, R ¹ and R ² represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, which are the same or different, and each of these groups may have one or more substituents. .. R ³ , R ⁴ , R ⁵ and R ⁶ represent the same or different hydrogen atoms, alkyl or aryl groups, each of which may have one or more substituents. n represents an integer of 0 to 2. ]
Item 26.
A hypocalifying agent containing an azomethine imine compound represented by the following general formula (1) or a salt thereof.

[In the formula, R ¹ and R ² represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, which are the same or different, and each of these groups may have one or more substituents. .. R ³ , R ⁴ , R ⁵ and R ⁶ represent the same or different hydrogen atoms, alkyl or aryl groups, each of which may have one or more substituents. n represents an integer of 0 to 2. ]
Item 27.
An anti-fever agent containing an azomethine imine compound represented by the following general formula (1) or a salt thereof.

[In the formula, R ¹ and R ² represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, which are the same or different, and each of these groups may have one or more substituents. .. R ³ , R ⁴ , R ⁵ and R ⁶ represent the same or different hydrogen atoms, alkyl or aryl groups, each of which may have one or more substituents. n represents an integer of 0 to 2. ]
Item 28.
A fever suppressant containing an azomethine imine compound represented by the following general formula (1) or a salt thereof.

[In the formula, R ¹ and R ² represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, which are the same or different, and each of these groups may have one or more substituents. .. R ³ , R ⁴ , R ⁵ and R ⁶ represent the same or different hydrogen atoms, alkyl or aryl groups, each of which may have one or more substituents. n represents an integer of 0 to 2. ]

The present invention can provide an additive for imparting low heat generation to a rubber component. The additive contains an azomethine imine-based compound, and the additive disperses an inorganic filler and / or carbon black in the rubber component.

The present invention can provide a rubber composition capable of exhibiting low heat generation and a modified polymer capable of imparting low heat generation.

INDUSTRIAL APPLICABILITY The present invention provides a fuel-efficient tire because the rolling resistance of the tire can be reduced and the heat generation of the tire can be reduced by producing the tire using a rubber composition capable of exhibiting low heat generation. can do. Further, since a rubber composition highly filled with silica also exhibits high heat generation, it is possible to provide a fuel-efficient tire having high exercise performance.

Hereinafter, the present invention will be described in detail.

1. 1. Additives for imparting low heat generation to rubber components Additives for imparting low heat generation to rubber components of the present invention (hereinafter, may also be referred to as "additives of the present invention") have the following general formulas. The compound represented by (1) or a salt thereof (hereinafter, may also be referred to as "azomethineimine compound (1)") is included.

[In the formula, R ¹ and R ² represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, which are the same or different, and each of these groups may have one or more substituents. .. R ³ , R ⁴ , R ⁵ and R ⁶ represent the same or different hydrogen atoms, alkyl or aryl groups, each of which may have one or more substituents. n represents an integer of 0 to 2. ]

In the present specification, the "alkyl group" is not particularly limited, and examples thereof include linear, branched or cyclic alkyl groups, and specific examples thereof include methyl group, ethyl group and n-propyl. Group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, 1-ethylpropyl group, n-pentyl group, neopentyl group, n-hexyl group, isohexyl group, 3-methylpentyl group Linear or branched alkyl groups having 1 to 6 carbon atoms (particularly 1 to 4 carbon atoms); cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, etc. Examples thereof include a cyclic alkyl group having ~ 8 (particularly 3 to 6 carbon atoms). Preferred alkyl groups are linear or branched alkyl groups having 1 to 6 carbon atoms, more preferably methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, isobutyl groups or n-. It is a pentyl group, particularly preferably a methyl group or an ethyl group.

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. A more preferable aryl group is a phenyl group or a naphthyl group, and a more preferable phenyl group.

In the present specification, the "heterocyclic group" is not particularly limited, and for example, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrazinyl group, 2-pyrimidyl group, 4-pyrimidyl group, and the like. 5-pyrimidyl group, 3-pyridadyl group, 4-pyridadyl group, 4- (1,2,3-triazil) group, 5- (1,2,3-triazil) group, 2- (1,3,5-) Triazil) group, 3- (1,2,4-triazil) group, 5- (1,2,4-triazil) group, 6- (1,2,4-triazil) group, 2-quinolyl group, 3- Kinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group, 6- Isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, 2-quinoxalyl group, 3-quinoxalyl group, 5-quinoxalyl group, 6-quinoxalyl group, 7-quinoxalyl group, 8-quinoxalyl group, 3-cinnolyl group, 4- Synnolyl group, 5-cinnolyl group, 6-cinnolyl group, 7-cinnolyl group, 8-cinnolyl group, 2-quinazolyl group, 4-quinazolyl group, 5-quinazolyl group, 6-quinazolyl group, 7-quinazolyl group, 8- Thiadiazole group, 1-phthalazyl group, 4-phthalazyl group, 5-phthalazyl group, 6-phthalazyl group, 7-phthalazyl group, 8-phthalazyl group, 1-tetrahydroquinolyl group, 2-tetrahydroquinolyl group, 3-tetrahydro Kinolyl group, 4-tetrahydroquinolyl group, 5-tetrahydroquinolyl group, 6-tetrahydroquinolyl group, 7-tetrahydroquinolyl group, 8-tetrahydroquinolyl group, 1-pyrrrolyl group, 2-pyrrolill group, 3 -Pyrrolyl group, 2-furyl group, 3-furyl group, 2-thienyl group, 3-thienyl group, 1-imidazolyl group, 2-imidazolyl group, 4-imidazolyl group, 5-imidazolyl group, 1-pyrazolyl group, 3 -Pyrazolyl group, 4-pyrazolyl group, 5-pyrazolyl group, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl group, 5-thiazolyl group, 3-isooxazolyl group, 4-isooxazolyl group, 5-isooxazolyl group, 3-isothiazolyl group, 4-isothiazolyl group, 5-isothiazolyl group, 4- (1,2,3-thiadiazole) group, 5- (1,2,3-thiadiazolyl) group, 3- (1) , 2,5-Thiadiazole) group, 2- (1,3,4-thiadiazole) group, 4- (1,2,3-oxadiazolyl) group, 5- (1,2,3-oxadiazolyl) group, 3- (1,2,4-oxadiazolyl) group, 5- (1,2,4-oxadiazolyl) Group, 3- (1,2,5-oxadiazolyl) group, 2- (1,3,4-oxadiazolyl) group, 1- (1,2,3-triazolyl) group, 4- (1,2,3- Triazolyl) group, 5- (1,2,3-triazolyl) group, 1- (1,2,4-triazolyl) group, 3- (1,2,4-triazolyl) group, 5- (1,2, 4-triazolyl) group, 1-tetrazolyl group, 5-tetrazolyl group, 1-indrill group, 2-indrill group, 3-indrill group, 4-indrill group, 5-indrill group, 6-indrill group, 7-indrill group , 1-isoindrill group, 2-isoindrill group, 3-isoindrill group, 4-isoindrill group, 5-isoindrill group, 6-isoindrill group, 7-isoindrill group, 1-benzoimidazolyl group, 2-benzoimidazolyl group, 4-benzoimidazolyl group , 5-benzoimidazolyl group, 6-benzoimidazolyl group, 7-benzoimidazolyl group, 2-benzofuranyl group, 3-benzofuranyl group, 4-benzofuranyl group, 5-benzofuranyl group, 6-benzofuranyl group, 7-benzofuranyl group, 1-isobenzo Furanyl group, 3-isobenzofuranyl group, 4-isobenzofuranyl group, 5-isobenzofuranyl group, 6-isobenzofuranyl group, 7-isobenzofunyl group, 2-benzothienyl group, 3-benzo Thienyl group, 4-benzothienyl group, 5-benzothienyl group, 6-benzothienyl group, 7-benzothienyl group, 2-benzoxazolyl group, 4-benzoxazolyl group, 5-benzoxazolyl group , 6-benzoxazolyl group, 7-benzoxazolyl group, 2-benzothiazolyl group, 4-benzothiazolyl group, 5-benzothiazolyl group, 6-benzothiazolyl group, 7-benzothiazolyl group, 1-indazolyl group, 3-indazolyl Group, 4-indazolyl group, 5-indazolyl group, 6-indazolyl group, 7-indazolyl group, 2-morpholic group, 3-morpholic group, 4-morpholic group, 1-piperazyl group, 2-piperazyl group, 1-piperidyl Group, 2-piperidyl group, 3-piperidyl group, 4-piperidyl group, 2-tetrahydropyranyl group, 3-tetrahydropyranyl group, 4-tetrahydropyranyl group, 2-tetrahydrothiopyranyl group, 3 -Tetrahydrothiopyranyl group, 4-tetrahydrothiopyranyl group, 1-pyrrolidyl group, 2-pyrrolidyl group, 3-pyrrolidyl group, 2-tetrahydrofuranyl group, 3-tetrahydrofuranyl group, 2-tetrahydrothienyl group, 3- Examples include a tetrahydrothienyl group. Among them, a preferred heterocyclic group is a pyridyl group.

Each of these alkyl group, aryl group, and heterocyclic group may have one or more substituents. The "substituent" is not particularly limited, and is, for example, a halogen atom, an amino group, an aminoalkyl group, an alkoxycarbonyl group, an acyl group, an acyloxy group, an amide group, a carboxyl group, a carboxyalkyl group, a formyl group, or a 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 preferably have 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, and preferably a chlorine atom, a bromine atom and an iodine atom.

In the present specification, the "amino group" includes _{not only the amino group represented by -NH 2} , but also, for example, a methylamino group, an ethylamino group, an n-propylamino group, an isopropylamino group, and an n-butylamino group. , Isobutylamino group, s-butylamino group, t-butylamino group, 1-ethylpropylamino group, n-pentylamino group, neopentylamino group, n-hexylamino group, isohexylamino group, 3-methylpentyl Linear or branched monoalkylamino groups having 1 to 6 carbon atoms (particularly 1 to 4 carbon atoms) such as amino groups; 1 to 6 carbon atoms such as dimethylamino groups, ethylmethylamino groups and diethylamino groups (particularly). Substituted amino groups such as a dialkylamino group having two linear or branched alkyl groups having 1 to 4 carbon atoms are also included.

In the present specification, the "aminoalkyl group" is not particularly limited, and examples thereof include aminoalkyl groups such as aminomethyl group, 2-aminoethyl group, and 3-aminopropyl group.

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

In the present specification, the "acyl group" is not particularly limited, and examples thereof include a linear or branched alkylcarbonyl group having 1 to 4 carbon atoms such as an acetyl group, a propionyl group, and a pivaloyl group.

In the present specification, the "acyloxy group" is not particularly limited, and examples thereof include an acetyloxy group, a propionyloxy group, and an n-butyryloxy group.

In the present specification, the "amide group" is not particularly limited, and for example, a carboxylic acid amide group such as an acetamido group or a benzamide group; a thioamide group such as a thioacetamide group or a thiobenzamide group; an N-methylacetamide group or N. Examples thereof include an N-substituted amide group such as a −benzylacetamide group.

In the present specification, the "carboxyalkyl group" is not particularly limited, and for example, a carboxymethyl group, a 2-carboxyethyl group, a 3-carboxypropyl group, a 4-carboxybutyl group, a 5-carboxypentyl group, 6- Examples thereof include a carboxy-alkyl group such as a carboxyhexyl group (preferably an alkyl group having a carboxy group and having 1 to 6 carbon atoms).

In the present specification, the "hydroxyalkyl group" is not particularly limited, and for example, a hydroxy-alkyl group such as a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, or a 4-hydroxybutyl group (preferably). Alkyl groups having 1 to 6 carbon atoms having a hydroxy group) can be mentioned.

In the present specification, the "alkoxy group" is not particularly limited, and examples thereof include linear, branched or cyclic alkoxy groups, and specific examples thereof include methoxy group, ethoxy group and n-propoxy. A linear group having 1 to 6 carbon atoms (particularly 1 to 4 carbon atoms) of a group, an isopropoxy group, an n-butoxy group, a t-butoxy group, an n-pentyloxy group, a neopentyloxy group, and an n-hexyloxy group. Or a branched alkoxy group; having 3 to 8 carbon atoms (particularly 3 to 6 carbon atoms) such as a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group. Cyclic alkoxy groups and the like can be mentioned.

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

In the present specification, the "alkylthio group" is not particularly limited, and examples thereof include linear, branched or cyclic alkylthio groups, and specifically, for example, methylthio group, ethylthio group and n-propylthio. Group, isopropylthio group, n-butylthio group, isobutylthio group, s-butylthio group, t-butylthio group, 1-ethylpropylthio group, n-pentylthio group, neopentylthio group, n-hexylthio group, isohexylthio Linear or branched alkylthio groups having 1 to 6 carbon atoms (particularly 1 to 4 carbon atoms) such as groups and 3-methylpentylthio groups; cyclopropylthio groups, cyclobutylthio groups, cyclopentylthio groups, cyclohexylthios. Examples thereof include a cyclic alkylthio group having 3 to 8 carbon atoms (particularly 3 to 6 carbon atoms) such as a group, a cycloheptylthio group and a cyclooctylthio group. The preferred alkylthio group is a methylthio group, an ethylthio group, an isopropylthio group or an isobutylthio group, and more preferably a methylthio group or an ethylthio group.

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

The "salt" of the azomethine imine compound represented by the general formula (1) 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. Alkaline earth metal salts such as salts; ammonium salts such as dimethylammonium and triethylammonium can be mentioned.

Among these azomethine imine compounds (1), a compound in which R ¹ is an aryl group which may have a substituent or a heterocyclic group which may have a substituent is preferable, and R ¹ is a substituent. A compound having a heterocyclic group which may be possessed is more preferable, and a compound having a pyridyl group is particularly preferable.

Among these azomethine imine compounds (1), compounds in which R ³ , R ⁴ , R ⁵ and R ⁶ are hydrogen atoms or alkyl groups are preferable, and any one of ^{R 3} , R ⁴ , R ⁵ and R ^{6 is alkyl.} The compound that is the group is more preferable.

Among these azomethine imine compounds (1), a compound in which n is 0 or 1 is preferable, and a compound in which n is 0 is more preferable.

Among these azomethine imine compounds (1), a compound in which R ¹ is a pyridyl group, ^{at least one of R 3} and R ⁴ , R ⁵ and R ⁶ is an alkyl group, and n is 0 is preferable.

Among these azomethine imine compounds (1), R ¹ is a 2-pyridyl group, R ² , R ⁵ and R ⁶ are hydrogen atoms, ^{and at least one of R 3} and R ⁴ is a methyl group, and n is 0. Is more preferable.

Among these azomethine imine compounds (1), R ¹ is a 2-pyridyl group, R ² , R ³ and R ⁴ are hydrogen atoms, ^{and at least one of R 5} and R ⁶ is a methyl group, and n is 0. Is more preferable.

Specifically, examples of the azomethine imine compound (1) include 1- (2-pyridinylmethylidene) -3-oxopyrazolidinium ylide and 4-methyl-1- (2-pyridinylmethylide). Den) -3-oxopyrazolidinium ylide, 4-methyl-1- (3-pyridinyl methylidene) -3-oxopyrazolidinium ylide, 4-methyl-1- (4-pyridinyl methylidene) Den) -3-oxopyrazolidinium ylide, 1-benziliden-4-methyl-3-oxopyrazolidinium ylide, 1- (2-hydroxybenzylidene) -4-methyl-3-oxopyrazolidinium ylide , 1- (4-Hydroxybenzylene) -4-methyl-3-oxopyrazolidinium ylide, 1- (4-dimethylaminobenzylidene) -4-methyl-3-oxopyrazolidinium ylide, 1- (2) −Franylmethylidene) -4-methyl-3-oxopyrazolidinium ylide, 1- (2-carboxybenzylidene) -4-methyl-3-oxopyrazolidinium ylide, 1- (4-carboxybenzylidene) -4-Methyl-3-oxopyrazolidinium ylide, 4-methyl-1- (3-nitrobenzylene) -3-oxopyrazolidinium ylide, 4-methyl-1- (4-nitrobenzylene) -3 -Oxopyrazolidinium ylide, 5-methyl-1- (2-pyridinyl methylidene) -3-oxopyrazolidinium ylide, 5,5-dimethyl-1- (2-pyridinyl methylidene) Examples thereof include -3-oxopyrazolidinium ylide and 1- (2-pyridinyl methylidene) -3-oxopyridazinium ylide.

Among them, the preferred azomethine imine compound (1) is 4-methyl-1- (2-pyridinyl methylidene) -3-oxopyrazolidinium ylide, 4-methyl-1- (3-pyridinyl methylidene). -3-oxopyrazolidinium ylide, 4-methyl-1- (4-pyridinyl methylidene) -3-oxopyrazolidinium ylide, 1- (2-hydroxybenzylidene) -4-methyl-3-3 Oxopyrazolidinium ylide, 5-methyl-1- (2-pyridinyl methylidene) -3-oxopyrazolidinium ylide and 5,5-dimethyl-1- (2-pyridinyl methylidene)- 3-oxopyrazolidinium ylides, more preferred azomethine imine compounds (1) are 4-methyl-1- (2-pyridinylmethylidene) -3-oxopyrazolidinium ylides and 5-methyl-. 1- (2-pyridinyl methylidene) -3-oxopyrazolidinium ylide.

In addition, 4-methyl-1- (3-pyridinylmethylidene) -3-oxopyrazolidinium ylide, 4-methyl-1- (4-pyridinylmethylidene) -3-oxopyrazolidinium Ylide, 1- (2-carboxybenzylidene) -4-methyl-3-oxopyrazolidinium ylide, 1- (4-carboxybenzylidene) -4-methyl-3-oxopyrazolidinium ylide, 5-methyl- 1- (2-pyridinylmethylidene) -3-oxopyrazolidinium ylide, 5,5-dimethyl-1- (2-pyridinylmethylidene) -3-oxopyrazolidinium ylide, 1- (2-Pyridinyl methylidene) -3-oxopyridazinium ylide is a novel compound not described in the literature.

Further, in the azomethine imine compound represented by the general formula (1) and a salt thereof, resonance structures represented by the following general formulas (1-1) to (1-3) may exist, but in the present invention, these structures are present. The compound having is also included in the azomethine imine compound represented by the general formula (1) and its salt.

[In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and n are the same as described above. ]

By adding the azomethine imine compound (1) to the rubber component, low heat generation can be imparted to the rubber component. A tire produced (manufactured) from a rubber composition containing such an azomethine imine compound (1) can impart low heat generation, so that rolling resistance is reduced, and as a result, low fuel consumption performance is exhibited.

The additive of the present invention includes the case where it consists only of the azomethine imine compound (1).

Rubber component In the present specification, the rubber component is not particularly limited, and for example, natural rubber (NR), synthetic diene rubber, diene rubber such as a mixture of natural rubber and synthetic diene rubber, and other than these. Non-diene rubber can be mentioned.

Examples of natural rubber include natural rubber latex, technically rated rubber (TSR), smoked sheet (RSS), backlash, Tochu-derived natural rubber, Guayur-derived natural rubber, Russian dandelion-derived natural rubber, and resin component fermented rubber. Further, the natural rubber of the present invention also includes modified natural rubber such as epoxidized natural rubber, methacrylic acid modified natural rubber, and styrene modified natural rubber obtained by modifying these natural rubbers.

Examples of synthetic diene rubbers include styrene-butadiene copolymer rubber (SBR), butadiene rubber (BR), isoprene rubber (IR), nitrile rubber (NBR), chloroprene rubber (CR), and ethylene-propylene-diene ternary products. 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, single-ended modification, and double-ended 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, a hydroxyl group, a polyether group and a carboxyl group, and these functional groups are one or two. More than a seed may be contained in the modified synthetic diene 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. Further, the glass transition point of the synthetic diene rubber is not particularly limited.

Further, the ratio of cis / trans / vinyl in 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 is preferably 500 to 3000000 and the molecular weight distribution is preferably 1.5 to 15.

As the non-diene rubber, known rubbers can be widely used.

From the viewpoint of low heat generation, the rubber component contains diene-based rubber. Specifically, 100 parts by mass of the rubber component preferably contains 70 parts by mass or more of diene-based rubber, more preferably 75 parts by mass or more, and 80 to 100 parts by mass. Especially preferable.

Further, at the glass transition point of the diene rubber, those in the range of −120 ° C. to −15 ° C. are particularly effective from the viewpoint of low heat generation. The rubber composition of the present invention is preferably a diene-based rubber in which 50% by mass or more of the diene-based rubber has a glass transition point in the range of −70 ° C. to −20 ° C.

The rubber component can be used alone or in combination of two or more. Among them, the preferable rubber component is natural rubber, IR, SBR, BR or a mixture of two or more kinds selected from these, and more preferably natural rubber, SBR, BR or a mixture of two or more kinds selected from these. .. The blending ratio thereof is not particularly limited, but it is preferable to mix SBR, BR or a mixture thereof in 100 parts by mass of the rubber component at a ratio of 50 to 100 parts by mass, preferably 75 to 100 parts by mass. It is particularly preferable to blend. When blending a mixture of SBR and BR, the total amount of SBR and BR is preferably in the above range. Further, the SBR at this time is 50 to 100 parts by mass, and the BR is preferably in the range of 0 to 50 parts by mass.

2. Modified Polymer The modified polymer of the present invention is prepared by using a rubber mixture containing a rubber component and the above-mentioned additive of the present invention.

That is, the modified polymer of the present invention is a modified polymer in which the rubber component is treated with the azomethine imine compound (1).

A 1,3-dipolar cyclization addition reaction proceeds between the azomethine imine compound (1) and the double bond in the rubber component, for example, as shown in the following reaction formula to form a modified polymer.

[In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and n are the same as described above. A ¹ , A ² , A ³ and A ⁴ represent the same or different hydrogen atoms, halogen atoms, alkyl groups or diene-based rubber residues. However, ^{at least one of A 1} , A ² , A ³ and A ⁴ indicates a diene-based rubber residue. ]

According to the above reaction formula, the azomethine imine compound represented by the formula (1) and its salt and the diene rubber represented by the formula (A) are five-membered by a 1,3-dipolar cycloaddition reaction. A ring structure is formed, and a modified polymer represented by the formula (2) is produced.

The modified polymer of the present invention thus formed preferably has at least one selected from the compound structures represented by the following formulas (2-1) to (2-7).

[In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and n are the same as described above. X represents a halogen atom or an alkyl group. ]

The modified polymer of the present invention has a heteroatom such as an oxygen atom and a nitrogen atom, and since this heteroatom strongly interacts with silica and carbon black, the silica or carbon black to the diene rubber component can be used. The dispersibility can be enhanced to impart high low heat generation to the modified polymer.

The method for producing a modified polymer of the production method the present invention modified polymers is not particularly limited. The modified polymer of the present invention is produced, for example, using a rubber mixture containing at least one rubber component selected from the group consisting of natural rubber and synthetic diene-based rubber, and the azomethine imine compound (1).

As a specific method for producing the modified polymer of the present invention, when the rubber component is a solid, the rubber component and the azomethineimine compound (1) are mixed (solid mixing method); the rubber component is liquid (liquid). In this case, a method of mixing the solution or emulsion (suspension) of the rubber component with the azomethine imine compound (1) (liquid mixing method) and the like can be mentioned. In this specification, "mixing" includes "kneading".

The mixing temperature is not particularly limited. For example, in the case of the solid mixing method, the discharge temperature of the rubber composition is preferably 80 to 190 ° C, more preferably 90 to 160 ° C, and 100. It is more preferably ~ 150 ° C. In the case of the liquid mixing method, the discharge temperature of the liquid rubber composition is preferably 80 to 190 ° C., more preferably 90 to 160 ° C., and even more preferably 100 to 150 ° C.

The mixing time is not particularly limited. For example, in the case of the solid mixing method, it is preferably 10 seconds to 20 minutes, more preferably 30 seconds to 10 minutes, and 60 seconds to 7 minutes. Is even more preferable. In the case of the liquid mixing method, it is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 40 minutes, and even more preferably 60 seconds to 30 minutes. After the mixing reaction by the liquid mixing method, for example, the solvent in the mixture can be blown off (removed) under reduced pressure to recover the solid rubber composition.

In the method for producing a modified polymer of the present invention, the amount of the azomethine imine compound (1) to be blended is not particularly limited, and is usually 0.1 to 10 parts by mass with respect to 100 parts by mass of the diene rubber. It is preferably 0.25 to 5 parts by mass, and more preferably 0.5 to 2 parts by mass.

Further, the modified polymer of the present invention includes those formed in the process of producing the rubber composition described later.

3. 3. Rubber Composition The rubber composition of the present invention contains a rubber component, the above-mentioned additives of the present invention, and an inorganic filler and / or carbon black.

In addition, the rubber composition of the present invention contains the above-mentioned modified polymer and an inorganic filler and / or carbon black.

The rubber component, the additive of the present invention, and the modified polymer are as described above.

The blending amount of the additive of the present invention is usually 0.1 to 10 parts by mass, preferably 0.25 to 5 parts by mass, more preferably with respect to 100 parts by mass of the rubber component in the rubber composition. Is 0.5 to 2 parts by mass.

The blending amount of the inorganic filler is usually 20 to 150 parts by mass, preferably 30 to 120 parts by mass, and more preferably 40 to 90 parts by mass with respect to 100 parts by mass of the rubber component.

The blending amount of carbon black is usually 1 to 150 parts by mass, preferably 2 to 120 parts by mass, and more preferably 3 to 100 parts by mass with respect to 100 parts by mass of the rubber component.

In the rubber composition of the present invention, the inorganic filler and / or carbon black is the total amount of both components, for example, usually 20 to 150 parts by mass, preferably 40 parts by mass with respect to 100 parts by mass of the rubber component. It may be appropriately adjusted within the range of the above-mentioned blending amount of each component so as to be ~ 130 parts by mass, more preferably 45 to 100 parts by mass.

When the blending amount of the inorganic filler and / or carbon black is 20 parts by mass or more, it is preferable from the viewpoint of improving the reinforcing property of the rubber composition, and when it is 150 parts by mass or less, it is preferable from the viewpoint of reducing rolling resistance. When blending the inorganic filler and / or carbon black, a master batch in which the polymer is mixed wet or dry in advance may be used.

The inorganic filler or carbon black is usually used to improve the reinforcing property of rubber. In this specification, carbon black is not included in the inorganic filler.

Inorganic filler The inorganic filler is not particularly limited as long as it is an inorganic compound usually used in the rubber industry. Examples of the 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); gibsite. , Aluminum hydroxide [Al (OH) ₃ ] such as bayarite; Aluminum carbonate [Al ₂ (CO ₃ ) ₂ ], Magnesium hydroxide [Mg (OH) ₂ ], Magnesium oxide (MgO), Magnesium carbonate (MgCO ₃₎ ), talc _{(3MgO · 4SiO 2 · H 2} O), attapulgite _{(5MgO · 8SiO 2 · 9H 2} O), titanium white _(TiO 2), titanium black _{(TiO 2n-1),} calcium oxide (CaO), hydroxide calcium [Ca _(OH) 2], magnesium aluminum 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.), Aluminium aluminum silicate (Al ₂ O ₃ · CaO · _{2SiO 2} etc.), Calcium magnesium 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 aluminosilicates containing hydrogen, alkali metals or alkaline earth metals that correct the charge like 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, more preferably silica alone, or silica and one or more kinds of inorganic compounds usually used in the rubber industry can be used in combination. When the above-mentioned inorganic compound other than silica and silica is used in combination as the inorganic filler, it may be appropriately adjusted so that the total amount of all the components of the inorganic filler is 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 preferably 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 examples thereof include a range of ^{40 to 350 m 2 / g.} Silica having a BET specific surface area in this range has an advantage that both rubber reinforcing property and dispersibility in a rubber component can be achieved at the same time. The BET specific surface area is measured according to ISO 5794/1.

From this point of view, the preferred silica is a silica having a BET specific surface area in ^{the range of 50 to 300 m 2} / g, more preferably a silica having a BET specific surface area of 100 to 270 m ² / g, and particularly preferably. , BET specific surface area is silica in the range of ^{110-270 m 2 / g.} Commercially available products of such silica include Quechen Silica Chemical Co., Ltd. , Ltd. Product names "HD165MP" (BET specific surface area = 165m ² / g), "HD115MP" (BET specific surface area = 115m ² / g), "HD200MP" (BET specific surface area = 200m ² / g), "HD250MP" ( BET specific surface area = 250 m ² / g), trade name "Nip Seal AQ" (BET specific surface area = 205 m ² / g), "Nip Seal KQ" (BET specific surface area = 240 m ² / g), Degussa manufactured by Toso Silica Co., Ltd. Product name "Ultra Jill VN3" (BET specific surface area = 175 m ² / g), product name "Z1085 Gr" (BET specific surface area = 90 m ² / g), "Z Premium 200MP" (BET specific surface area =) ^{215m 2} / g), "Z HRS 1200MP" (BET specific surface area = 200m ² / g) and the like.

The blending amount of silica is usually 20 to 120 parts by mass, preferably 30 to 100 parts by mass, and more preferably 40 to 90 parts by mass with respect to 100 parts by mass of the rubber component.

Usually, the addition of silica improves the steering stability performance, but the addition of a large amount tends to worsen the low heat generation. However, by using the additive of the present invention, excellent low heat generation is exhibited even if a large amount of silica is blended.

In particular, the amount of silica blended in order to achieve both kinetic performance and fuel efficiency is usually 40 to 120 parts by mass, preferably 60 to 115 parts by mass, based on 100 parts by mass of the rubber component. It is preferably 70 to 110 parts by mass.

By blending the azomethine imine compound (1) in the rubber composition containing an inorganic filler, particularly silica, the dispersibility of silica can be significantly improved, and the low heat generation property of the rubber composition can be remarkably improved. That is, the additive of the present invention can be used as a dispersant, a low heat generating agent, a heat generation inhibitor or a heat generation inhibitor for an inorganic filler and / or carbon black, and preferably a dispersant for rubber and low heat generation for rubber. It can be used as an agent, a heat generation inhibitor for rubber, or a heat generation inhibitor for rubber.

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 lowering the electric resistance of the rubber, suppressing the charge, and further 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, SRF grade carbon. Black and the like can be mentioned. Among them, preferable carbon blacks are SAF, ISAF, IISAF, N134, N234, N330, N339, N375, HAF or FEF grade carbon blacks.

The DBP absorption of carbon black (measured in conformity with JISK6217), not particularly limited, preferably 60~200cm ³ / 100g, more preferably 70~180cm ³ / 100g or more, particularly preferably 80～160Cm ³ / 100g.

The nitrogen adsorption specific surface area of carbon black (measured according to N2SA, JIS K 6217-2: 2001) is preferably 30 to 200 m ² / g, more preferably 40 to 180 m ² / g, and particularly preferably. It is 50 to 160 m ² / g.

In the rubber composition containing carbon black, it is considered that the azomethine imine compound (1) or the reaction product of the rubber component and the azomethine imine compound (1) strongly interacts with carbon black. Therefore, according to the rubber composition of the present invention, the dispersibility of carbon black is significantly improved, and the low heat generation property of the rubber composition can be remarkably improved.

Other Blending Agents In addition to the azomethine imine compound (1) and the inorganic filler and / or carbon black, the rubber composition of the present invention contains a compounding agent commonly used in the rubber industry, such as sulfur. A vulcanizing agent can be blended. Further, the rubber composition of the present invention may contain other compounding agents such as antiaging agent, ozone deterioration inhibitor, softening agent, processing aid, wax, resin, foaming agent, oil, stearic acid, zinc stearate, and the like. Zinc oxide (ZnO), a vulcanization accelerator, a vulcanization retarder, and the like can be appropriately selected and blended within a range that does not impair the object of the present invention. As these compounding agents, commercially available products can be preferably used.

Further, in a rubber composition containing an inorganic filler such as silica, silane coupling is used for the purpose of enhancing the reinforcing property of the rubber composition by silica, or for the purpose of enhancing the wear resistance as well as the low heat generation of the rubber composition. The agent may be blended.

The silane coupling agent that can be used in combination with the inorganic filler is not particularly limited, and a commercially available product 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, and bis ( 2-Triethoxysilylethyl) tetrasulfide, bis (3-triethoxysilylpropyl) disulfide, bis (3-trimethoxysilylpropyl) disulfide, bis (3-methyldimethoxysilylpropyl) disulfide, bis (2-triethoxysilylpropyl) 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 can be mentioned. 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, and 3-mercaptopropylmethyldimethoxysilane. Examples of the olefin-based silane coupling agent include dimethoxymethylvinylsilane, vinyltrimethoxysilane, dimethylethoxyvinylsilane, diethoxymethylvinylsilane, triethoxyvinylsilane, vinyltris (2-methoxyethoxy) silane, allyltrimethoxysilane, and allyltri. 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 the epoxy-based silane coupling agent include 3-glycidyloxypropyl (dimethoxy) methylsilane, 3-glycidyloxypropyltrimethoxysilane, diethoxy (3-glycidyloxypropyl) methylsilane, and triethoxy (3-glycidyloxypropyl) silane. , 2- (3,4-epylcyclohexyl) ethyltrimethoxysilane and the like. Of these, 3-glycidyloxypropyltrimethoxysilane is preferable.

Examples of the amino-based silane coupling agent 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)- Examples thereof include 2-aminoethyl-3-aminopropyltrimethoxysilane. Of these, 3-aminopropyltriethoxysilane is preferable.

Examples of the alkyl-based 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, n-decyltrimethoxysilane and the like. Of these, methyltriethoxysilane is preferred.

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

In the present invention, one type of silane coupling agent may be used alone, or two or more types may be used in combination.

The blending 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 inorganic filler. If it is 0.1 part by mass or more, the effect of improving the low heat generation of the rubber composition can be more preferably exhibited, and if it is 20 parts by mass or less, the cost of the rubber composition is reduced and the economy is economical. Because it improves.

Further, in the case where the braking characteristic is particularly important, a resin or the like may be added. Specific examples of the resin include natural resins such as rosin-based resins and terpene-based resins, petroleum-based resins, phenol-based resins, coal-based resins, and xylene-based resins. Examples of the rosin-based resin include gum rosin, tall oil rosin, wood rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, and modified rosin, and glycerin esters and pentaerythritol esters thereof. Examples of the terpene-based resin include α-pinene-based, β-pinene-based, and dipentene-based terpene resins, aromatic-modified terpene resins, terpene phenol resins, and hydrogenated terpene resins.

In cases where processability is important, as processing aids, mineral oil, petroleum, paraffin wax, petroleum resin, fatty acid, fatty acid ester, fatty alcohol, metal soap, fatty acid amide, phenol resin, polyethylene, polybutene, peptizer, etc. Deliquescent agents, regenerating agents, organosiloxanes and the like can be added.

Uses of rubber composition The use of the rubber composition of the present invention is not particularly limited, and examples thereof include tires, anti-vibration rubbers, seismic isolation rubbers, conveyor belts, and rubber portions thereof. Of these, a preferred application is a tire.

Method for manufacturing rubber composition
Step (I)
Step (I) is a step of mixing the rubber component, the additive of the present invention, and a raw material component containing an inorganic filler and / or carbon black, if necessary, and is a step before blending the vulcanizing agent. It means that.

In the step (I), the above-mentioned other compounding agents and the like can be further added, if necessary.

Examples of the mixing method in the step (I) include a method of mixing a composition containing a rubber component, an additive of the present invention, and a raw material component containing an inorganic filler and / or carbon black, if necessary. Be done. In this mixing method, the entire amount of each component may be mixed at once, or each component may be divided and added and mixed depending on the purpose such as viscosity adjustment. Further, after mixing the rubber component with the inorganic filler and / or carbon black, the additive of the present invention is added and mixed, or after the rubber component and the additive of the present invention are mixed, the inorganic filler and / or the additive of the present invention are mixed. / Or carbon black may be added and mixed. The mixing operation may be repeated in order to uniformly disperse each component.

Further, as another mixing method in the step (I), there is a step (I-1) of mixing the rubber component and the additive of the present invention, and a mixture (modified polymer) obtained in the step (I-1). A two-step mixing method including a step (I-2) of mixing an inorganic filler and / or a raw material component containing carbon black can be mentioned.

The discharge temperature when the rubber composition is mixed in the step (I) is not particularly limited, and for example, the discharge temperature of the rubber composition is preferably 60 to 190 ° C, preferably 80 to 175 ° C. More preferably, it is 100 to 170 ° C.

The mixing time in the step (I) is not particularly limited, and is preferably, for example, 10 seconds to 20 minutes, more preferably 30 seconds to 10 minutes, and further preferably 2 minutes to 7 minutes. preferable.

The discharge temperature at the time of mixing the rubber component and the additive of the present invention in the step (I-1) is preferably 80 to 190 ° C, more preferably 90 to 160 ° C, and 100 to 150. It is more preferably ° C. By keeping the discharge temperature within the above range, the reaction can proceed without deteriorating the rubber.

The mixing time in the step (I-1) is preferably 10 seconds to 20 minutes, more preferably 30 seconds to 10 minutes, and even more preferably 60 seconds to 7 minutes. By setting the mixing time within the above range, the reaction can be sufficiently proceeded without lowering the productivity.

Discharge temperature at the time of mixing the mixture (modified polymer) obtained in the step (I-1) in the step (I-2) with the raw material components including the inorganic filler and / or carbon black to be blended as needed. The temperature of the mixture is not particularly limited, and the discharge temperature of the mixture is preferably 60 to 190 ° C., more preferably 80 to 175 ° C., and even more preferably 100 to 170 ° C.

The mixing time in the step (I-2) is not particularly limited, and is preferably, for example, 10 seconds to 20 minutes, more preferably 30 seconds to 10 minutes, and 2 minutes to 7 minutes. Is even more preferable.

It is also possible to carry out the step (I-2) without discharging the mixture (modified polymer) obtained in the step (I-1).

In the step (I), the blending amount of the tetrazine compound (1), which is the additive of the present invention, is not particularly limited, and is, for example, 0.1 to 10 parts by mass with respect to 100 parts by mass of the rubber component. It is preferably 0.25 to 5 parts by mass, and more preferably 0.5 to 2 parts by mass.

In step (I), a mixture in which the double bond portion of the rubber component (diene rubber) reacts with the additive of the present invention to form a modified polymer, and the inorganic filler and / or carbon black is preferably dispersed. Can be obtained.

Step (II)
Step (II) is a step of mixing the mixture obtained in step (I) and the vulcanizing agent, and means the final step of mixing.

In step (II), a vulcanization accelerator, zinc oxide and the like can be further added, if necessary.

The discharge temperature in the step (II) is not particularly limited, and is, for example, 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, for example, 10 seconds to 20 minutes, more preferably 30 seconds to 10 minutes, and even more preferably 60 seconds to 5 minutes.

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

In the method for producing a rubber composition of the present invention, various compounding agents such as stearic acid, zinc oxide, a vulcanization accelerator, and an antiaging agent, which are usually blended in the rubber composition, are used in step (I), if necessary. Alternatively, it can be added in step (II).

By the above steps (I) and (II), a rubber composition containing a modified polymer obtained by treating a rubber component with the additive of the present invention, and an inorganic filler and / or carbon black is produced. Can be done.

The rubber composition in the present invention is mixed using a Banbury mixer, a roll, an intensive mixer, a kneader, a twin-screw extruder and the like. After that, it is extruded and processed in an extrusion process, and is molded as, for example, a tread member or a sidewall member. Subsequently, the raw tire is molded by pasting and molding on a tire molding machine by a usual method. The raw tire is heated and pressurized in a vulcanizer to obtain a tire.

4. Tire The tire of the present invention is a tire manufactured by using the above-mentioned additive, rubber composition or modified polymer of the present invention.

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

The use of the tire is not particularly limited, and examples thereof include a passenger car tire, a high load tire, a motorcycle (motorcycle) tire, a studless tire, and the like, and among them, the tire can be preferably used for a passenger car tire.

The shape, structure, size and material of the tire of the present invention are not particularly limited and may be appropriately selected depending on the intended purpose.

In the tire of the present invention, the additive, rubber composition or modified polymer of the present invention is used particularly 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. Be done.

Among them, one of the preferred embodiments is to form the tire tread portion or sidewall portion of the pneumatic tire with the rubber composition.

The tread portion is a portion having a tread pattern and in direct contact with the road surface, and is a tire outer skin portion that protects the carcass and prevents wear and trauma, and is a cap tread and / or cap tread that constitutes the ground contact portion of the tire. A base tread that is placed inside.

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

The bead area 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 strongly tightened like a tub to increase 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 of withstanding the load, impact, and filling air pressure received by the tire.

The shoulder part is the shoulder part 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 or air with adjusted oxygen partial pressure; an inert gas such as nitrogen, argon or helium can be used.

Since the tire of the present invention has low heat generation and the rolling resistance of the tire is reduced, it is possible to reduce the fuel consumption of the automobile. Further, since a rubber composition highly filled with silica also exhibits high heat generation, it is possible to provide a fuel-efficient tire having high exercise performance.

Hereinafter, the present invention will be specifically described with reference to Production Examples and Examples. However, the examples are merely examples, and the present invention is not limited to the examples.

Production Example 1: Production of 4-Methyl-1- (2-pyridinylmethylidene) -3- oxopyrazolidinium irid (1a) In a 300 mL eggplant flask, 15.0 mL (0.31 mol) of hydrated hydrazine. , And 150 mL of ethanol were added, and 35.5 mL (1.1 eq) of methyl methacrylate was added while stirring the obtained mixture in an ice bath, and the mixture was heated under reflux for 16 hours and then cooled to room temperature. While stirring the reaction solution in an ice bath, 29.5 mL (1.0 eq) of 2-pyridinecarboxyaldehyde was added, the temperature was raised to room temperature, and the mixture was stirred for 24 hours. The reaction mixture was concentrated under reduced pressure, the solid was collected by filtration, and the collected solid was washed with ethyl acetate to obtain 41.6 g (pale yellow solid) of the target compound (1a).
Melting point: 174 ° C,
^{1 1} H-NMR (300 MHz, CDCl ₃ , δ ppm):
1.44 (d, J = 7.2Hz, 3H), 3.00 (m, 1H), 4.22 (ddd, J = 1.5, 6.6, 13.2Hz, 1H), 4.76 (Ddd, J = 1.2,9.3,13.2Hz, 1H), 7.34 (ddd, J = 0.9,4.8,7.5Hz, 1H), 7.37 (s, 1H) ) 7.84 (ddd, J = 1.5, 7.8, 7.8Hz, 1H), 8.69 (m, 1H), 9.24 (d, J = 7.8Hz, 1H)

Production Example 2: Production of 4-Methyl-1- (3-pyridinylmethylidene) -3- oxopyrazolidinium irid (1b) In a 300 mL eggplant flask, 15.0 mL (0.31 mol) of hydrated hydrazine. , And 150 mL of ethanol were added, and 35.5 mL (1.1 eq) of methyl methacrylate was added while stirring the obtained mixture in an ice bath, and the mixture was heated under reflux for 16 hours and then cooled to room temperature. While stirring the reaction solution in an ice bath, 29.0 mL (1.0 eq) of 3-pyridinecarboxyaldehyde was added, the temperature was raised to room temperature, and the mixture was stirred for 6 hours. The reaction mixture was concentrated under reduced pressure, the solid was collected by filtration, and the collected solid was washed with ethyl acetate to obtain 35.3 g (white solid) of the target compound (1b).
Melting point: 166 ° C,
^{1 1} H-NMR (300 MHz, CDCl ₃ , δ ppm):
1.42 (d, J = 7.2Hz, 3H), 2.99 (m, 1H), 4.22 (ddd, J = 1.5, 6.9, 13.2Hz, 1H), 4.77 (Ddd, J = 1.2,9.3,12.9Hz, 1H), 7.18 (s, 1H), 7.43 (dd, J = 4.8,8.1Hz, 1H), 8. 64 (dd, J = 1.5, 4.8Hz, 1H), 8.92 (d, J = 2.1Hz, 1H), 9.21 (m, 1H)

Production Example 3: Production of 4-Methyl-1- (4-pyridinylmethylidene) -3- oxopyrazolidinium irid (1c) In a 300 mL eggplant flask, 15.0 mL (0.31 mol) of hydrated hydrazine. , And 150 mL of ethanol were added, and 35.5 mL (1.1 eq) of methyl methacrylate was added while stirring the obtained mixture in an ice bath, and the mixture was heated under reflux for 16 hours and then cooled to room temperature. While stirring the reaction solution in an ice bath, 29.0 mL (1.0 eq) of 4-pyridinecarboxyaldehyde was added, the temperature was raised to room temperature, and the mixture was stirred for 9 hours. The reaction mixture was concentrated under reduced pressure, the solid was collected by filtration, and the collected solid was washed with ethyl acetate. Then, the washed solid was dissolved in hot chloroform, then ethyl acetate was added and the precipitated solid was collected by filtration, and the collected solid was washed with ethyl acetate to obtain 36.8 g (light) of the target compound (1c). Yellow solid) was obtained.
Melting point: 168 ° C,
^{1 1} H-NMR (300 MHz, CDCl ₃ , δ ppm):
1.43 (d, J = 7.2Hz, 3H), 2.99 (m, 1H), 4.21 (ddd, J = 1.5, 6.6, 13.2Hz, 1H), 4.76 (Ddd, J = 1.2,9.3,13.2Hz, 1H), 7.04 (s, 1H), 8.10 (m, 2H), 8.75 (m, 2H)

Production Example 4: Production of 1-benzylidene-4-methyl-3- oxopyrazolidinium ilide (1d) Add 20.0 mL (0.41 mol) of hydrated hydrazine and 200 mL of ethanol to a 500 mL eggplant flask to obtain the product. Methyl methacrylate (47.4 mL (1.1 eq)) was added to the mixture while stirring in an ice bath, and the mixture was heated under reflux for 16 hours and then cooled to room temperature. While stirring the reaction solution in an ice bath, 41.7 mL (1.0 eq) of benzaldehyde was added, the temperature was raised to room temperature, and the mixture was stirred for 2 hours. The reaction mixture was concentrated under reduced pressure, ethyl acetate was added, and the precipitated solid was collected by filtration, and the collected solid was washed with ethyl acetate to obtain 50.4 g (white solid) of the target compound (1d).
Melting point: 138 ° C,
^{1 1} H-NMR (300 MHz, CDCl ₃ , δ ppm):
1.41 (d, J = 7.2Hz, 3H), 2.96 (m, 1H), 4.15 (ddd, J = 1.5, 6.9, 12.9Hz, 1H), 4.69 (Ddd, J = 1.2,9.3,12.6Hz, 1H), 7.12 (s, 1H), 7.43-7.51 (m, 3H), 8.28-8.34 ( m, 2H)

Production Example 5: Production of 1- (2-Hydroxybenzylidene) -4-methyl-3- oxopyrazolidinium ilide (1e) In a 300 mL eggplant flask, 15.0 mL (0.31 mol) of hydrated hydrazine and ethanol. 150 mL was added, and 35.5 mL (1.1 eq) of methyl methacrylate was added while stirring the resulting mixture in an ice bath, and the mixture was heated under reflux for 16 hours and then cooled to room temperature. While stirring the reaction solution in an ice bath, 37.7 g (1.0 eq) of salicylaldehyde was added, the temperature was raised to room temperature, and the mixture was stirred for 3 hours. The reaction mixture was concentrated under reduced pressure, the solid was collected by filtration, and the collected solid was washed with ethyl acetate to obtain 43.6 g (pale yellow solid) of the target compound (1e).
Melting point: 203 ° C,
_{^{1 H-NMR (300MHz, d}} 6 -DMSO, δppm):
1.18 (d, J = 7.2Hz, 3H), 2.78 (m, 1H), 4.22 (ddd, J = 1.5, 9.3, 13.2Hz, 1H), 4.77 (Dd, 1H), 6.90-6.95 (m, 2H), 7.37 (m, 1H), 7.75 (s, 1H), 8.36 (dd, J = 1.8, 8) .4Hz, 1H), 11.63 (brs, 1H)

Production Example 6: Production of 1- (4-Hydroxybenzylidene) -4-methyl-3- oxopyrazolidinium ilide (1f) In a 300 mL eggplant flask, 15.0 mL (0.31 mol) of hydrated hydrazine and ethanol. 150 mL was added, and 35.5 mL (1.1 eq) of methyl methacrylate was added while stirring the resulting mixture in an ice bath, and the mixture was heated under reflux for 16 hours and then cooled to room temperature. While stirring the reaction solution in an ice bath, 37.7 g (1.0 eq) of 4-hydroxybenzaldehyde was added, the temperature was raised to room temperature, and the mixture was stirred for 7 hours. The reaction mixture was concentrated under reduced pressure, the solid was collected by filtration, and the collected solid was washed with ethyl acetate to obtain 52.5 g (pale yellow solid) of the target compound (1f).
Melting point: 320 ° C (decomposition),
_{^{1 H-NMR (300MHz, d}} 6 -DMSO, δppm):
1.16 (d, J = 7.2Hz, 3H), 2.69 (m, 1H), 4.11 (ddd, J = 1.2, 7.2, 13.2Hz, 1H), 4.66 (Ddd, J = 0.9, 9.6, 13.2 Hz, 1H), 6.90-6.93 (m, 2H), 7.53 (s, 1H), 8.15-8.19 ( m, 2H), 10.41 (brs, 1H)

Production Example 7: Production of 1- (2-carboxybenzylidene) -4-methyl-3- oxopyrazolidinium ilide (1 g) In a 300 mL eggplant flask, 15.0 mL (0.31 mol) of hydrated hydrazine and ethanol. 150 mL was added, and 35.5 mL (1.1 eq) of methyl methacrylate was added while stirring the resulting mixture in an ice bath, and the mixture was heated under reflux for 16 hours and then cooled to room temperature. While stirring the reaction solution in an ice bath, 46.3 g (1.0 eq) of phthalaldehyde acid was added, the temperature was raised to room temperature, and the mixture was stirred for 24 hours. The reaction mixture was concentrated under reduced pressure, the solid was collected by filtration, and the collected solid was washed with ethyl acetate to obtain 48.1 g (pale yellow solid) of the target compound (1 g).
Melting point: 154 ° C (decomposition),
^{1 1} H-NMR (300 MHz, MeOD, δ ppm):
1.15 (d, J = 6.2Hz, 3H), 3.05 (brs, 1H), 3.35 (brs, 1H), 3.89 (brs, 1H), 6.51 (s, 1H) , 7.65-7.91 (m, 4H)

Production Example 8: Production of 1- (4-carboxybenzylidene) -4-methyl-3- oxopyrazolidinium ilide (1h) In a 300 mL eggplant flask, 15.0 mL (0.31 mol) of hydrated hydrazine and ethanol. 150 mL was added, and 35.5 mL (1.1 eq) of methyl methacrylate was added while stirring the resulting mixture in an ice bath, and the mixture was heated under reflux for 16 hours and then cooled to room temperature. While stirring the reaction solution in an ice bath, 46.3 g (1.0 eq) of terephthalaldehyde acid was added, the temperature was raised to room temperature, and the mixture was stirred for 24 hours. The solid was collected by filtration, and the collected solid was washed with methanol and then crushed and washed with chloroform and methanol to obtain 59.4 g (pale orange solid) of the target compound (1h).
Melting point: 280 ° C,
_{^{1 H-NMR (300MHz, d}} 6 -DMSO, δppm):
1.19 (d, J = 7.2Hz, 3H), 2.77 (m, 1H), 4.27 (ddd, J = 1.5, 6.9, 13.5Hz, 1H), 4.79 (Ddd, J = 1.2,9.3,13.5Hz, 1H), 7.73 (s, 1H), 8.05-8.08 (m, 2H), 8.38-8.41 ( m, 2H), 13.15 (brs, 1H)

Production Example 9: Production of 1- (4-dimethylaminobenzylidene) -4-methyl-3- oxopyrazolidinium irid (1i) In a 300 mL eggplant flask, 15.0 mL (0.31 mol) of hydrated hydrazine, and 150 mL of ethanol was added, 35.5 mL (1.1 eq) of methyl methacrylate was added while stirring the resulting mixture in an ice bath, and the mixture was heated under reflux for 16 hours and then cooled to room temperature. While stirring the reaction solution in an ice bath, 46.0 g (1.0 eq) of 4-dimethylaminobenzaldehyde was added, the temperature was raised to room temperature, and the mixture was stirred for 24 hours. The reaction mixture was concentrated under reduced pressure, ethyl acetate was added, and the precipitated solid was collected by filtration, and the collected solid was washed with ethyl acetate to obtain 43.8 g (yellow solid) of the target compound (1i).
Melting point: 193 ° C,
^{1 1} H-NMR (300 MHz, CDCl ₃ , δ ppm):
1.39 (d, J = 7.2Hz, 3H), 2.94 (m, 1H), 3.08 (s, 6H), 4.01 (dd, J = 7.2, 12.3Hz, 1H) ), 4.55 (dd, J = 9.3,12.3Hz, 1H), 6.68 (d, J = 9.3Hz, 2H), 6.95 (s, 1H), 8.18-8 .21 (m, 2H)

Production Example 10: Production of 4-Methyl-1- (3-Nitrobenzylidene) -3- oxopyrazolidinium irid (1j) In a 300 mL eggplant flask, 15.0 mL (0.31 mol) of hydrated hydrazine and ethanol. 150 mL was added, and 35.5 mL (1.1 eq) of methyl methacrylate was added while stirring the resulting mixture in an ice bath, and the mixture was heated under reflux for 16 hours and then cooled to room temperature. While stirring the reaction solution in an ice bath, 46.6 g (1.0 eq) of 3-nitrobenzaldehyde was added, the temperature was raised to room temperature, and the mixture was stirred for 23 hours. The solid was collected by filtration, and the collected solid was washed with ethanol and ethyl acetate to obtain 39.1 g (yellow solid) of the target compound (1j).
Melting point: 190 ° C,
^{1 1} H-NMR (300 MHz, CDCl ₃ , δ ppm):
1.44 (d, J = 7.2Hz, 3H), 3.01 (m, 1H), 4.23 (ddd, J = 1.2, 6.6, 12.9Hz, 1H), 4.78 (Ddd, J = 1.2,9.3,12.9Hz, 1H), 7.19 (s, 1H), 7.68 (t, J = 8.1Hz, 1H), 8.29 (m, 1H), 8.77 (m, 1H), 9.07 (d, J = 8.1Hz, 1H)

Production Example 11: Production of 4-Methyl-1- (4-Nitrobenzylidene) -3- oxopyrazolidinium irid (1k) In a 300 mL eggplant flask, 15.0 mL (0.31 mol) of hydrated hydrazine and ethanol. 150 mL was added, and 35.5 mL (1.1 eq) of methyl methacrylate was added while stirring the resulting mixture in an ice bath, and the mixture was heated under reflux for 16 hours and then cooled to room temperature. While stirring the reaction solution in an ice bath, 46.6 g (1.0 eq) of 4-nitrobenzaldehyde was added, the temperature was raised to room temperature, and the mixture was stirred for 23 hours. The solid was collected by filtration, and the solid was washed with ethanol and ethyl acetate, and then crushed and washed with ethyl acetate at 40 ° C. The solid was filtered and washed with ethyl acetate to obtain 22.4 g (yellow solid) of the target compound (1k).
Melting point: 178 ° C,
^{1 1} H-NMR (300 MHz, CDCl ₃ , δ ppm):
1.44 (d, J = 7.2Hz, 3H), 3.01 (m, 1H), 4.24 (ddd, J = 1.2, 6.6, 12.9Hz, 1H), 4.78 (Ddd, J = 1.2,9.3,13.2Hz, 1H), 7.16 (s, 1H), 8.27-8.32 (m, 2H), 8.46-8.51 ( m, 2H)

Production Example 12: Production of 1- (2-furanylmethylidene) -4-methyl-3- oxopyrazolidinium irid (1 l) In a 300 mL eggplant flask, 15.0 mL (0.31 mol) of hydrated hydrazine, And 150 mL of ethanol were added, and 35.5 mL (1.1 eq) of methyl methacrylate was added while stirring the obtained mixture in an ice bath, and the mixture was heated under reflux for 16 hours and then cooled to room temperature. While stirring the reaction solution in an ice bath, 25.6 mL (1.0 eq) of furfural was added, the temperature was raised to room temperature, and the mixture was stirred for 9 hours. The reaction mixture was concentrated under reduced pressure, ethyl acetate was added, and the precipitated solid was collected by filtration, and the collected solid was washed with ethyl acetate to obtain 37.4 g (pale orange solid) of the target compound (1 l).
Melting point: 178 ° C,
^{1 1} H-NMR (300 MHz, CDCl ₃ , δ ppm):
1.41 (d, J = 7.5Hz, 3H), 3.00 (m, 1H), 4.08 (ddd, J = 1.2, 6.9, 12.9Hz, 1H), 4.63 (Ddd, J = 0.9, 9.6, 12.9Hz, 1H), 6.66 (m, 1H) 7.20 (s, 1H), 7.60 (d, J = 1.5Hz, 1H) ), 7.95 (d, J = 3.6Hz, 1H)

Production Example 13: Production of 5-Methyl-1- (2-pyridinyl methylidene) -3-oxopyrazolidinium irid (1 m) In a 300 mL eggplant flask, 15.0 mL (0.31 mol) of hydrated hydrazine. , And 150 mL of ethanol were added, and 42.1 mL (1.1 eq) of ethyl crotonate was added to the resulting mixture while stirring in an ice bath, and the mixture was heated under reflux for 16 hours and then cooled to room temperature. While stirring the reaction solution in an ice bath, 29.5 mL (1.0 eq) of 2-pyridinecarboxyaldehyde was added, the temperature was raised to room temperature, and the mixture was stirred for 6 hours. The reaction mixture was concentrated under reduced pressure, extracted with chloroform, and washed with water. The organic phase is dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and then ethyl acetate and hexane are added to filter the precipitated solid, and the collected solid is washed with ethyl acetate to obtain the desired compound (1 m). 34.4 g (pale yellow solid) was obtained.
Melting point: 144 ° C,
^{1 1} H-NMR (300 MHz, CDCl ₃ , δ ppm):
1.74 (d, J = 6.9Hz, 3H), 2.52 (dd, J = 4.5, 16.8Hz, 1H), 3.07 (dd, J = 9.3, 16.8Hz, 1H), 4.79 (m, 1H), 7.34 (ddd, J = 1.2, 4.8, 7.8Hz, 1H), 7.37 (s, 1H), 7.85 (ddd, J = 1.5, 7.8, 7.8Hz, 1H), 8.70 (m, 1H), 9.24 (d, J = 8.4Hz, 1H)

Production Example 14: Production of 1- (2-pyridinylmethylidene) -3- oxopyrazolidinium irid (1n) In a 300 mL eggplant flask, 15.0 mL (0.31 mol) of hydrated hydrazine and 150 mL of ethanol Was added, and 40.7 mL (1.1 eq) of methyl acrylate was added to the obtained mixture while stirring in an ice bath, and the mixture was heated under reflux for 16 hours and then cooled to room temperature. While stirring the reaction solution in an ice bath, 39.4 mL (1.0 eq) of 2-pyridinecarboxyaldehyde was added, the temperature was raised to room temperature, and the mixture was stirred for 23 hours. The reaction mixture was concentrated under reduced pressure, the solid was collected by filtration, and the collected solid was washed with ethyl acetate to obtain 34.7 g (pale orange solid) of the target compound (1n).
Melting point: 180 ° C (decomposition),
^{1 1} H-NMR (300 MHz, CDCl ₃ , δ ppm):
2.87 (m, 2H), 4.61 (m, 2H), 7.34 (ddd, J = 1.2, 4.5, 7.5Hz, 1H), 7.38 (s, 1H), 7.85 (ddd, J = 1.5, 7.8, 7.8Hz, 1H), 8.69 (m, 1H), 9.22 (d, J = 8.1Hz, 1H)

Production Example 15: Production of 5,5-dimethyl-1- (2-pyridinyl methylidene) -3-oxopyrazolidinium irid (1o) In a 300 mL eggplant flask, 15.0 mL (0.31) of hydrated hydrazine. Mol) and 150 mL of ethanol were added, and 47.3 mL (1.1 eq) of ethyl 3-methylcrotonate was added while stirring the resulting mixture in an ice bath, and the mixture was heated under reflux for 16 hours and then cooled to room temperature. While stirring the reaction solution in an ice bath, 29.5 mL (1.0 eq) of 2-pyridinecarboxyaldehyde was added, the temperature was raised to room temperature, and the mixture was stirred for 22 hours. The reaction mixture was concentrated under reduced pressure, and the solid was filtered and washed with ethyl acetate. Then, it was dissolved in hot chloroform, concentrated under reduced pressure, and the solid was collected by filtration, and the collected solid was washed with ethyl acetate to obtain 40.4 g (yellow solid) of the target compound (1o).
Melting point: 223 ° C,
^{1 1} H-NMR (300 MHz, CDCl ₃ , δ ppm):
1.76 (s, 6H), 2.78 (s, 2H), 7.35 (s, 1H), 7.36 (ddd, J = 1.2, 4.8, 8.7Hz, 1H), 7.86 (ddd, J = 1.5, 7.5, 7.5Hz, 1H), 8.71 (m, 1H), 9.27 (ddd, J = 0.9, 0.9, 8. 1Hz, 1H)

Production Example 16: Production of 1- (2-pyridinyl methylidene) -3-oxopyridazinium irid (1p) In a 1 L eggplant flask, 16.9 mL (1.0 equivalent) of hydrated hydrazine, triethylamine 60. 7 mL (1.25 eq) and 465 mL of ethanol were added and 50.0 mL (0.35 mol) of ethyl 4-bromobutyrate was added with stirring. After stirring at 45 ° C. for 4.5 hours, the mixture was heated under reflux for 4.5 hours and then cooled to room temperature. While stirring the reaction solution in an ice bath, 33.3 mL (1.0 eq) of 2-pyridinecarboxyaldehyde was added, the temperature was raised to room temperature, and the mixture was stirred for 17 hours. The reaction mixture was concentrated under reduced pressure, the precipitated salt was filtered, and washing with ethyl acetate was repeated 3 times. The filtrate was concentrated under reduced pressure, chloroform was added, and the filtrate was concentrated under reduced pressure again. Ethyl acetate was added and the precipitated solid was collected by filtration, and the collected solid was washed with a mixed solution of ethyl acetate / hexane = 1/1 to obtain 17.6 g (pale yellow solid) of the target compound (1p). rice field.
Melting point: 134 ° C,
^{1 1} H-NMR (300 MHz, CDCl ₃ , δ ppm):
2.25 (m, 2H), 2.64 (m, 2H), 3.78 (m, 2H), 7.28 (ddd, J = 1.2, 4.8, 7.2Hz, 1H), 7.73 (ddd, J = 0.6, 8.1, 8.1Hz, 1H), 7.88 (s, 1H), 8.20 (ddd, J = 0.9, 0.9, 7. 8Hz, 1H), 8.60 (m, 1H)

Examples 1 to 16: Preparation of Modified Polymer Each rubber component shown in Tables 1 and 2 and the azomethine imine compound produced in Production Examples 1 to 16 were mixed at their ratios (parts by mass) using a Banbury mixer. From the time when the temperature of the mixture reached 130 to 150 ° C., the mixture was mixed for about 2 minutes while adjusting to maintain the temperature, and then cooled with a roll mill to produce a modified polymer.

Examples 17-32
Each component shown in steps (I) of Tables 3 and 4 below was mixed at that ratio (part by mass), and mixed for 5 minutes while adjusting the rotation speed so that the maximum temperature of the mixture became 160 ° C. with a Banbury mixer. .. After curing until the temperature of the mixture becomes 80 ° C. or lower, each component shown in steps (II) of Tables 3 and 4 is added at the ratio (part by mass), and the maximum temperature of the mixture becomes 110 ° C. or lower. The rubber composition was produced by mixing while adjusting the above.

Low heat buildup (tan δ index) test For the rubber compositions of Examples 17 to 32, tan δ was measured at a temperature of 40 ° C., a dynamic strain of 5%, and a frequency of 15 Hz using a viscoelasticity measuring device (manufactured by Metravib). For comparison, rubber compositions (references) were prepared by the same formulation and the same production method as in each example except that the azomethine imine compound was not added, and the reciprocal of tan δ was set to 100. The low exothermic index was calculated based on the following formula. The larger the value of the low heat generation index, the lower the heat generation and the smaller the hysteresis loss. Further, the low heat generation property of the vulcanized rubber composition of each reference is set to 100.
Formula: Low exothermic index = {(tan δ of rubber composition to which azomethine imine compound (1) is not added) / (tan δ of rubber composition of the present invention)} × 100

The rubber compositions of all the examples showed low heat generation with respect to the comparative rubber compositions to which the azomethine imine compound was not added. Among them, Examples 17, 29 and 31 showed further excellent low heat generation and showed low heat generation indices 116, 124 and 115, respectively.

[Explanation of symbols in the table]
The raw materials used in the examples (in the table) are shown below.
* 1: Solution polymerization SBR (S-SBR), manufactured by PetroChina Dushanzi Petrochemical Company, trade name "RC2557S"
* 2: Butadiene rubber (BR), Sinopec Qil Petrochemical Co., Ltd. , Ltd. Made, product name "BR9000"
* 3: Azomethine imine compound (1a): 4-methyl-1- (2-pyridinyl methylidene) -3-oxopyrazolidinium ylide (compound produced in Production Example 1)
* 4: Azomethine imine compound (1b): 4-methyl-1- (3-pyridinyl methylidene) -3-oxopyrazolidinium ylide (compound produced in Production Example 2)
* 5: Azomethine imine compound (1c): 4-methyl-1- (4-pyridinyl methylidene) -3-oxopyrazolidinium ylide (compound produced in Production Example 3)
* 6: Azomethine imine compound (1d): 1-benzylidene-4-methyl-3-oxopyrazolidinium ylide (compound produced in Production Example 4)
* 7: Azomethine imine compound (1e): 1- (2-hydroxybenzylidene) -4-methyl-3-oxopyrazolidinium ylide (compound produced in Production Example 5)
* 8: Azomethine imine compound (1f): 1- (4-hydroxybenzylidene) -4-methyl-3-oxopyrazolidinium ylide (compound produced in Production Example 6)
* 9: Azomethine imine compound (1 g): 1- (2-carboxybenzylidene) -4-methyl-3-oxopyrazolidinium ylide (compound produced in Production Example 7)
* 10: Azomethine imine compound (1h): 1- (4-carboxybenzylidene) -4-methyl-3-oxopyrazolidinium ylide (compound produced in Production Example 8)
* 11: Azomethine imine compound (1i): 1- (4-dimethylaminobenzylidene) -4-methyl-3-oxopyrazolidinium ylide (compound produced in Production Example 9)
* 12: Azomethine imine compound (1j): 4-methyl-1- (3-nitrobenzylidene) -3-oxopyrazolidinium ylide (compound produced in Production Example 10)
* 13: Azomethine imine compound (1k): 4-methyl-1- (4-nitrobenzylidene) -3-oxopyrazolidinium ilide (compound produced in Production Example 11)
* 14: Azomethine imine compound (1 l): 1- (2-furanylmethylidene) -4-methyl-3-oxopyrazolidinium ylide (compound produced in Production Example 12)
* 15: Azomethine imine compound (1 m): 5-methyl-1- (2-pyridinyl methylidene) -3-oxopyrazolidinium ylide (compound produced in Production Example 13)
* 16: Azomethine imine compound (1n): 1- (2-pyridinyl methylidene) -3-oxopyrazolidinium ylide (compound produced in Production Example 14)
* 17: Azomethine imine compound (1o): 5,5-dimethyl-1- (2-pyridinyl methylidene) -3-oxopyrazolidinium ylide (compound produced in Production Example 15)
* 18: Azomethine imine compound (1p): 1- (2-pyridinyl methylidene) -3-oxopyridazinium ylide (compound produced in Production Example 16)
* 19: Modified S-SBR / BR produced in Example 1.
* 20: Modified S-SBR / BR produced in Example 2
* 21: Modified S-SBR / BR produced in Example 3
* 22: Modified S-SBR / BR produced in Example 4
* 23: Modified S-SBR / BR produced in Example 5
* 24: Modified S-SBR / BR produced in Example 6
* 25: Modified S-SBR / BR produced in Example 7.
* 26: Modified S-SBR / BR produced in Example 8
* 27: Modified S-SBR / BR produced in Example 9
* 28: Modified S-SBR / BR produced in Example 10
* 29: Modified S-SBR / BR produced in Example 11
* 30: Modified S-SBR / BR produced in Example 12
* 31: Modified S-SBR / BR produced in Example 13
* 32: Modified S-SBR / BR produced in Example 14
* 33: Modified S-SBR / BR produced in Example 15
* 34: Modified S-SBR / BR produced in Example 16
* 35: Quachen Silicon Chemical Co., Ltd. , Ltd. Made, product name "HD165MP"
* 36: Product name "Si69" manufactured by Evonik Industries AG
* 37: Carbon black, manufactured by Cabot, trade name "N234"
* 38: Rhein Chemie Rheinau GmbH, trade name "Antilux 111"
* 39: Product name "Vivatec 700" manufactured by Hansen & Rosenthal.
* 40: Keimai Chemical Co., Ltd. , Ltd. Made, product name "6-PPD"
* 41: Sichuan Tianyu Grease Chemical Co., Ltd. , Ltd. * 42: Dalian Zinc Oxide Co., Ltd. , Ltd. * 43: Keimai Chemical Co., Ltd. , Ltd. Made, product name "DPG"
* 44: Keimai Chemical Co., Ltd. , Ltd. Made, product name "CBS"
* 45: Shanghai Jinghai Chemical Co., Ltd. , Ltd. Made

By blending the azomethine imine compound (1), the rubber composition of the present invention has improved dispersibility of an inorganic filler (for example, silica or the like) and / or carbon black, and is excellent in low heat generation. Therefore, it can be used as a member of various pneumatic tires of various automobiles, particularly a tread member, a sidewall member, a bead area member, a belt member, a carcass member, and a shoulder member of a pneumatic radial tire. ..

Claims (13)

It is an additive for imparting low heat generation to the rubber component.
An additive containing an azomethine imine compound represented by the following general formula (1) or a salt thereof.

[In the formula, R ¹ is an aryl group or a heterocyclic group, R ² is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and each of these groups has one or more substituents. You may. R ³ , R ⁴ , R ⁵ and R ⁶ represent the same or different hydrogen atoms, alkyl or aryl groups, each of which may have one or more substituents. n represents an integer of 0 to 2. ] The additive according to claim 1, wherein R1 is an aryl group or a heterocyclic group. The additive according to claim 1 or 2, wherein the rubber component is a diene-based rubber. A modified polymer prepared by using a rubber mixture containing a rubber component and the additive according to any one of claims 1 to 3. The modified polymer according to claim 4, wherein the rubber component is a diene-based rubber. A modified polymer having at least one selected from the compound structures represented by the following general formulas (2-1) to (2-7).

[In the formula, R ¹ is an aryl group or a heterocyclic group, R ² is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and each of these groups has one or more substituents. You may. R ³ , R ⁴ , R ⁵ and R ⁶ represent the same or different hydrogen atoms, alkyl or aryl groups, each of which may have one or more substituents. X represents a halogen atom or an alkyl group. n represents an integer of 0 to 2. ] A rubber composition containing a rubber component, the additive according to any one of claims 1 to 3, an inorganic filler and / or carbon black. The rubber composition according to claim 7, wherein the rubber component is a diene-based rubber. A rubber composition containing the modified polymer according to any one of claims 4 to 6 and an inorganic filler and / or carbon black. The rubber composition according to any one of claims 7 to 9, which 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. A tire produced by using the rubber composition according to any one of claims 7 to 10. The step (I) of mixing the rubber component, the additive according to any one of claims 1 to 3, and the raw material component containing the inorganic filler and / or carbon black, and the mixture obtained in the step (I). A method for producing a rubber composition, which comprises the step (II) of mixing the vulcanizing agent and the vulcanizing agent. Step (I) is the step (I-1) of mixing the rubber component and the additive according to any one of claims 1 to 3, the mixture obtained in step (I-1), and the inorganic substance. The production method according to claim 12, which is a step (I-2) of mixing the filler and / or carbon black.