TW201313803A - Rubber composition - Google Patents

Abstract

Provided is a rubber composition containing: at least one compound selected from among the group comprising a compound represented by formula (I-1), a compound represented by formula (I-2) and a compound represented by formula (I-3); a rubber component; and a filler.

Description

Rubber composition

The present invention relates to a rubber composition and the like.

In recent years, due to the demand for environmental protection, it is required to improve the fuel efficiency of automobiles (ie, low fuel consumption). Moreover, it is known that in the field of automobile tires, the fuel efficiency of the automobile can be improved by improving the viscoelastic properties of the vulcanized rubber used in the tire manufacturing (refer to the Japan Rubber Association's "Introduction to Rubber Technology" Maruzen Co., Ltd. Ltd., 124 pages).

The present invention encompasses the following inventions.

[1] A rubber composition selected from the group consisting of a compound represented by the formula (I-1), a compound represented by the formula (I-2), and a compound represented by the formula (I-3). One or more kinds of compounds are mixed with a rubber component and a filler, and [In the formula (I-1), A ¹ and A ² each independently represent an alkanediyl group having 2 to 12 carbon atoms which may have a substituent, a cycloalkanediyl group having 3 to 12 carbon atoms which may have a substituent, or -B ^1- Ar-B ² - group, -CH ₂ - contained in the alkanediyl group having 2 to 12 carbon atoms may be substituted by -NH-, -O- or -S-; B ¹ and B ² are each independently represented by a single a bond or a C2 1 to 6 alkanediyl group; Ar represents a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent; and R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, and a carbon number of 1 to 2; 6 alkyl, aryl group having 6 to 12 carbon atoms, hydroxyl group or alkoxy group having 1 to 6 carbon atoms, or bonded to each other to form an alkanediyl group having 1 to 12 carbon atoms; X ¹ and X ² are each independently represented - NH- or -O-].

[In the formula (I-2), A ³ and A ⁴ each independently represent an alkanediyl group having 2 to 12 carbon atoms which may have a substituent, a cycloalkanediyl group having 3 to 12 carbon atoms which may have a substituent, or -B ^3- Ar ¹ -B ⁴ -yl, -CH ₂ - contained in the alkanediyl group having 2 to 12 carbon atoms may be substituted by -NH-, -O- or -S-; B ³ and B ⁴ are independently represented by a single bond or a C 2 to 6 alkanediyl group; Ar ¹ represents a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent; and R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, and a carbon number; An alkyl group of 1 to 6, an aryl group having 6 to 12 carbon atoms, a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms; and X ³ and X ⁴ each independently represent -NH- or -O-].

[In the formula (I-3), A ⁵ represents an alkanediyl group having 2 to 12 carbon atoms which may have a substituent, a cycloalkyldiyl group having 3 to 12 carbon atoms which may have a substituent, or ^* -B ⁵ -Ar ² -B ⁶ - group, -CH ₂ - contained in the alkyl 2 to 12 alkanediyl group may be substituted by -NH-, -O- or -S-, ^* represents a bond with X ⁵ ; B ⁵ Represents a single bond or an alkyldiyl group having 1 to 6 carbon atoms; B ⁶ represents a single bond or an alkyl 2 group having 1 to 6 carbon atoms; and Ar ² represents a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent. X ⁵ represents -CO-NH- ^* , -CO-O- ^* , -CO- ^* or a single bond, ^* represents a bonding bond with A ⁵ ; R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, An alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms, or bonded to each other to form an alkanediyl group having 1 to 12 carbon atoms.

[2] The rubber composition according to [1], wherein R ¹ and R ² are a hydrogen atom.

[3] The rubber composition according to [1] or [2], wherein A ¹ and A ² are each independently a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms.

[4] The rubber composition according to any one of [1] to [3] wherein X ¹ and X ² are -NH-.

[5] The rubber composition according to [1], wherein R ³ and R ⁴ are a hydrogen atom.

[6] The rubber composition according to [1] or [5], wherein A ³ and A ⁴ are each independently a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms.

[7] The rubber composition of [1], [5] or [6], wherein X ³ and X ⁴ are -NH-.

[8] The rubber composition according to [1], wherein R ⁵ and R ⁶ are a hydrogen atom.

[9] The rubber composition according to [1] or [8], wherein A ⁵ is a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent.

[10] The rubber composition of [1], [8] or [9], wherein X ⁵ represents a single bond, and A ⁵ represents a ^* -B ⁵ -Ar ² -B ⁶ - group (B ⁵ represents a single bond, B ⁶ represents a single bond or an alkyl group).

[11] The rubber composition according to any one of [1] to [10] wherein the rubber component It is natural rubber.

[12] The rubber composition according to any one of [1] to [11] which further contains a sulfur component.

[13] A vulcanized rubber obtained by subjecting the rubber composition of [12] to heat treatment.

[14] A tire produced by processing the rubber composition of [12].

[15] A belt for a tire comprising a steel cord coated with a vulcanized rubber as in [13].

[16] A carcass for a tire comprising a carcass fiber rope coated with a vulcanized rubber as in [13].

[17] A sidewall for a tire, an inner liner for an tire, a cap tread for a tire, or an under tread for a tire, which includes Such as vulcanized rubber of [13].

[18] A tire comprising the vulcanized rubber of [13].

[19] A method for improving viscoelastic properties of a vulcanized rubber, which comprises a compound represented by the formula (I-1), a compound represented by the formula (I-2), and a formula (I-3) a step of kneading a rubber component and a filler with a sulfur component, and a step of heat-treating the kneaded material obtained by the previous step, [In the formula (I-1), A ¹ and A ² each independently represent an alkanediyl group having 2 to 12 carbon atoms which may have a substituent, a cycloalkanediyl group having 3 to 12 carbon atoms which may have a substituent, or -B ^1- Ar-B ² - group, -CH ₂ - contained in the alkanediyl group having 2 to 12 carbon atoms may be substituted by -NH-, -O- or -S-; B ¹ and B ² are each independently represented by a single a bond or a C 2 to 6 alkanediyl group; Ar represents a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent; and R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, and a carbon number of 1 to 2; 6 alkyl, aryl group having 6 to 12 carbon atoms, hydroxyl group or alkoxy group having 1 to 6 carbon atoms, or bonded to each other to form an alkanediyl group having 1 to 12 carbon atoms; X ¹ and X ² are each independently represented - NH- or -O-].

[In the formula (I-2), A ³ and A ⁴ each independently represent an alkanediyl group having 2 to 12 carbon atoms which may have a substituent, a cycloalkanediyl group having 3 to 12 carbon atoms which may have a substituent, or -B ^3- Ar ¹ -B ⁴ -yl, -CH ₂ - contained in the alkanediyl group having 2 to 12 carbon atoms may be substituted by -NH-, -O- or -S-; B ³ and B ⁴ are independently represented by a single bond or a C 2 to 6 alkanediyl group; Ar ¹ represents a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent; and R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, and a carbon number; An alkyl group of 1 to 6, an aryl group having 6 to 12 carbon atoms, a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms; and X ³ and X ⁴ each independently represent -NH- or -O-].

[In the formula (I-3), A ⁵ represents an alkanediyl group having 2 to 12 carbon atoms which may have a substituent, a cycloalkyldiyl group having 3 to 12 carbon atoms which may have a substituent, or ^* -B ⁵ -Ar ² -B ⁶ - group, -CH ₂ - contained in the alkyl 2 to 12 alkanediyl group may be substituted by -NH-, -O- or -S-, ^* represents a bond with X ⁵ ; B ⁵ Represents a single bond or an alkyldiyl group having 1 to 6 carbon atoms; B ⁶ represents a single bond or an alkyl 2 group having 1 to 6 carbon atoms; and Ar ² represents a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent. X ⁵ represents -CO-NH- ^* , -CO-O- ^* , -CO- ^* or a single bond, ^* represents a bonding bond with A ⁵ ; R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, An alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms, or bonded to each other to form an alkanediyl group having 1 to 12 carbon atoms.

[20] A compound selected from the group consisting of a compound represented by the formula (I-1), a compound represented by the formula (I-2), and a compound represented by the formula (I-3). Use to improve the viscoelastic properties of vulcanized rubber. [In the formula (I-1), A ¹ and A ² each independently represent an alkanediyl group having 2 to 12 carbon atoms which may have a substituent, a cycloalkanediyl group having 3 to 12 carbon atoms which may have a substituent, or -B ^1- Ar-B ² - group, -CH ₂ - contained in the alkanediyl group having 2 to 12 carbon atoms may be substituted by -NH-, -O- or -S-; B ¹ and B ² each independently represent a single a bond or a C 2 to 6 alkanediyl group; Ar represents a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent; and R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, and a carbon number of 1 to 2; 6 alkyl, aryl group having 6 to 12 carbon atoms, hydroxyl group or alkoxy group having 1 to 6 carbon atoms, or bonded to each other to form an alkanediyl group having 1 to 12 carbon atoms; X ¹ and X ² are each independently represented - NH- or -O-].

[In the formula (I-2), A ³ and A ⁴ each independently represent an alkanediyl group having 2 to 12 carbon atoms which may have a substituent, a cycloalkanediyl group having 3 to 12 carbon atoms which may have a substituent, or -B ^3- Ar ¹ -B ⁴ -yl, -CH ₂ - contained in the alkanediyl group having 2 to 12 carbon atoms may be substituted by -NH-, -O- or -S-; B ³ and B ⁴ are independently represented by a single bond or a C 2 to 6 alkanediyl group; Ar ¹ represents a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent; and R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, and a carbon number; An alkyl group of 1 to 6, an aryl group having 6 to 12 carbon atoms, a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms; and X ³ and X ⁴ each independently represent -NH- or -O-].

[In the formula (I-3), A ⁵ represents an alkanediyl group having 2 to 12 carbon atoms which may have a substituent, a cycloalkyldiyl group having 3 to 12 carbon atoms which may have a substituent, or ^* -B ⁵ -Ar ² -B ⁶ - group, -CH ₂ - contained in the alkyl 2 to 12 alkanediyl group may be substituted by -NH-, -O- or -S-, ^* represents a bond with X ⁵ ; B ⁵ Represents a single bond or an alkyldiyl group having 1 to 6 carbon atoms; B ⁶ represents a single bond or an alkyl 2 group having 1 to 6 carbon atoms; and Ar ² represents a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent. X ⁵ represents -CO-NH- ^* , -CO-O- ^* , -CO- ^* or a single bond, ^* represents a bonding bond with A ⁵ ; R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, An alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms, or bonded to each other to form an alkanediyl group having 1 to 12 carbon atoms.

[21] A vulcanized rubber viscoelastic property improving agent comprising a compound selected from the group consisting of a compound represented by the formula (I-1), a compound represented by the formula (I-2), and a compound represented by the formula (I-3). One or more compounds in the group are used as active ingredients,

[In the formula (I-1), A ¹ and A ² each independently represent an alkanediyl group having 2 to 12 carbon atoms which may have a substituent, a cycloalkanediyl group having 3 to 12 carbon atoms which may have a substituent, or -B ^1- Ar-B ² - group, -CH ₂ - contained in the alkanediyl group having 2 to 12 carbon atoms may be substituted by -NH-, -O- or -S-; B ¹ and B ² are each independently represented by a single a bond or a C2 1 to 6 alkanediyl group; Ar represents a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent; and R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, and a carbon number of 1 to 2; 6 alkyl, aryl group having 6 to 12 carbon atoms, hydroxyl group or alkoxy group having 1 to 6 carbon atoms, or bonded to each other to form an alkanediyl group having 1 to 12 carbon atoms; X ¹ and X ² are each independently represented - NH- or -O-].

[In the formula (I-2), A ³ and A ⁴ each independently represent an alkanediyl group having 2 to 12 carbon atoms which may have a substituent, a cycloalkanediyl group having 3 to 12 carbon atoms which may have a substituent, or -B ^3- Ar ¹ -B ⁴ -yl, -CH ₂ - contained in the alkanediyl group having 2 to 12 carbon atoms may be substituted by -NH-, -O- or -S-; B ³ and B ⁴ are independently represented by a single bond or a C 2 to 6 alkanediyl group; Ar ¹ represents a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent; and R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, and a carbon number; An alkyl group of 1 to 6, an aryl group having 6 to 12 carbon atoms, a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms; and X ³ and X ⁴ each independently represent -NH- or -O-].

[In the formula (I-3), A ⁵ represents an alkanediyl group having 2 to 12 carbon atoms which may have a substituent, a cycloalkyldiyl group having 3 to 12 carbon atoms which may have a substituent, or ^* -B ⁵ -Ar ² -B ⁶ - group, -CH ₂ - contained in the carbon number 2 to 12 alkanediyl group may be substituted by -NH-, -O- or -S-, ^* represents a bond with X ⁵ ; B ⁵ Represents a single bond or an alkyldiyl group having 1 to 6 carbon atoms; B ⁶ represents a single bond or an alkyl 2 group having 1 to 6 carbon atoms; and Ar ² represents a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent. X ⁵ represents -CO-NH- ^* , -CO-O- ^* , -CO- ^* or a single bond, ^* represents a bonding bond with A ⁵ ; R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, An alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms, or bonded to each other to form an alkanediyl group having 1 to 12 carbon atoms.

[22] a compound of the formula (I-1), [In the formula (I-1), A ¹ and A ² each independently represent an alkanediyl group having 2 to 12 carbon atoms which may have a substituent, a cycloalkanediyl group having 3 to 12 carbon atoms which may have a substituent, or -B ^1- Ar-B ² - group, -CH ₂ - contained in the alkanediyl group having 2 to 12 carbon atoms may be substituted by -NH-, -O- or -S-; B ¹ and B ² are each independently represented by a single a bond or a C 2 to 6 alkanediyl group; Ar represents a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent; and R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, and a carbon number of 1 to 2; 6 alkyl, aryl group having 6 to 12 carbon atoms, hydroxyl group or alkoxy group having 1 to 6 carbon atoms, or bonded to each other to form an alkanediyl group having 1 to 12 carbon atoms; X ¹ and X ² are each independently represented - NH- or -O-].

In the present invention, the term "improving the viscoelastic property" means, for example, changing the loss factor (tan δ, loss factor) of the vulcanized rubber described later.

Hereinafter, one or more compounds selected from the group consisting of a compound represented by the formula (I-1), a compound represented by the formula (I-2), and a compound represented by the formula (I-3) may be selected. It is called "compound (I)".

<The compound represented by the formula (I-1) (hereinafter, sometimes referred to as "compound (I-1)")>

Examples of the alkanediyl group having 2 to 12 carbon atoms in A ¹ and A ² include a linear alkane such as an ethyl group, a trimethylene group, a tetramethylene group, a pentamethylene group or a hexamethylene group. a branched alkyl such as isopropyl, isobutyl, 2-methyltrimethylene, isopentyl, isohexyl, isooctyl, 2-ethylexyl, or isodecyl. Second base. The carbon number of the alkanediyl group is preferably from 3 to 12, more preferably from 3 to 6. Further, a linear alkanediyl group (polymethylene group) is preferred.

Examples of the substituent which the alkanediyl group may have include alkoxy groups having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, and a butoxy group; and a halogen atom such as a hydroxyl group, a chlorine group, a bromine group, an iodine group or a fluorine group; An alkenyl group having 6 to 12 carbon atoms such as naphthyl or biphenyl. Examples of the alkanediyl group having a substituent include the following groups. ^* indicates the key combination.

The -CH ₂ - contained in the alkanediyl group having 2 to 12 carbon atoms may be substituted by -NH-, -O- or -S-. When the -CH ₂ - contained in the alkanediyl group is substituted by -NH-, -O- or -S-, the carbon number of the alkanediyl group is preferably from 3 to 12, and -NH ₂ group, -X ^{The 1} -CH- or -X ² - group-bonded -CH ₂ - is not substituted by -NH-, -O- or -S-. In the case where -CH ₂ - contained in the alkanediyl group is substituted by -NH-, -O- or -S-, the hetero atoms are not adjacent to each other.

Examples of the alkanediyl group containing -NH-, -O- or -S- include the following groups. ^* indicates the key combination.

Examples of the cycloalkanediyl group having 3 to 12 carbon atoms in A ¹ and A ² include a cyclopropyl group, a cyclopentylene group, a cyclohexylene group, a stretched dodecyl group, and the like.

Examples of the substituent which the cycloalkyldiyl group having 3 to 12 carbon atoms may have include a methyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a n-propyl group, a n-butyl group and a t-butyl group; and a phenyl group; An alkyl group having 6 to 10 carbon atoms such as 4-methylphenyl or naphthyl; an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group or a butoxy group; an ethyl fluorenyl group and a benzamidine group; a mercapto group having 1 to 7 carbon atoms such as a mercapto group or a trimethylethenyl group; an alkoxycarbonyl group having a carbon number of 3 to 4 such as a methoxycarbonyl group or an ethoxycarbonyl group; a phenoxycarbonyl group and a naphthyloxy group; An aryloxycarbonyl group having 7 to 11 carbon atoms such as a carbonyl group; an anthraceneoxy group having 2 to 7 carbon atoms such as an ethoxy group or a benzyl group;

The cycloalkyldiyl group having 3 to 12 carbon atoms which may have a substituent is preferably a cyclopentyl group, a cyclohexylene group, a methylcyclohexylene group, or a tert-butylcyclohexylene group.

Examples of the alkanediyl group having 1 to 6 carbon atoms in B ¹ and B ² include the same as those of the alkanediyl group having 2 to 6 carbon atoms in the alkanediyl group having 2 to 12 carbon atoms.

Examples of the aromatic hydrocarbon group having a carbon number of 6 to 12 in Ar include a stretching phenyl group, a stretching naphthyl group, and a stretching biphenyl group.

The aromatic hydrocarbon group having a carbon number of 6 to 12 may have a substituent, and examples thereof include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a nitro group, a cyano group, and a carboxyl group. A sulfo group, a halogen atom, -CO ₂ M, -SO ₃ M (M represents an alkali metal such as Na or a cation such as an organic base such as NH ₄ ).

As A ¹ and A ² , an alkanediyl group having a carbon number of 2 to 12 or a -B ¹ -Ar-B ² - group is preferred, and a -B ^{1 '} -Ar'-B ^{2 '} - group is more preferred (B ^{1 '} Expresss a single bond, Ar' denotes a phenyl group, B ^2' denotes a single bond or a methylene group), and particularly preferably a phenyl group.

Examples of the halogen atom in R ¹ and R ² include fluorine, chlorine, bromine and iodine.

Examples of the alkyl group having 1 to 6 carbon atoms in R ¹ and R ² include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a second butyl group, and a third butyl group. Base, n-pentyl, isopentyl, n-hexyl, and the like.

Examples of the aryl group having 6 to 12 carbon atoms in R ¹ and R ² include a monocyclic or condensed polycyclic aromatic hydrocarbon having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and a biphenyl group.

Examples of the alkoxy group having 1 to 6 carbon atoms in R ¹ and R ² include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, and an isobutoxy group. Dibutoxy, tert-butoxy, n-pentyloxy, isopentyloxy, n-hexyloxy and the like.

Examples of the alkanediyl group having 1 to 12 carbon atoms which are formed by bonding R ¹ and R ^{2 to} each other include the same group and methylene group as those described above, and preferably an alkanediyl group having 3 or 4 carbon atoms. Further, examples of the cyclic structure in which R ¹ and R ² are bonded to each other and formed by the carbon atoms to be bonded thereto include a cyclopentene ring and a cyclohexene ring.

Preferably, R ¹ is a hydrogen atom, R ² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably R ¹ and R ² are a hydrogen atom.

Preferably, X ¹ and X ² are -NH-.

Specific examples of the compound (I-1) are exemplified.

The compound (I-1) can form a solvate together with a lower alcohol such as methanol or ethanol or water.

The compound (I-1) can be produced by the method shown by the following formula.

(wherein A ¹ , A ² , R ¹ and R ^{2 have} the same meanings as defined above; P ¹ and P ² each independently represent a protecting group such as a third butoxycarbonyl group; and WSCI HCl means 1-ethyl-3-( 3-dimethylaminopropyl)-carbodiimide hydrochloride).

In the above production method, the functional group can be protected by a protecting group. The protecting group can be removed by a general method.

<The compound represented by the formula (I-2) (hereinafter, sometimes referred to as "compound (I-2)")>

Examples of A ³ and A ⁴ include the same as those of A ¹ and A ² in the compound (I-1).

Examples of B ³ and B ⁴ include the same as B ¹ and B ² in the compound (I-1).

Examples of Ar ¹ include the same as those of the compound (I-1).

As A ³ and A ⁴ , an alkanediyl group having a carbon number of 2 to 12 or a -B ³ -Ar ¹ -B ⁴ - group is preferred, and more preferably -B ^{3 '} -Ar ^{1 '} -B ^4' -(B ^3' represents a single bond, Ar ^{1 '} represents a phenyl group, B ^{4 '} represents a single bond or a methylene group), and particularly preferably a phenyl group.

Examples of R ³ and R ⁴ include the same as those of R ¹ and R ² in the compound (I-1).

Preferably, R ³ is a hydrogen atom, R ⁴ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably R ³ and R ⁴ are a hydrogen atom.

Preferably, X ³ and X ⁴ are -NH-.

Specific examples of the compound (I-2) are exemplified.

The compound (I-2) can form a solvate together with a lower alcohol such as methanol or ethanol or water.

The compound (I-2) can be produced by the method shown by the following formula.

(wherein A ³ , A ⁴ , R ³ and R ^{4 have} the same meanings as defined above; and P ³ , P ⁴ , P ⁵ and P ⁶ each independently represent a protecting group such as a third butoxycarbonyl group; DCC represents a dicyclohexyl group; Carboimine

In the above production method, the functional group can be protected by a protecting group. The protecting group can be removed by a general method.

<The compound represented by the formula (I-3) (hereinafter, sometimes referred to as "compound (I-3)")>

The two -X ⁵ -A ⁵ -NH ₂ groups contained in the compound (I-3) represent the same group.

Examples of A ⁵ include the same as those of A ¹ and A ² in the compound (I-1).

Examples of B ⁵ and B ⁶ include the same as B ¹ and B ² in the compound (I-1).

As Ar ² , the same as Ar in the compound (I-1) is listed.

As A ⁵ , an alkanediyl group having a carbon number of 2 to 12 or a ^* -B ⁵ -Ar ² -B ⁶ - group is preferred, and more preferably a ^* -B ^5' -Ar ^2' -B ^6' - group (B) ^5' represents a single bond, Ar ^{2 '} represents a phenyl group, B ^{6 '} represents a single bond or a methylene group, ^* represents a bond with X ⁵ ), and particularly preferably a phenyl group.

Examples of R ⁵ and R ⁶ include the same as those of R ¹ and R ² in the compound (I-1).

Preferably, R ⁵ is a hydrogen atom, R ⁶ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably R ⁵ and R ⁶ are a hydrogen atom.

X ⁵ is -CO-NH- ^* , -CO-O- ^* , -CO- ^* or a single bond, preferably -CO-NH- ^* or a single bond.

Specific examples of the compound (I-3) are exemplified.

The compound (I-3) can form a solvate together with a lower alcohol such as methanol or ethanol or water.

The compound (I-3) can be produced by the method shown by the following formula.

(wherein, A ⁵ , Ar ² , B ⁵ , R ⁵ and R ^{6 have} the same meanings as defined above; P ⁷ and P ⁸ and P ⁹ each independently represent a protecting group such as a third butoxycarbonyl group; WSCI HCl represents 1 Ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride).

In the above production method, the functional group can be protected by a protecting group. The protecting group can be removed by a general method.

The rubber composition of the present invention contains the compound (I) and a rubber component and a filler. The rubber composition of the present invention is preferably a rubber composition obtained by kneading a compound (I) with a rubber component and a filler. The rubber composition of the present invention preferably further contains a sulfur component, and more preferably further contains a vulcanization accelerator and zinc oxide.

As a rubber component, in addition to natural rubber, epoxidized natural rubber, deproteinized natural rubber and other modified natural rubber, polyisoprene rubber (IR), styrene ‧ butadiene copolymer rubber (SBR) can also be exemplified ), polybutadiene rubber (BR), acrylonitrile ‧ butadiene copolymer rubber (NBR), isoprene Synthetic rubber such as isobutylene copolymer rubber (IIR), ethylene ‧ propylene-diene copolymer rubber (EPDM), halogenated butyl rubber (HR), preferably natural rubber, styrene ‧ butadiene copolymer rubber, polybutadiene rubber Wait. Especially good for natural rubber. Further, a combination of natural rubber and styrene ‧ butadiene copolymer rubber, and a combination of natural rubber and polybutadiene rubber are also effective.

Examples of the natural rubber include natural rubbers of the ranks of RSS #1, RSS #3, TSR20, and SIR20. As the epoxidized natural rubber, it is preferred that the degree of epoxidation is 10 to 60 mol%, and ENR25 or ENR50 manufactured by Kumpulan Guthrie Co., Ltd. can be exemplified. As the deproteinized natural rubber, a deproteinized natural rubber having a total nitrogen content of 0.3% by weight or less is preferable. As the modified natural rubber, it is preferred to previously make the natural rubber with 4-vinylpyridine, N,N-dialkylaminoethyl acrylate (for example, N,N-diethylaminoethyl acrylate), acrylic acid 2 A modified natural rubber containing a polar group which is reacted with a hydroxy ester or the like.

Examples of the SBR include emulsion polymerization SBR and solution polymerization SBR disclosed in pages 210 to 211 of the Rubber Industry Handbook <Fourth Edition> by the Japan Rubber Association.

As the rubber composition for a tread, a solution polymerization SBR is preferred. As a solution polymerization SBR, a solution polymerization of molecular end modification by 4,4'-bis-(dialkylamino)benzophenone, such as "Nipol (registered trademark) NS116" manufactured by Japan ZEON Co., Ltd., is preferable. SBR; a solution polymerization SBR such as "SL574" manufactured by JSR Corporation, which is modified by a halogenated tin compound; and a decane modified solution polymerization SBR such as "E10" and "E15" manufactured by Asahi Kasei Corporation; From an indoleamine compound, a guanamine compound, a urea compound, an N,N-dialkyl acrylamide compound, an isocyanate compound, a quinone compound, a decane compound having an alkoxy group (a trialkoxy decane compound, etc.) Or an amino decane compound, which is obtained by modifying a molecular end to obtain a solution-polymerized SBR having a nitrogen, tin or antimony at the molecular end; a tin compound and a decane compound having an alkoxy group or an alkyl acrylamide compound and having A solution-polymerized SBR having two or more kinds of different kinds of compounds, such as alkoxy decane compound, which are modified at the molecular end to have two or more elements at the molecular end. Further, after the polymerization, an oil-added SBR such as a process oil or an aromatherapy oil is added to the emulsion polymerization SBR and the solution polymerization SBR, and it can be preferably used as a rubber composition for a tread.

As the BR, a solution polymerization BR such as a cis 1,4 bond having a high cis BR of 90% or more or a cis bond of about 35% of a low cis BR can be exemplified, and a high vinyl content is preferably low. Formula BR. As the BR, it is preferably a tin-modified BR such as "Nipol (registered trademark) BR 1250H" manufactured by ZEON, Japan; by 4,4'-bis-(dialkylamino)benzophenone, a tin halide compound, a decylamine compound, a guanamine compound, a urea compound, an N,N-dialkyl acrylamide compound, an isocyanate compound, a quinone compound, a decane compound having an alkoxy group (a trialkoxy decane compound, etc.) or An amino decane compound, which is obtained by modifying a molecular end to obtain a solution polymerization BR having nitrogen, tin or bismuth at the molecular end; by a tin compound and a decane compound or an alkyl acrylamide compound having an alkoxy group and having an alkane A solution polymerization BR in which two or more kinds of different compounds, such as an oxo decane compound, are modified at the molecular end to have two or more elements at the molecular end. BR can be preferably used as The rubber composition for a tread or the rubber composition for a sidewall is usually used in combination with SBR and/or natural rubber. The blending ratio is preferably 60 to 100% by weight of SBR and/or natural rubber and 0 to 40% by weight of BR in the rubber composition for the tread, relative to the total rubber weight, and the rubber composition for the sidewall Preferably, the SBR and/or the natural rubber is 10 to 70% by weight, the BR is 90 to 30% by weight, and more preferably 40 to 60% by weight relative to the total rubber weight, relative to the total rubber weight. , BR is 60~40% by weight. The blending of the modified SBR with the unmodified SBR or the blending of the modified BR with the unmodified BR is also preferred.

As the filler, carbon black, cerium oxide, talc, clay, aluminum hydroxide, titanium oxide or the like which is usually used in the rubber field can be exemplified, and carbon black and cerium oxide are preferable, and carbon black is particularly preferable. As the carbon black, it can be cited in the "Rubber Industry Handbook <Fourth Edition>" edited by the Japan Rubber Association, 494 pages, preferably HAF (High Abrasion Furnace), SAF (Super Abrasion Furnace, Super Wear-resistant furnace black), ISAF (Intermediate SAF), ISAF-HM (Intermediate SAF-High Modulus), FEF (Fast Extrusion Furnace), Carbon black such as MAF, GPF (General Purpose Furnace), SRF (Semi-Reinforcing Furnace).

The carbon black contained in the rubber composition for a tire tread preferably has a CTAB surface area of 40 to 250 m ² /g, a nitrogen adsorption specific surface area of 20 to 200 m ² /g, and a particle diameter of 10 to 50 nm. Carbon black is more preferably a carbon black having a CTAB surface area of 70 to 180 m ² /g. Examples of the carbon black include carbon blacks such as N110, N220, N234, N299, N326, N330, N330T, N339, N343, and N351. Further, surface-treated carbon black having 0.1 to 50% by weight of cerium oxide adhered to the surface of the carbon black is also preferable. Further, in combination with carbon black and cerium oxide, a combination of several fillers is also effective, and a combination of carbon black and cerium oxide is preferred.

The carbon black contained in the rubber composition for a carcass or a sidewall is preferably a carbon black having a CTAB surface area of 20 to 60 m ² /g and a particle diameter of 40 to 100 nm. Examples of the carbon black include carbon blacks such as N330, N339, N343, N351, N550, N568, N582, N630, N642, N660, N662, N754, and N762.

The amount of the filler to be used is preferably in the range of 5 to 100 parts by weight based on 100 parts by weight of the rubber component. In the case where only carbon black is used as the filler, the amount of the filler to be used is preferably from 30 to 80 parts by weight, and in the case of using carbon black and cerium oxide in the tread member application, it is preferably from 5 to 50 parts by weight. Share.

As the cerium oxide, cerium oxide having a CTAB specific surface area of 50 to 180 m ² /g or a nitrogen adsorption specific surface area of 50 to 300 m ² /g can be exemplified, and preferably "AQ" manufactured by TOSOH SILICA Co., Ltd. "AQ-N", "Ultrasil (registered trademark) VN3", "Ultrasil (registered trademark) VN3-G", "Ultrasil (registered trademark) 360", "Ultrasil (registered trademark) 7000" manufactured by Degussa, Rhodia "Zeosil (registered trademark) 115GR", "Zeosil (registered trademark) 1115MP", "Zeosil (registered trademark) 1205MP", "Zeosil (registered trademark) Z85MP" manufactured by the company, and manufactured by Nippon Oxide (NIPPONSILICA) Co., Ltd. Nipsil (registered trademark) AQ" and so on. Further, cerium oxide having a pH of 6 to 8, cerium oxide containing 0.2 to 1.5% by weight of sodium, spherical cerium oxide having a roundness of 1 to 1.3, eucalyptus oil such as dimethyl hydrazine, and the like An organic hydrazine compound of a oxyalkylene group, a cerium oxide surface-treated with an alcohol such as ethanol or polyethylene glycol, and two or more kinds of cerium oxide having different nitrogen adsorption specific surface areas are also preferred.

The amount of the filler to be used is preferably 10 to 120 parts by weight based on 100 parts by weight of the rubber component. Further, in the case of preparing cerium oxide, it is preferred to formulate 5 to 50 parts by weight of carbon black, and particularly preferably cerium oxide/carbon black in a ratio of 0.7/1 to 1/0.1. Further, in the case of using ceria as a filler, it is preferred to add a bis (3-triethoxydecylpropyl) tetrasulfide ("Si-69" manufactured by Degussa Co., Ltd.), double ( 3-triethoxydecylpropyl)disulfide ("Si-75" manufactured by Degussa Co., Ltd.), bis(3-diethoxymethyldecylpropyl) tetrasulfide, bis(3-di Ethoxymethyl decyl propyl) disulfide, octyl sulfate S-[3-(triethoxydecyl)propyl] ester ("NXT silane" manufactured by general electronic silicons), octane sulphate S-[3-{(2-methyl-1,3-propane dialkoxy)ethoxy oxime alkyl}propyl] ester and octyl sulfate S-[3-{(2-methyl-1, 3-propane dialkoxy)methyl decyl} propyl] phenyl triethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, methyl triethoxy decane, A Tris-butoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, isobutyl trimethoxy decane, isobutyl triethoxy decane, n-octyltrimethoxy decane, n-octyl Triethoxy decane, vinyl trimethoxy decane, vinyl triethoxy fluorene , vinyl tris(methoxyethoxy)decane, phenyltrimethoxydecane, phenyltriethoxydecane, phenyltriethoxydecane, 3-methylpropenyloxypropyltrimethoxy Baseline, 3-methylpropenyloxypropyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyl Triethoxy decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyltriethoxydecane , (3-glycidoxypropyl)trimethoxydecane, (3-glycidoxypropyl)triethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane 1 of a group consisting of 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, 3-isocyanatepropyltrimethoxydecane and 3-isocyanatepropyltriethoxydecane a decane coupling agent or the like having a functional group such as an anthracene bonded to cerium oxide or a functional group such as an alkoxy decane, and particularly preferably a bis(3-triethoxydecylpropyl) tetrasulfide. ("Si-69" manufactured by Degussa Corporation), bis(3-triethoxydecylpropyl) disulfide ("Si-75" manufactured by Degussa Corporation), 3-octylthiopropyltriethoxylate Alkane ("NXT silane" manufactured by general electronic silicons). The addition time of the compounds is preferably carried out in the rubber at the same time as the cerium oxide, and the amount is preferably from 2 to 10% by weight, more preferably from 7 to 9% by weight, based on the cerium oxide. In the case of blending, the blending temperature is preferably from 80 to 200 ° C, more preferably from 110 to 180 ° C. Further, when cerium oxide is used as a filler, in addition to cerium oxide, a compound having a functional group such as an anthracene which may be bonded to cerium oxide or a functional group such as an alkoxy decane, ethanol or butyl may be preferably blended. Alcohol, octanol and other monohydric alcohols or ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, pentaerythritol, polyether polyol, etc., N-alkylamines, amines A liquid polybutadiene having a base acid, a molecular terminal modified by a carboxyl group or an amine.

As the aluminum hydroxide, aluminum hydroxide having a nitrogen adsorption specific surface area of 5 to 250 m ² /g and a DOP oil supply of 50 to 100 ml/100 g can be exemplified.

Examples of the sulfur component include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur. The sulfur component is preferably powder sulfur, and is preferably insoluble sulfur when used in a tire member having a large sulfur content such as a member for an endless belt.

As a vulcanization accelerator, a thiazole-based vulcanization accelerator and a sulfoximine-based vulcanization disclosed in pages 412 to 413 of the Rubber Industry Handbook <Fourth Edition> (issued by the Japan Rubber Association, January 20, 1994) Promoter, lanthanide vulcanization accelerator.

Examples of the vulcanization accelerator include N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), N-t-butyl-2-benzothiazolylsulfenamide (BBS), and N. N-Dicyclohexyl-2-benzothiazolylsulfenamide (DCBS), 2-mercaptobenzothiazole (MBT), dibenzothiazyl disulfide (MBTS) and diphenylphosphonium (DPG). In the case of using carbon black as a filler, N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), N-t-butyl-2-benzothiazolylsulfenamide is preferred. (BBS), N,N-dicyclohexyl-2-benzothiazolylsulfenamide (DCBS) or a combination of dibenzothiazyl disulfide (MBTS) and diphenylphosphonium (DPG) in combination with cerium oxide In the case of carbon black as a filler, N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), N-t-butyl-2-benzothiazolylsulfenamide (N-butylidene-2-benzothiazolyl) BBS), N,N-dicyclohexyl-2-benzothiazolylsulfenamide (DCBS) or a combination of dibenzothiazyl disulfide (MBTS) and diphenylphosphonium (DPG).

The ratio of sulfur to the vulcanization accelerator is not particularly limited, and is preferably in the range of sulfur/vulcanization accelerator = 2/1 to 1/2 by weight. Further, as a method for improving heat resistance in a rubber member mainly composed of natural rubber, a sulfur/vulcanization accelerator The EV vulcanization having a ratio of 1 or less is preferably used in the present invention in applications where heat resistance is particularly required.

The procedure for kneading each component includes a kneading rubber component and a filler (hereinafter sometimes referred to as "program 1"), and then the composition obtained in the kneading procedure 1 and the sulfur component (hereinafter sometimes referred to as The program for "Program 2"). Any of the kneaded product obtained in the procedure 1 and the kneaded product obtained in the procedure 2 is the rubber composition of the present invention.

Compound (I) can be formulated in Procedure 2, but is preferably formulated in Procedure 1 along with a filler or zinc oxide. The amount of the compound (I) used is preferably in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the rubber component. More preferably, it is in the range of 0.3 to 3 parts by weight. The mixing temperature in the case of the preparation in the procedure 1 is preferably from 80 to 200 ° C, more preferably from 110 to 180 ° C. The mixing temperature in the case of the preparation in the procedure 2 is preferably 50 to 100 °C.

The compound (I) may be preliminarily supported on a carrier and then compounded and kneaded. Examples of the carrier agent include the above-mentioned fillers and "inorganic fillers and reinforcing agents" disclosed in pages 510 to 513 of "Rubber Industry Handbook <Fourth Edition>" by the Japan Rubber Association. Preferred are carbon black, cerium oxide, calcined clay, and aluminum hydroxide. The amount of the carrier used is preferably in the range of 10 to 1000 parts by weight based on 100 parts by weight of the compound (I).

When the melting point of the compound (I) is high, in order to ensure sufficient dispersibility during kneading, it is preferred to pulverize the compound (I) into particles having a particle diameter of 100 μm or less.

For example, the compound (I) is mixed with carbon black, cerium oxide, calcined clay or aluminum hydroxide, and the resulting mixture is pulverized, whereby the compound (I) can be produced. Particles with a particle size of 100 μm or less.

It can also be blended with a viscoelastic property improving agent which is usually used in the rubber field. As a viscoelastic property improving agent, N,N'-bis(2-methyl-2-nitropropyl)-1,6-hexanediamine (Sumifine (registered trademark) 1162) manufactured by Sumitomo Chemical Co., Ltd. is mentioned. The dithiouracil compound disclosed in Japanese Laid-Open Patent Publication No. SHO63-23942, and the 5-nitroso-8-hydroxyquinoline (NQ-58) disclosed in Japanese Patent Laid-Open No. Hei 60-82406 Nitroquinoline compound, "TACKIROL (registered trademark) AP, V-200" manufactured by Takooka Chemical Co., Ltd., and "VULTAC 2, 3, 4, 5, 7, 710" manufactured by Penwalt Co., Ltd., etc., Japanese Patent Laid-Open No. 2009-138148 The alkylphenol sulphide condensate disclosed in the publication, and bis(3-triethoxydecylpropyl) tetrasulfide ("Si-69" manufactured by Degussa Co., Ltd.), bis(3-triethoxydecane) Propyl) disulfide ("Si-75" manufactured by Degussa), bis(3-diethoxymethyldecylpropyl) tetrasulfide, bis(3-diethoxymethyldecyl) Propyl) disulfide, octyl sulfate S-[3-(triethoxydecyl)propyl], octane sulfate S-[3-{(2-methyl-1,3-propanediodane) Oxy)ethoxy ethoxyalkyl}propyl] ester and octyl sulfate S-[3-{(2-methyl-1,3-propanediodane) Methyl decyl}propyl] phenyl phenyl triethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, methyl triethoxy decane, methyl tributoxy decane , ethyltrimethoxydecane, ethyltriethoxydecane, isobutyltrimethoxydecane, isobutyltriethoxydecane, n-octyltrimethoxydecane, n-octyltriethoxydecane, Vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris (methoxyethoxy) decane, phenyl trimethoxy decane, phenyl triethoxy decane, phenyl triethoxy methoxy Decane, 3-methacryloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyl Triethoxy decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyltriethoxydecane , (3-glycidoxypropyl)trimethoxydecane, (3-glycidoxypropyl)triethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane 2-(3,4-epoxycyclohexyl)ethyltriethoxyfluorene a decane coupling agent such as 3-isocyanatepropyltrimethoxydecane or 3-isocyanatepropyltriethoxydecane, 1,6-bis(N,N'-dibenzylthioaminemethanyl disulfide Hexane ("KA9188" manufactured by Bayer Corporation), 1,6-hexamethylenedithiosulfate disodium salt dihydrate, 1,3-bis[xampampinoiminemethyl)benzene (Flexsys) Manufactured "Perkalink 900"), 1-benzylidene-2-phenylindole, 1- or 3-hydroxy-N'-(1-methylethylidene)-2-naphthoquinone, Japan 1- or 3-hydroxy-N'-(1-methylpropylene)-2-naphthoquinone, 1- or 3-hydroxy-N'-(1, disclosed in Japanese Laid-Open Patent Publication No. 2004-91505 3-dimethylbutylene)-2-naphthoquinone and a carboxylic acid hydrazine derivative such as 1- or 3-hydroxy-N'-(2-furylmethylene)-2-naphthoquinone, 3-hydroxy-N'-(1,3-dimethylbutylidene)-2-naphthoguanidine, 3-hydroxy-N'-(1,3-di) disclosed in Japanese Patent Laid-Open Publication No. 2000-190704 Phenylethylene)-2-naphthoquinone and 3-hydroxy-N'-(1-methylethylidene)-2-naphthoquinone, disclosed in Japanese Patent Laid-Open No. 2006-328310 Base The oxadiazole compound, the pyrithione salt compound disclosed in Japanese Laid-Open Patent Publication No. 2009-40898, and the cobalt hydroxide compound disclosed in JP-A-2006-249361.

Among them, preferred is N,N'-bis(2-methyl-2-nitropropyl)-1,6-hexanediamine (live "Sumifine (registered trademark) 1162" manufactured by UF Chemical Co., Ltd., 5-nitroso-8-hydroxyquinoline (NQ-58), bis(3-triethoxydecylpropyl) tetrasulfide (Degussa) "Si-69" manufactured by the company, bis(3-triethoxydecylpropyl) disulfide ("Si-75" manufactured by Degussa), 1,6-double (N, N'-di Benzyl thioamine-methyl sulfonyl disulfide)-hexane ("KA9188" manufactured by Bayer Co., Ltd.), hexamethylene dithiosulfate disodium salt dihydrate, 1,3-bis (citrine) Methyl)benzene ("Perkalink 900" manufactured by Flexsys) and "Alkoxide ‧ sulfur chloride condensate such as "TACKIROL (registered trademark) AP, V-200" manufactured by Takaoka Chemical Co., Ltd.

When formulating zinc oxide, it is formulated in the first step, and in the case of formulating the vulcanization accelerator, it is preferably formulated in the procedure 2.

It can also be blended in a blending agent commonly used in the rubber field. Examples of the preparation agent include anti-aging agents such as "ANTIGENE (registered trademark) 6C" manufactured by Sumitomo Chemical Co., Ltd.; oils; fatty acids such as stearic acid; and coumarone resin (coumarone resin) of Nippon Steel Chemical Co., Ltd. ) NG4 (softening point 81 ~ 100 ° C), Kobe Oil Chemical Industry (stock) process resin AC5 (softening point 75 ° C) and other coumarone ‧ 茚 resin; terpene resin, terpene ‧ phenol resin, aromatic modification Terpene resin such as terpene resin; rosin derivative such as Mitsubishi Gas Chemical Co., Ltd. "Nikanol (registered trademark) A70" (softening point 70 to 90 ° C); hydrogenated rosin derivative; novolac type alkylphenol resin; A phenolic phenolic resin; a C5 petroleum resin; a liquid polybutadiene. These formulations can be formulated in either of Program 1 and Program 2.

Examples of the oil include treated oils, vegetable oils, and the like. Examples of the treatment oil include paraffin-based treatment oil, naphthenic treatment oil, and aromatic treatment oil. For example, an aromatic hydrocarbon oil ("NC-140" manufactured by Cosmo Oil Co., Ltd.) and a processing oil ("Diana Process PS32" manufactured by Idemitsu Kosan Co., Ltd.) can be cited.

As an anti-aging agent, those disclosed in the "Rubber Industry Handbook <Fourth Edition>" edited by the Japan Rubber Association can be cited on pages 436 to 443. Among them, N-phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine (6PPD), reaction product of aniline with acetone (TMDQ), poly(2, 2, 4) can be preferably used. -Trimethyl-1,2-)dihydroquinoline ("Antioxidant FR" manufactured by Matsubara Industries, Ltd.), synthetic wax (paraffin wax, etc.), plant wax.

Examples of the wax include "SUNNOC (registered trademark) WAX" manufactured by OUCHI SHINKO CHEMICAL INDUSTRIAL, and "OZOACE-0355" manufactured by Nippon Fine Chemicals Co., Ltd. (NIPPON SEIRO).

It can also be formulated into the disulfide commonly used in the rubber field. Mixing with a vulcanizing agent such as a porphyrin. These are preferably formulated in the program 2.

Further, a peptizing agent or a retarding agent may be blended and kneaded, and if necessary, various kinds of rubber chemicals or softeners may be blended as needed.

As the retarding agent, phthalic anhydride, benzoic acid, salicylic acid, N-nitrosodiphenylamine, N-(cyclohexylthio)-phthalimide (CTP), and sulfonium sulfonate can be exemplified. An amine derivative, diphenylurea, bis(tridecyl)pentaerythritol-diphosphite, etc., preferably N-(cyclohexylthio)-phthalimide (CTP).

The retarding agent can be compounded in the procedure 1, but it is preferred to mix and mix in the procedure 2.

The amount of the retardation agent used is preferably in the range of 0.01 to 1 part by weight based on 100 parts by weight of the rubber component. More preferably, it is 0.05 to 0.5 parts by weight.

The temperature condition in the procedure 1 is preferably 200 ° C or less. More preferably 120~180 °C. The temperature condition in the procedure 2 is preferably 60 to 120 °C.

The vulcanized rubber of the present invention is obtained by heat-treating the rubber composition obtained in the procedure 2.

The temperature condition in the heat treatment is preferably from 120 to 180 °C. The heat treatment is usually carried out under normal pressure or under pressure.

The vulcanized rubber of the present invention contains a vulcanized rubber obtained by subjecting the rubber composition processed into a specific state to heat treatment.

Here, "the rubber composition processed into a specific state", in the field of tires, "a rubber composition coated on a wire rope", "a rubber composition coated on a carcass fiber rope", and " A rubber composition processed into a shape of a member for a tread" or the like. Further, each member such as an endless belt, a carcass, an inner liner, a sidewall, a tread (tread crown or a tread base) obtained by heat treatment, usually together with other members, is generally carried out in the field of tires. The method is further molded into the shape of a tire, that is, the rubber composition is incorporated into a tire, and heat treatment is performed in a state in which the rubber composition contains the green tire. The heat treatment is usually carried out under pressure.

In a preferred rubber composition suitable for a tread member of a truck or a bus, a light truck, or a large tire for construction, as the rubber component, it is preferred to use natural rubber alone or a natural rubber as a main component and blend SBR and/or Or BR. Further, as the filler, it is preferred to use carbon black alone or ruthenium dioxide as a main component and blend carbon black. Further, it is preferred to use N, N'-double (2-A Benzyl-2-nitropropyl)-1,6-hexanediamine ("Sumifine (registered trademark) 1162" manufactured by Sumitomo Chemical Co., Ltd.), 5-nitroso-8-hydroxyquinoline (NQ-58), double (3-triethoxydecylpropyl)tetrasulfide (Si-69), bis(3-triethoxydecylpropyl)disulfide (Si-75), 1,6-double (N , N'-dibenzylthioamine methyl sulfonyl disulfide)-hexane ("KA9188" manufactured by Bayer Corporation), hexamethylene dithiosulfate disodium salt dihydrate, 1,3-double ( Viscoelastic modifiers such as sulphate and sulphide condensate such as "TACKIROL (registered trademark) AP, V-200" manufactured by Takaoka Chemical Co., Ltd. ("Perkalink 900" manufactured by Flexsys) .

In a preferred rubber composition suitable for a tread member of a passenger car tire, as the rubber component, it is preferred to use a solution polymerization SBR modified with a ruthenium compound or a solution polymerization SBR having a terminal modification as a main component. And blending at least one rubber selected from the group consisting of unmodified solution polymerization SBR, emulsion polymerization SBR, natural rubber, and BR. Further, as the filler, carbon dioxide is preferably blended with cerium oxide as a main component. Further, it is preferred to use N,N'-bis(2-methyl-2-nitropropyl)-1,6-hexanediamine ("Sumifine (registered trademark) 1162" manufactured by Sumitomo Chemical Co., Ltd.), 5- Nitroso-8-hydroxyquinoline (NQ-58), bis(3-triethoxydecylpropyl)tetrasulfide (Si-69), bis(3-triethoxydecylpropyl) Disulfide (Si-75), 1,6-bis(N,N'-dibenzylthiocarbamoyldisulfide)-hexane ("KA9188" manufactured by Bayer Corporation), hexamethylene double Thiosulfate disodium salt dihydrate, 1,3-bis(citraconazole iminomethyl)benzene ("Perkalink 900" manufactured by Flexsys), "TACKIROL (registered trademark) AP, manufactured by Takooka Chemical Co., Ltd., V- Viscoelastic modifier such as 200" alkanophene ‧ sulfur sulfide condensate.

In the preferred rubber composition of the sidewall member, as the rubber component, it is preferably a BR-based component, and blended with at least one selected from the group consisting of unmodified solution polymerization SBR, emulsion polymerization SBR, and natural rubber. a rubber. Further, as the filler, it is preferred to use carbon black alone or carbon black as a main component and to incorporate cerium oxide. Further, it is preferred to use N,N'-bis(2-methyl-2-nitropropyl)-1,6-hexanediamine ("Sumifine (registered trademark) 1162" manufactured by Sumitomo Chemical Co., Ltd.), 5- Nitroso-8-hydroxyquinoline (NQ-58), bis(3-triethoxydecylpropyl)tetrasulfide (Si-69), bis(3-triethoxydecylpropyl) Disulfide (Si-75), 1,6-bis(N,N'-dibenzylthiocarbamoyldisulfide)-hexane ("KA9188" manufactured by Bayer Corporation), hexamethylene double Thiosulfate disodium salt dihydrate, 1,3-bis(citraconazole iminomethyl)benzene ("Perkalink 900" manufactured by Flexsys), "TACKIROL (registered trademark) AP, manufactured by Takooka Chemical Co., Ltd., V- Viscoelastic modifier such as 200" alkanophene ‧ sulfur sulfide condensate.

In the preferred rubber composition of the carcass and the endless belt member, as the rubber component, it is preferred to use natural rubber alone or a natural rubber as a main component and blend BR. Further, as the filler, it is preferred to use carbon black alone or carbon black as a main component and to incorporate cerium oxide. Further, it is preferred to use N,N'-bis(2-methyl-2-nitropropyl)-1,6-hexanediamine ("Sumifine (registered trademark) 1162" manufactured by Sumitomo Chemical Co., Ltd.), 5- Nitroso-8-hydroxyquinoline (NQ-58), bis(3-triethoxydecylpropyl)tetrasulfide (Si-69), bis(3-triethoxydecylpropyl) Disulfide (Si-75), 1,6-bis(N,N'-dibenzylthiocarbamoyldisulfide)-hexane ("KA9188" manufactured by Bayer Corporation), hexamethylene double Thiosulfate disodium salt dihydrate, 1,3-bis(citrine iminomethyl) Benzene ("Perkalink 900" manufactured by Flexsys) and a viscoelastic modifier such as alkane phenol sulfur chloride condensate such as "TACKIROL (registered trademark) AP, V-200" manufactured by Takooka Chemical Co., Ltd.

The rubber composition of the present invention before the vulcanization treatment is extruded to a member for a tread, processed, and attached to a tire molding machine by a usual method to form a green tire, and the green tire is subjected to a vulcanizer. Heating and pressurizing, thereby obtaining a tire.

Examples of the tire include a pneumatic tire, a solid tire, and the like.

The fuel efficiency of the car equipped with the tire thus obtained is improved, and fuel consumption can be achieved.

When the compound (I) is added to the rubber composition, the viscoelastic property of the vulcanized rubber obtained by vulcanizing it can be improved. Moreover, vulcanized rubber can be used not only for tire applications, but also for anti-vibration rubber applications, rubber belt applications, damper applications, and vibration-isolating rubber applications. Examples of the anti-vibration rubber include an anti-vibration rubber for automobiles such as an engine mount, a strut mount, a bush, and an exhaust hanger. The anti-vibration rubber is usually obtained by processing the kneaded material into a shape of the anti-vibration rubber and then supplying it to the heat treatment. Examples of the rubber belt application include a transmission belt, a conveyor belt, and a V-belt.

The compound (I) also has anti-aging properties and can be used as an anti-aging agent for rubber. When the compound (I) is added as a rubber anti-aging agent to the rubber composition, the compound (I) and the anti-aging agent generally used in the rubber field can be used in combination.

Vulcanized rubber obtained from rubber composition containing compound (I), anti-reversion Excellent performance.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, test examples, and production examples.

Production Example (1-1): Production of (Z)-3-(4-aminophenylaminecarbamyl)acrylic acid

Under a nitrogen atmosphere, 25.17 g (0.233 mol) of 1,4-phenylenediamine and 230 ml of tetrahydrofuran were placed in a reaction vessel. After a solution of 22.84 g (0.233 mol) of maleic anhydride dissolved in 50 ml of tetrahydrofuran was added dropwise thereto under ice cooling for about 1 hour, the mixture was stirred at room temperature overnight. After completion of the reaction, the precipitated crystals were collected by filtration, washed twice with 40 ml of tetrahydrofuran, and dried at 40 ° C for 5 hours to obtain a crude (Z)-3-(4-aminophenylaminecarbamyl) as an orange powder. ) Acrylic 46.92 g. 250 ml of methanol was added to 46.92 g of crude (Z)-3-(4-aminophenylaminocarbamimidyl)acrylic acid, and the mixture was stirred at 50 ° C for 1 hour, cooled, filtered and washed twice with methanol 20 ml. . The obtained crystals were dried to obtain 42.67 g of (Z)-3-(4-aminophenylaminecarbamyl)acrylic acid as a yellow-orange powder. The yield was 88.8%.

Example (1-1): Production of N,N'-bis(4-aminophenyl)cis-decylamine

In a reaction vessel, 13.85 g (67.2 mmol) of (Z)-3-(4-aminophenylaminecarbamimidyl)acrylic acid synthesized in Production Example (1-1) in a reaction vessel, and put 1, 4-phenylenediamine 6.90 g (67.2 mmol), dimethylaminopyridine 0.82 g and two Methylformamide 130 ml. 1-Ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride 12.88 g (67.2 mmol) was added thereto under ice-cooling, and stirred at room temperature overnight. After completion of the reaction, 560 ml of water was added, and the mixture was extracted four times with 500 ml of ethyl acetate. The organic layer was combined, washed with brine (500 ml), dried over sodium sulfate, and evaporated. 50 ml of chloroform was added thereto, and the mixture was concentrated under reduced pressure three times, and then, to the obtained residue, 80 ml of methanol was added, and the precipitated solid was separated by filtration. The filtrate was concentrated under reduced pressure, and then applied to a silica gel column chromatography to obtain 5.30 g of N,N'-bis(4-aminophenyl)-s-succinamine as a dark red solid. The yield was 26.6%.

¹ H-NMR (300.13 MHz, DMSO-d6) δ _ppm : 10.75 (2H, s), 7.30 (4H, d, J = 8.7 Hz), 6.52 (4H, d, J = 8.7 Hz), 6.29 (2H, s), 4.95 (4H, s)

Example (1-2): Production of rubber composition

<Program 1>

Using a Banbury mixer (600 ml of labo plastomill manufactured by Toyo Seiki), blending and blending 100 parts by weight of natural rubber (RSS #1) and HAF (manufactured by Asahi Carbon Co., Ltd., trade name "旭#70"), 45 parts by weight, 3 parts by weight of stearic acid, 5 parts by weight of zinc oxide, and an anti-aging agent (N-phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine: trade name "ANTIGENE (registered trademark) 6C" 1 part by weight of 1 part by weight of N,N'-bis(4-aminophenyl)butyl decylamine obtained in the example (1-1), and a rubber composition was obtained. This procedure 1 is carried out by kneading the number of revolutions of a mixer of 50 rpm 5 minutes after the input of various components, at this time. The rubber temperature is 160~170 °C.

<Program 2>

The rubber composition obtained by the procedure 1 and the vulcanization accelerator (N-cyclohexyl-2-benzothiazolylsulfenamide) 1 part by weight and sulfur are compounded in an open roller machine at a temperature of 60 to 80 ° C. 2 parts by weight, a rubber composition was obtained.

Example (1-3): Manufacture of vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (1-2) was subjected to a vulcanization treatment at 145 ° C to obtain a vulcanized rubber.

Reference example (1-1)

A rubber composition was obtained in the same manner as in Example (1-2) except that N,N'-bis(4-aminophenyl)-cis-decylamine was not used in Example (1-2).

Reference example (1-2)

The rubber composition obtained in the procedure 2 of Reference Example (1-1) was subjected to a vulcanization treatment at 145 ° C to obtain a vulcanized rubber.

The coking time and viscoelastic properties were measured as follows.

(1) Coking time

The measurement was carried out at 125 ° C according to JIS-K6300-1.

The larger the value of the coking time, the more difficult it is to cause rubber scorching, and the processing stability is good.

Test example (1-1)

The rubber composition obtained in Reference Example (1-1) was used as a control, and the coking time of the rubber composition obtained in Reference Example (1-1) was set to 100, and the rubber obtained in Example (1-2) was used. For the composition, the relative value of the coking time is expressed as an index and the result is 89.

(2) Viscoelastic properties

The measurement was carried out using a viscoelastic analyzer manufactured by Ushimashima Co., Ltd.

Conditions: Temperature -5 ° C ~ 80 ° C (heating rate: 2 ° C / min) initial strain 10%, dynamic strain 2.5%, frequency 10 Hz

The vulcanized rubber obtained in Reference Example (1-2) was used as a control, and for the vulcanized rubber obtained in Example (1-3), the viscoelastic property of the vulcanized rubber obtained in Reference Example (1-2) was measured (at 60 ° C) The rate of decrease (%) of tan δ) results in a rate of decrease of 33%.

Example (1-4)

The steel cord which was subjected to the brassing treatment was coated with the rubber composition obtained in the procedure 2 of Example (1-2) to obtain an endless belt. Using the obtained endless belt, a green tire was molded according to a usual production method, and the obtained green tire was heated and pressurized in a vulcanizer, whereby a vulcanized tire was obtained.

Example (1-5)

The rubber composition obtained in the procedure 2 of Example (1-2) was subjected to extrusion processing to obtain a member for a tread. Using the obtained tread member, a green tire is molded according to a usual production method, and the obtained green tire is heated and pressurized in a vulcanizer to obtain a vulcanized tire.

Example (1-6)

The rubber composition obtained in the procedure 2 of the embodiment (1-2) is subjected to extrusion processing to prepare a rubber composition having a shape corresponding to the shape of the carcass, which is attached to the top of the carcass fiber rope of polyester. This obtains the carcass. Using the obtained carcass, according to the usual manufacturing method, the raw tire is formed, and the obtained raw tire is The vulcanizer is heated and pressurized to obtain a vulcanized tire.

Example (1-7)

Except in the procedure 2 of the embodiment (1-2), and further mixing 0.2 parts by weight of N-(cyclohexylthio)-phthaliminimide (CTP), and in the same manner as in the example (1-2) In the same manner, a rubber composition was obtained.

Example (1-8)

The rubber composition obtained in the procedure 2 of Example (1-7) was subjected to a vulcanization treatment at 145 ° C to obtain a vulcanized rubber.

Example (1-9): Production of rubber composition

<Program 1>

Mixing styrene with a Banbury mixer (600 ml of labo plastomill made by Toyo Seiki). Butadiene copolymer rubber SBR #1502 (manufactured by Sumitomo Chemical Co., Ltd.) 100 parts by weight, ISAF-HM (manufactured by Asahi Carbon Co., Ltd., trade name "旭#80"), 45 parts by weight, stearic acid 2 parts by weight, zinc oxide, 3 parts by weight 1 part by weight of N,N'-bis(4-aminophenyl)cisantamine, anti-aging agent (N-phenyl-N'-1,3-dimethylbutyl-p-phenylene) Amine (6PPD): The product name "ANTIGENE (registered trademark) 6C, manufactured by Sumitomo Chemical Co., Ltd.) was used in an amount of 2 parts by weight and wax ("OZOACE-0355" manufactured by Nippon Seiko Co., Ltd.) to obtain a rubber composition. This step was carried out by kneading at a number of revolutions of a mixer of 50 rpm 5 minutes after the components were charged, and the rubber temperature at this time was 160 to 175 °C.

<Program 2>

The rubber composition obtained by the procedure 1 and the vulcanization accelerator N-cyclohexyl-2-benzothiazolyl are compounded in an open roller machine at a temperature of 60 to 80 ° C. 3 parts by weight of sulfoximine (CBS) and 2 parts by weight of sulfur were used to obtain a rubber composition.

Example (1-10): Manufacture of vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (1-9) was heat-treated at 145 ° C, whereby a vulcanized rubber was obtained. The obtained vulcanized rubber is preferably used as a tread cap.

Example (1-11): Production of rubber composition

<Program 1>

Mixing styrene with a Banbury mixer (600 ml of labo plastomill made by Toyo Seiki). 100 parts by weight of butadiene copolymer rubber SBR #1502 (manufactured by Sumitomo Chemical Co., Ltd.), 35 parts by weight of ISAF-HM (manufactured by Asahi Carbon Co., Ltd., trade name "旭#80"), 2 parts by weight of stearic acid, and 3 parts by weight of zinc oxide 1 part by weight of N,N'-bis(4-aminophenyl)cisantamine, anti-aging agent (N-phenyl-N'-1,3-dimethylbutyl-p-phenylene) Amine (6PPD): The product name "ANTIGENE (registered trademark) 6C, manufactured by Sumitomo Chemical Co., Ltd.) was used in an amount of 2 parts by weight and wax ("OZOACE-0355" manufactured by Nippon Seiko Co., Ltd.) to obtain a rubber composition. This step was carried out by kneading at a number of revolutions of a mixer of 50 rpm 5 minutes after the components were charged, and the rubber temperature at this time was 160 to 175 °C.

<Program 2>

2 parts by weight of the rubber composition obtained by the procedure 1 and the vulcanization accelerator N-cyclohexyl-2-benzothiazolylsulfenamide (CBS) were mixed and kneaded in an open roller machine at a temperature of 60 to 80 ° C. 0.5 parts by weight of a vulcanization accelerator diphenyl sulfonium (DPG), 0.8 parts by weight of a vulcanization accelerator dibenzothiazyl disulfide (MBTS), and 1 part by weight of sulfur were used to obtain a rubber composition.

Example (1-12): For the manufacture of a tread base for a vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (1-11) was subjected to heat treatment at 145 ° C, whereby a vulcanized rubber was obtained. The obtained vulcanized rubber is preferably used as the base of the tread.

Example (1-13): Production of Rubber Composition

<Program 1>

Using a Banbury mixer (600 ml of labo plastomill manufactured by Toyo Seiki), blending and blending 100 parts by weight of natural rubber (RSS #1) and HAF (manufactured by Asahi Carbon Co., Ltd., trade name "旭#70"), 45 parts by weight, 3 parts by weight of stearic acid, 5 parts by weight of zinc oxide, 1 part by weight of N,N'-bis(4-aminophenyl)succinimide, and aqueous cerium oxide (manufactured by TOSOH SILICA Co., Ltd.) 10 parts by weight of Nipsil (registered trademark) AQ, 2 parts by weight of anti-aging agent FR ("Antioxidant FR" manufactured by Matsubara Sangyo Co., Ltd.), 2 parts by weight of resorcin and 2 parts by weight of cobalt naphthenate, and a rubber composition was obtained. This step was carried out by kneading at a number of revolutions of a mixer of 50 rpm 5 minutes after the components were charged, and the rubber temperature at this time was 160 to 175 °C.

<Program 2>

The rubber composition obtained by the procedure 1 and the vulcanization accelerator N,N-dicyclohexyl-2-benzothiazolylsulfenamide (DCBS) 1 were mixed in an open roller machine at a temperature of 60 to 80 ° C. A rubber composition was obtained in an amount of 3 parts by weight based on parts by weight, sulfur 6 parts by weight, and methoxymethylol melamine resin ("Sumikanol 507AP" manufactured by Sumitomo Chemical Co., Ltd.).

Example (1-14): Manufacture of vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (1-13) was subjected to 145 ° C Heat treatment is performed, whereby a vulcanized rubber is obtained. The obtained vulcanized rubber is preferably used as an endless belt.

Example (1-15): Production of Rubber Composition

<Program 1>

Using a Banbury mixer (600 ml of labo plastomill manufactured by Toyo Seiki), 100 parts by weight of a halogenated butyl rubber ("Br-IIR2255" manufactured by Exxon Mobil Co., Ltd.), 60 parts by weight of GPF, and 1 weight of stearic acid were blended. a part by weight, 3 parts by weight of zinc oxide, 1 part by weight of N,N'-bis(4-aminophenyl)butylammonium, and 10 parts by weight of paraffin oil ("Diana Process Oil" manufactured by Idemitsu Kosan Co., Ltd.). A rubber composition was obtained. This step was carried out by kneading at a number of revolutions of a mixer of 50 rpm 5 minutes after the components were charged, and the rubber temperature at this time was 160 to 175 °C.

<Program 2>

The rubber composition obtained by the procedure 1, the anti-aging agent (condensation of aniline and acetone (TMDQ)), 1 part by weight, and the vulcanization accelerator disulfide diphenyl sulfide are blended in an open roller machine at a temperature of 60 to 80 ° C. 1 part by weight of thiazole (MBTS) and 2 parts by weight of sulfur were used to obtain a rubber composition.

Example (1-16): Manufacture of vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (1-15) was subjected to heat treatment at 145 ° C, whereby a vulcanized rubber was obtained. The obtained vulcanized rubber is preferably used as an inner liner.

Example (1-17): Production of rubber composition

<Program 1>

Use a Banbury mixer (a 600 ml labo made by Toyo Seiki) Plastomill), blending 40 parts by weight of natural rubber (RSS #3), 60 parts of polybutadiene rubber ("BR150B" manufactured by Ube Industries, Ltd.), 50 parts by weight of FEF, 2.5 parts by weight of stearic acid, and zinc oxide 3 Parts by weight, N,N'-bis(4-aminophenyl)butylammonium, 1 part by weight, anti-aging agent (N-phenyl-N'-1,3-dimethylbutyl-p-benzene) Diamine (6PPD): trade name "ANTIGENE (registered trademark) 6C" manufactured by Sumitomo Chemical Co., Ltd.) 2 parts by weight, 10 parts by weight of aromatic oil ("NC-140" manufactured by Cosmo Oil Co., Ltd.) and wax 2 parts by weight of "SUNNOC (registered trademark) WAX" manufactured by Chemical Industry Co., Ltd.), and a rubber composition was obtained. This step was carried out by kneading at a number of revolutions of a mixer of 50 rpm 5 minutes after the components were charged, and the rubber temperature at this time was 160 to 175 °C.

<Program 2>

The rubber composition obtained by the procedure 1 and the vulcanization accelerator N-t-butyl-2-benzothiazolylsulfenamide (BBS) 0.75 weight are compounded in an open roller machine at a temperature of 60 to 80 ° C. Parts and sulfur were 1.5 parts by weight to obtain a rubber composition.

Example (1-18): Manufacture of vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (1-17) was subjected to heat treatment at 145 ° C, whereby a vulcanized rubber was obtained. The obtained vulcanized rubber is preferably used as a sidewall.

Example (1-19): Production of rubber composition

<Program 1>

Using a Banbury mixer (600 ml of labo plastomill manufactured by Toyo Seiki), blending and blending natural rubber (TSR20) with 70 parts by weight, benzene Alkene. 30 parts by weight of butadiene copolymer rubber SBR #1502 (manufactured by Sumitomo Chemical Co., Ltd.), 60 parts by weight of N339 (manufactured by Mitsubishi Chemical Corporation), 2 parts by weight of stearic acid, 5 parts by weight of zinc oxide, and treated oil (manufactured by Idemitsu Kosan Co., Ltd.) "Diana Process PS32") 7 parts by weight and 1 part by weight of N,N'-bis(4-aminophenyl)butylammoniumamine were used to obtain a rubber composition. This step was carried out by kneading at a number of revolutions of a mixer of 50 rpm 5 minutes after the components were charged, and the rubber temperature at this time was 160 to 175 °C.

<Program 2>

The rubber composition obtained by the procedure 1 and the vulcanization accelerator N-t-butyl-2-benzothiazolylsulfenamide (BBS) 1 weight are blended in an open roller machine at a temperature of 60 to 80 ° C. Parts, sulfur 3 parts by weight, anti-aging agent (N-phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine (6PPD): trade name "ANTIGENE (registered trademark) 6C" Sumitomo Chemical Co., Ltd. 1 part by weight and an anti-aging agent (condensation of aniline and acetone (TMDQ)) (1 part by weight) to obtain a rubber composition.

Example (1-20): Manufacture of vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (1-19) was subjected to heat treatment at 145 ° C, whereby a vulcanized rubber was obtained. The obtained vulcanized rubber is preferably used as a carcass.

Example (1-21): Production of Rubber Composition

<Program 1>

Mixing styrene with a Banbury mixer (600 ml of labo plastomill made by Toyo Seiki). Butadiene copolymer rubber SBR #1500 (manufactured by JSR Corporation) 100 parts by weight, cerium oxide (trade name: "Ultrasil (registered trademark) VN3-G", manufactured by Degussa Co., Ltd.) 78.4 parts by weight, carbon black (trade name "N-339" manufactured by Mitsubishi Chemical Corporation), 6.4 parts by weight, decane coupling agent (bis(3-triethoxydecyl) Base) tetrasulfide: 4.6 parts by weight, processing oil (trade name "NC-140" Cosmo Oil Co., Ltd.), 47.6 parts by weight, anti-aging agent (N-phenyl-N, manufactured by Degussa Co., Ltd.) '-1,3-Dimethylbutyl-p-phenylenediamine (6PPD): trade name "ANTIGENE (registered trademark) 6C" manufactured by Sumitomo Chemical Co., Ltd.) 1.5 parts by weight, zinc oxide 2 parts by weight, stearic acid 2 parts by weight and 3 parts by weight of N,N'-bis(4-aminophenyl)butylammoniumamine were used to obtain a rubber composition. This step is carried out by operating in a temperature range of 70 ° C to 120 ° C for 5 minutes after the components are put into operation, and mixing is performed at a rotation number of the mixer of 80 rpm, followed by 5 minutes, and the number of rotations of the mixer at 100 rpm is performed. Implemented by mixing.

<Program 2>

The rubber composition obtained by the procedure 1 and the vulcanization accelerator N-cyclohexyl-2-benzothiazolylsulfenamide (CBS) are blended in an open roller at a temperature of 30 to 80 ° C, and 1 part by weight, 1 part by weight of a vulcanization accelerator (DPG), 1.5 parts by weight of a wax (trade name "SUNNOC (registered trademark) N" manufactured by Ouchi Shinko Chemical Co., Ltd.), and 1.4 parts by weight of sulfur were obtained to obtain a rubber composition.

Example (1-22): Manufacture of vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (1-21) was subjected to heat treatment at 160 ° C, whereby a vulcanized rubber was obtained. The obtained vulcanized rubber is preferably used as a tread cap.

Example (1-23): Production of rubber composition

Use solution polymerization SBR in addition to Example (1-21) ("Asaprene" Trademark) "made by Asahi Kasei Chemical Co., Ltd." instead of styrene. A rubber composition was obtained in the same manner as in Example (1-21) except for butadiene copolymer rubber SBR #1500 (manufactured by JSR Corporation).

Example (1-24): Manufacture of vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (1-23) was subjected to heat treatment at 160 ° C, whereby a vulcanized rubber was obtained. The obtained vulcanized rubber is preferably used as a tread cap.

Example (1-25): Production of rubber composition

In the example (1-21), SBR #1712 (manufactured by JSR Corporation) was used instead of styrene ‧ butadiene copolymer rubber SBR #1500 (manufactured by JSR Corporation), and the amount of the treatment oil was changed to 21 parts by weight. The rubber composition was obtained in the same manner as in Example (1-21) except that the time of zinc oxide was changed to the procedure 2.

Example (1-26): Manufacture of vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (1-25) was subjected to heat treatment at 160 ° C, whereby a vulcanized rubber was obtained. The obtained vulcanized rubber is preferably used as a tread cap.

Example (1-27): Production of rubber composition

<Program 1>

Using a Banbury mixer (600 ml of labo plastomill manufactured by Toyo Seiki), blending and blending 100 parts by weight of natural rubber (RSS #1) and HAF (manufactured by Asahi Carbon Co., Ltd., trade name "旭#70"), 45 parts by weight, 3 parts by weight of stearic acid, 5 parts by weight of zinc oxide, and 1 part by weight of N,N'-bis(4-aminophenyl)cisantamine obtained in Example (1-1), a rubber combination was obtained. Things. This procedure 1 was carried out by kneading at a number of revolutions of a mixer of 50 rpm 5 minutes after the introduction of various components, and the rubber temperature at this time was 160 to 170 °C.

<Program 2>

The rubber composition obtained by the procedure 1 and the vulcanization accelerator (N-cyclohexyl-2-benzothiazolylsulfenamide) 1 part by weight and sulfur are compounded in an open roller machine at a temperature of 60 to 80 ° C. 2 parts by weight, a rubber composition was obtained.

Example (1-28): Manufacture of vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (1-27) was subjected to heat treatment at 160 ° C, whereby a vulcanized rubber was obtained. The obtained vulcanized rubber has improved viscoelastic properties and is excellent in anti-aging properties.

Example (1-29): Production of rubber composition

<Program 1>

Using a Banbury mixer (600 ml of labo plastomill manufactured by Toyo Seiki), blending and blending 100 parts by weight of natural rubber (RSS #1) and HAF (manufactured by Asahi Carbon Co., Ltd., trade name "旭#70"), 50 parts by weight, 3 parts by weight of stearic acid, 5 parts by weight of zinc oxide, and an anti-aging agent (N-phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine (6PPD): trade name "ANTIGENE (registered trademark ) 6 parts by weight of 6C Sumitomo Chemical Co., Ltd. to obtain a rubber composition. This procedure 1 was carried out by kneading at a number of revolutions of a mixer of 50 rpm 5 minutes after the introduction of various components, and the rubber temperature at this time was 160 to 170 °C.

<Program 2>

In the open drum machine at 60~80 °C, mixing and mixing by program 1 The obtained rubber composition, 1 part by weight of N,N'-bis(4-aminophenyl)cisantamine obtained in Example (1-1), and a vulcanization accelerator (dibenzothiazole disulfide) 1 part by weight and 1 part by weight of sulfur, a rubber composition was obtained.

Example (1-30): Manufacture of vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (1-29) was subjected to heat treatment at 170 ° C, whereby a vulcanized rubber was obtained. The obtained vulcanized rubber is excellent in anti-reversion property.

Production Example (2-1): Production of 4-aminophenylaminocarbamic acid tert-butyl ester

Under a nitrogen atmosphere, 32.51 g (0.3 mol) of 1,4-phenylenediamine, 300 ml of tetrahydrofuran and 100 ml of dimethylformamide were placed in a reaction vessel. Further, after adding a solution of 15.2 g (0.11 mol) of potassium carbonate in 50 ml of water, 21.83 g (0.1 mol) of dibutyl butyl dicarbonate was dissolved in 40 ml of tetrahydrofuran by dropwise addition under water cooling for about 40 minutes. Solution. Thereafter, the reaction mixture obtained by reacting at room temperature for 4 hours was added to 400 ml of cold water, and extracted twice with chloroform (500 ml, 400 ml). The organic layer was washed with brine and dried over sodium sulfate. The filtrate separated by filtration of sodium sulfate was concentrated under reduced pressure, and the obtained dark-purified solid was purified by silica gel column chromatography to afford 19.84 g of 4-aminophenylaminocarbamic acid tributyl ester as a pale yellow solid. Yield 95.3%

Production Example (2-2): Production of N,N'-bis(4-aminophenyl)fubutenamine

Under a nitrogen atmosphere, 25.80 g (168.7 mmol) of fumaric acid chloride and 1000 ml of tetrahydrofuran were placed in a reaction vessel, and the mixture was added dropwise in an ice bath for about 30 minutes to be synthesized in the production example (2-1). A solution of 17.58 g (84.4 mmol) of aminobutylphenylcarbamic acid tert-butyl ester and 11.8 ml of triethylamine dissolved in 200 ml of tetrahydrofuran. After reacting for 15 minutes at the same temperature, 255 ml of a 1 N aqueous solution of sodium hydroxide was added dropwise, and 200 ml of water was added to the residue obtained by distillation under reduced pressure. 1000 ml of water was added to the obtained solid, and the mixture was stirred overnight at room temperature, and the solid was collected by filtration and washed twice with 150 ml of water and dried. 480 ml of tetrahydrofuran was added to the obtained solid at room temperature, and the mixture was stirred overnight and then filtered. 210 ml of tetrahydrofuran was added to the obtained solid, and the mixture was stirred at 40 ° C for 2 hours, filtered, and dried to obtain N,N'-bis(4-tert-butoxycarbonylaminophenyl)-butene as a gray-green solid. Diammonium 13.18 g. The yield is 62.9%

65 ml of trifluoroacetic acid was placed in the reaction vessel, and N,N'-bis(4-tert-butoxycarbonylaminophenyl)-butenediamine 13.0 was added in portions over 30 minutes under ice cooling. g (26.2 mmol), stirred at room temperature overnight. After completion of the reaction, the precipitated solid was collected by filtration, washed twice with ethyl acetate 10 ml, and dried to give a white solid. 70 ml of water was added to the obtained solid, aqueous ammonia was added to the suspension, and the pH was adjusted to 8, and the solid was collected by filtration, washed with water and dried to obtain N,N'-bis(4-aminobenzene) as a yellow solid. Base) fumaride 6.13 g. Yield 79.0%

Production Example (2-3): Production of 3-Aminopropylaminocarbamic acid tert-butyl ester

Under nitrogen atmosphere, 44.5 g (600 mmol) of 1,3-diaminopropane and 1500 ml of chloroform were placed in a reaction vessel, and 65.4 g of dibutyl butyl dicarbonate was added dropwise thereto under ice cooling for 2 hours. 300 mmol) was dissolved in 600 ml of chloroform and returned to room temperature and stirred overnight. After the completion of the reaction, the precipitated solid was separated by filtration, and the filtrate was concentrated under reduced pressure. The obtained crude material was purified by silica gel column chromatography to obtain 3-aminopropyl propyl carbamic acid as a pale yellow liquid. 35.5 g. The yield was 67.9%.

Production Example (2-4): Production of N,N'-bis(3-aminopropyl)-butenyldiamine

Under the nitrogen atmosphere, 5.4 g (46.6 mmol) of fumaric acid, 16.2 g (93.2 mmol) of 3-aminopropylaminocarbamic acid, and 0.57 g of dimethylaminopyridine were placed in the reaction vessel. 4.66 mmol), 160 ml of dichloromethane, 17.9 g (93.2 mmol) of 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride was added under ice-cooling. After the addition was completed, return to room temperature and stir overnight. After completion of the reaction, water was added and stirred for 30 minutes, and insoluble materials were collected by filtration. The obtained solid was re-pulverized with chloroform and aqueous methanol, and the solid was dried to obtain N,N'-bis(3-t-butoxycarbonylaminopropyl)-butenediamine 14.1 g as a pale red solid. . The yield was 70.6%.

Under a nitrogen atmosphere, put N,N'-bis(3-tert-butoxycarbonylaminopropyl)-butenediamine 13 g (30.3 mmol) and chloroform (200 ml) in an ice bath in a reaction vessel. After adding 41.5 ml of trifluoroacetic acid (363.6 mmol) under cooling, it was returned to room temperature and stirred overnight. The reaction solution was concentrated, tetrahydrofuran was added, and the precipitated crystals were collected by filtration and dried to obtain 13.9 g of N,N'-bis(3-aminopropyl). 2 Trifluoroacetate salt of fumarate. Dissolving the total amount of N,N'-bis(3-aminopropyl)-butenediamine 2 difluoroacetate in 80 ml of water, adding 60.6 ml of 1 N aqueous sodium hydroxide solution, and decompressing Distill off the water. The crystals precipitated were distilled off by filtration, and dried to give 4.5 g of N,N'-bis(3-aminopropyl)-butenamide as a white crystal. The yield was 65.1%.

Example (2-1): Production of rubber composition

<Program 1>

Using a Banbury mixer (600 ml of labo plastomill manufactured by Toyo Seiki), blending and blending 100 parts by weight of natural rubber (RSS #1) and HAF (manufactured by Asahi Carbon Co., Ltd., trade name "旭#70"), 45 parts by weight, 3 parts by weight of stearic acid, 5 parts by weight of zinc oxide, and an anti-aging agent (N-phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine: trade name "ANTIGENE (registered trademark) 6C" 1 part by weight of 1 part by weight of N,N'-bis(4-aminophenyl)fubutenol obtained in Production Example (2-2), and a rubber composition was obtained. This procedure 1 was carried out by kneading at a number of revolutions of a mixer of 50 rpm 5 minutes after the introduction of various components, and the rubber temperature at this time was 160 to 170 °C.

<Program 2>

The rubber composition obtained by the procedure 1 and the vulcanization accelerator (N-cyclohexyl-2-benzothiazolylsulfenamide) 1 part by weight and sulfur are compounded in an open roller machine at a temperature of 60 to 80 ° C. 2 parts by weight, a rubber composition was obtained.

Example (2-2): Production of vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (2-1) was subjected to a vulcanization treatment at 145 ° C to obtain a vulcanized rubber.

Example (2-3): Production of rubber composition

N,N'-bis(3-aminopropyl)-butenyldiamine obtained in Production Example (2-4) was used instead of N,N'-bis (4) in Example (2-1). A rubber composition was obtained in the same manner as in Example (2-1) except for -aminophenyl)m-butenediamine.

Example (2-4): Manufacture of vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (2-3) was heat-treated at 145 ° C to obtain a vulcanized rubber.

Reference example (2-1)

A rubber composition was obtained in the same manner as in Example (2-1) except that N,N'-bis(4-aminophenyl)fubutenamine was not used in Example (2-1). .

Reference example (2-2)

The rubber composition obtained in the procedure 2 of Reference Example (2-1) was subjected to a vulcanization treatment at 145 ° C to obtain a vulcanized rubber.

The coking time and viscoelastic properties were measured as follows.

(1) Coking time

The measurement was carried out at 125 ° C according to JIS-K6300-1.

The larger the value of the coking time, the more difficult it is to cause rubber scorching, and the processing stability is good.

Test example (2-1)

The rubber composition obtained in Reference Example (2-1) was used as a control, and the coking time of the rubber composition obtained in Reference Example (2-1) was set to 100, for Examples (2-1) and Examples ( The rubber composition obtained in 2-3), the relative value of the coking time is expressed by an index. The results are shown in Table 1.

(2) Viscoelastic properties

The measurement was carried out using a viscoelastic analyzer manufactured by Ushimashima Co., Ltd.

Conditions: Temperature -5 ° C ~ 80 ° C (heating rate: 2 ° C / min) initial strain 10%, dynamic strain 2.5%, frequency 10 Hz

The vulcanized rubber obtained in Reference Example (2-2) was used as a control, and the vulcanized rubber obtained in Reference Example (2-2) was measured for the vulcanized rubber obtained in Example (2-2) and Example (2-4). The rate of decrease (%) of the viscoelastic property (tan δ at 60 ° C). The results are shown in Table 2.

Example (2-5)

The steel cord which was subjected to the brassing treatment was coated with the rubber composition obtained in the procedure 2 of Example (2-1) to obtain an endless belt. Using the obtained endless belt, a green tire was molded according to a usual production method, and the obtained green tire was heated and pressurized in a vulcanizer, whereby a vulcanized tire was obtained.

Example (2-6)

The rubber composition obtained in the procedure 2 of Example (2-1) was subjected to extrusion processing to obtain a member for a tread. Use the resulting tread member, according to the usual In the production method, a green tire is formed, and the obtained green tire is heated and pressurized in a vulcanizer, whereby a vulcanized tire is obtained.

Example (2-7)

The rubber composition obtained in the procedure 2 of the embodiment (2-1) is subjected to extrusion processing to prepare a rubber composition having a shape corresponding to the shape of the carcass, which is attached to the upper and lower sides of the carcass fiber rope of polyester. This obtains the carcass. Using the obtained carcass, a green tire is formed according to a usual production method, and the obtained green tire is heated and pressurized in a vulcanizer, whereby a vulcanized tire is obtained.

Example (2-8)

Except that 0.2 parts by weight of N-(cyclohexylthio)-phthaliminimide (CTP) was further kneaded in the procedure 2 of Example (2-1), the same as in Example (2-1). The method obtains a rubber composition.

Example (2-9)

The rubber composition obtained in the procedure 2 of Example (2-8) was subjected to a vulcanization treatment at 145 ° C to obtain a vulcanized rubber.

Example (2-10): Production of Rubber Composition

<Program 1>

Mixing styrene with a Banbury mixer (600 ml of labo plastomill made by Toyo Seiki). Butadiene copolymer rubber SBR #1502 (manufactured by Sumitomo Chemical Co., Ltd.) 100 parts by weight, ISAF-HM (manufactured by Asahi Carbon Co., Ltd., trade name "旭#80"), 45 parts by weight, stearic acid 2 parts by weight, zinc oxide, 3 parts by weight Parts, N, N'-bis(4-aminophenyl) fumaride, 1 part by weight, anti-aging agent (N-phenyl-N'-1,3-dimethylbutyl-p-benzene) Diamine (6PPD): The trade name "ANTIGENE (registered trademark) 6C" Sumitomo Chemicals Unit 1 part by weight and 2 parts by weight of wax ("OZOACE-0355" manufactured by Nippon Seiko Co., Ltd.) were obtained, and a rubber composition was obtained. This step was carried out by kneading at a number of revolutions of a mixer of 50 rpm 5 minutes after the components were charged, and the rubber temperature at this time was 160 to 175 °C.

<Program 2>

3 parts by weight of the rubber composition obtained by the procedure 1 and the vulcanization accelerator N-cyclohexyl-2-benzothiazolylsulfenamide (CBS) were mixed and kneaded in an open roller machine at a temperature of 60 to 80 ° C and 2 parts by weight of sulfur, a rubber composition was obtained.

Example (2-11): Manufacture of vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (2-10) was heat-treated at 145 ° C, whereby a vulcanized rubber was obtained. The obtained vulcanized rubber is preferably used as a tread cap.

Example (2-12): Production of rubber composition

<Program 1>

Mixing styrene with a Banbury mixer (600 ml of labo plastomill made by Toyo Seiki). 100 parts by weight of butadiene copolymer rubber SBR #1502 (manufactured by Sumitomo Chemical Co., Ltd.), 35 parts by weight of ISAF-HM (manufactured by Asahi Carbon Co., Ltd., trade name "旭#80"), 2 parts by weight of stearic acid, and 3 parts by weight of zinc oxide Parts, N, N'-bis(4-aminophenyl) fumaride, 1 part by weight, anti-aging agent (N-phenyl-N'-1,3-dimethylbutyl-p-benzene) Diamine (6PPD): The product name "ANTIGENE (registered trademark) 6C, manufactured by Sumitomo Chemical Co., Ltd.) was used in an amount of 2 parts by weight and wax ("OZOACE-0355" manufactured by Nippon Seiko Co., Ltd.) to obtain a rubber composition. This step is performed by mixing the number of rotations of the mixer at 50 rpm 5 minutes after the components are put in. The rubber temperature at this time is 160 to 175 °C.

<Program 2>

2 parts by weight of the rubber composition obtained by the procedure 1 and the vulcanization accelerator N-cyclohexyl-2-benzothiazolylsulfenamide (CBS) were mixed and kneaded in an open roller machine at a temperature of 60 to 80 ° C. 0.5 parts by weight of a vulcanization accelerator diphenyl sulfonium (DPG), 0.8 parts by weight of a vulcanization accelerator dibenzothiazyl disulfide (MBTS), and 1 part by weight of sulfur were used to obtain a rubber composition.

Example (2-13): For the manufacture of a tread base for a vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (2-12) was subjected to heat treatment at 145 ° C, whereby a vulcanized rubber was obtained. The obtained vulcanized rubber is preferably used as the base of the tread.

Example (2-14): Production of rubber composition

<Program 1>

Using a Banbury mixer (600 ml of labo plastomill manufactured by Toyo Seiki), blending and blending 100 parts by weight of natural rubber (RSS #1) and HAF (manufactured by Asahi Carbon Co., Ltd., trade name "旭#70"), 45 parts by weight, 3 parts by weight of stearic acid, 5 parts by weight of zinc oxide, 1 part by weight of N,N'-bis(4-aminophenyl)fudodecylamine, and aqueous cerium oxide (manufactured by TOSOH SILICA Co., Ltd.) 10 parts by weight of "Nipsil (registered trademark) AQ", 2 parts by weight of anti-aging agent FR ("Antioxidant FR" manufactured by Matsubara Sangyo Co., Ltd.), 2 parts by weight of resorcin and 2 parts by weight of cobalt naphthenate, and a rubber composition was obtained. This step was carried out by kneading the number of revolutions of the mixer at 50 rpm 5 minutes after the components were charged, and the rubber temperature at this time was 160 to 175 °C.

<Program 2>

The rubber composition obtained by the procedure 1 and the vulcanization accelerator N,N-dicyclohexyl-2-benzothiazolylsulfenamide (DCBS) 1 were mixed in an open roller machine at a temperature of 60 to 80 ° C. A rubber composition was obtained in an amount of 3 parts by weight based on parts by weight, sulfur 6 parts by weight, and methoxymethylol melamine resin ("Sumikanol 507AP" manufactured by Sumitomo Chemical Co., Ltd.).

Example (2-15): Manufacture of vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (2-14) was subjected to heat treatment at 145 ° C, whereby a vulcanized rubber was obtained. The obtained vulcanized rubber is preferably used as an endless belt.

Example (2-16): Production of rubber composition

<Program 1>

Using a Banbury mixer (600 ml of labo plastomill manufactured by Toyo Seiki), 100 parts by weight of a halogenated butyl rubber ("Br-IIR2255" manufactured by Exxon Mobil Co., Ltd.), 60 parts by weight of GPF, and 1 weight of stearic acid were blended. 3 parts by weight of zinc oxide, 1 part by weight of N,N'-bis(4-aminophenyl) fumaride, and 10 parts by weight of paraffin oil ("Diana Process Oil" manufactured by Idemitsu Kosan Co., Ltd.) , a rubber composition is obtained. This step was carried out by kneading at a number of revolutions of a mixer of 50 rpm 5 minutes after the components were charged, and the rubber temperature at this time was 160 to 175 °C.

<Program 2>

The rubber composition obtained by the procedure 1, the anti-aging agent (condensation of aniline and acetone (TMDQ)), 1 part by weight, and the vulcanization accelerator disulfide diphenyl sulfide are blended in an open roller machine at a temperature of 60 to 80 ° C. Thiazole (MBTS) 1 A rubber composition was obtained in parts by weight and 2 parts by weight of sulfur.

Example (2-17): Manufacture of vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (2-16) was heat-treated at 145 ° C, whereby a vulcanized rubber was obtained. The obtained vulcanized rubber is preferably used as an inner liner.

Example (2-18): Production of rubber composition

<Program 1>

60 parts of natural rubber (RSS #3) and 40 parts of polybutadiene rubber ("BR150B" manufactured by Ube Industries Co., Ltd.) were blended with a Banbury mixer (a 600 ml labo plastomill manufactured by Toyo Seiki). 50 parts by weight of FEF, 2.5 parts by weight of stearic acid, 3 parts by weight of zinc oxide, 1 part by weight of N,N'-bis(4-aminophenyl)fudodecylamine, and an anti-aging agent (N-phenyl group) -N'-1,3-dimethylbutyl-p-phenylenediamine (6PPD): trade name "ANTIGENE (registered trademark) 6C" manufactured by Sumitomo Chemical Co., Ltd.) 2 parts by weight, aromatic oil (manufactured by Cosmo Oil Co., Ltd.) In the "NC-140", 2 parts by weight and wax ("SUNNOC (registered trademark) WAX" manufactured by Okinawa Chemical Industry Co., Ltd.) were added in an amount of 2 parts by weight to obtain a rubber composition. This step was carried out by kneading at a number of revolutions of a mixer of 50 rpm 5 minutes after the components were charged, and the rubber temperature at this time was 160 to 175 °C.

<Program 2>

The rubber composition obtained by the procedure 1 and the vulcanization accelerator N-t-butyl-2-benzothiazolylsulfenamide (BBS) 0.75 weight are compounded in an open roller machine at a temperature of 60 to 80 ° C. Parts and sulfur were 1.5 parts by weight to obtain a rubber composition.

Example (2-19): Manufacture of vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (2-18) was subjected to heat treatment at 145 ° C, whereby a vulcanized rubber was obtained. The obtained vulcanized rubber is preferably used as a sidewall.

Example (2-20): Production of rubber composition

<Program 1>

Using a Banbury mixer (600 ml of labo plastomill manufactured by Toyo Seiki), mix 70 parts by weight of natural rubber (TSR20) with styrene. 30 parts by weight of butadiene copolymer rubber SBR #1502 (manufactured by Sumitomo Chemical Co., Ltd.), 60 parts by weight of N339 (manufactured by Mitsubishi Chemical Corporation), 2 parts by weight of stearic acid, 5 parts by weight of zinc oxide, and treated oil (manufactured by Idemitsu Kosan Co., Ltd.) "Diana Process PS32") 7 parts by weight and 1 part by weight of N,N'-bis(4-aminophenyl) fumaride, and a rubber composition was obtained. This step was carried out by kneading at a number of revolutions of a mixer of 50 rpm 5 minutes after the components were charged, and the rubber temperature at this time was 160 to 175 °C.

<Program 2>

The rubber composition obtained by the procedure 1 and the vulcanization accelerator N-t-butyl-2-benzothiazolylsulfenamide (BBS) 1 weight are blended in an open roller machine at a temperature of 60 to 80 ° C. Parts, sulfur 3 parts by weight, anti-aging agent (N-phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine (6PPD): trade name "ANTIGENE (registered trademark) 6C" Sumitomo Chemical Co., Ltd. 1 part by weight and an anti-aging agent (condensation of aniline and acetone (TMDQ)) (1 part by weight) to obtain a rubber composition.

Example (2-21): Manufacture of vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (2-20) was subjected to heat treatment at 145 ° C, whereby a vulcanized rubber was obtained. The obtained vulcanized rubber is preferably used as a carcass.

Example (2-22): Production of Rubber Composition

<Program 1>

Mixing styrene with a Banbury mixer (600 ml of labo plastomill made by Toyo Seiki). 100 parts by weight of butadiene copolymer rubber SBR #1500 (manufactured by JSR Corporation), cerium oxide (trade name: "Ultrasil (registered trademark) VN3-G" manufactured by Degussa Co., Ltd.) 78.4 parts by weight, carbon black (trade name "N- 339" manufactured by Mitsubishi Chemical Corporation) 6.4 parts by weight of a decane coupling agent (bis(3-triethoxydecylpropyl) tetrasulfide: trade name "Si-69" manufactured by Degussa Co., Ltd.) 6.4 parts by weight, treated oil ( Product name "NC-140" manufactured by Cosmo Oil Co., Ltd.) 47.6 parts by weight, anti-aging agent (N-phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine (6PPD): trade name "ANTIGENE" (registered trademark) 6C" manufactured by Sumitomo Chemical Co., Ltd.) 1.5 parts by weight, 2 parts by weight of zinc oxide, 2 parts by weight of stearic acid, and N,N'-bis(4-aminophenyl) fumarate 3 parts by weight, a rubber composition was obtained. This step is carried out by operating in a temperature range of 70 ° C to 120 ° C for 5 minutes after the components are put into operation, and mixing is performed at a rotation number of the mixer of 80 rpm, followed by 5 minutes, and the number of rotations of the mixer at 100 rpm is performed. Implemented by mixing.

<Program 2>

The rubber composition obtained by the procedure 1 and the vulcanization accelerator N-cyclohexyl-2-benzothiazolylsulfenamide (CBS) are blended in an open roller at a temperature of 30 to 80 ° C, and 1 part by weight, Vulcanization accelerator diphenyl hydrazine (DPG) 1 weight 1.5 parts by weight of a wax (trade name "SUNNOC (registered trademark) N" manufactured by Ouchi Shinko Chemical Co., Ltd.) and 1.4 parts by weight of sulfur were obtained to obtain a rubber composition.

Example (2-23): Manufacture of vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (2-22) was subjected to heat treatment at 160 ° C, whereby a vulcanized rubber was obtained. The obtained vulcanized rubber is preferably used as a tread cap.

Example (2-24): Production of rubber composition

In addition to the styrene ‧ butadiene copolymer rubber SBR #1500 (manufactured by JSR Corporation), a solution polymerization SBR ("Asaprene (registered trademark)" Asahi Kasei Chemicals Co., Ltd.) was used instead of the solution (2-22). The rubber composition was obtained in the same manner as in Example (2-28).

Example (2-25): Manufacture of vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (2-30) was subjected to heat treatment at 160 ° C, whereby a vulcanized rubber was obtained. The obtained vulcanized rubber is preferably used as a tread cap.

Example (2-26): Production of rubber composition

In addition to the embodiment (2-22), SBR #1712 (manufactured by JSR Corporation) was used instead of styrene. Butadiene copolymer rubber SBR #1500 (manufactured by JSR Corporation), the amount of the treatment oil used was changed to 21 parts by weight, and the time for introducing zinc oxide was changed to the procedure 2, and the same method as in the example (2-28) was obtained. Rubber composition.

Example (2-27): Manufacture of vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (2-26) was subjected to heat treatment at 160 ° C, whereby a vulcanized rubber was obtained. The obtained vulcanized rubber is preferably used as a tread cap.

Example (2-28): Production of rubber composition

<Program 1>

Using a Banbury mixer (600 ml of labo plastomill manufactured by Toyo Seiki), blending and blending 100 parts by weight of natural rubber (RSS #1) and HAF (manufactured by Asahi Carbon Co., Ltd., trade name "旭#70"), 45 parts by weight, 3 parts by weight of stearic acid, 5 parts by weight of zinc oxide, and 1 part by weight of N,N'-bis(4-aminophenyl)fubutenol obtained in Production Example (2-2), a rubber combination was obtained. Things. This procedure 1 was carried out by kneading at a number of revolutions of a mixer of 50 rpm 5 minutes after the introduction of various components, and the rubber temperature at this time was 160 to 170 °C.

<Program 2>

The rubber composition obtained by the procedure 1 and the vulcanization accelerator (N-cyclohexyl-2-benzothiazolylsulfenamide) 1 part by weight and sulfur are compounded in an open roller machine at a temperature of 60 to 80 ° C. 2 parts by weight, a rubber composition was obtained.

Example (2-29): Manufacture of vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (2-28) was subjected to heat treatment at 160 ° C, whereby a vulcanized rubber was obtained. The obtained vulcanized rubber has improved viscoelastic properties and is excellent in anti-aging properties.

Example (2-30): Production of rubber composition

<Program 1>

Using a Banbury mixer (600 ml of labo plastomill manufactured by Toyo Seiki), blending and blending 100 parts by weight of natural rubber (RSS #1) and HAF (manufactured by Asahi Carbon Co., Ltd., trade name "旭#70"), 50 parts by weight, 3 parts by weight of stearic acid, 5 parts by weight of zinc oxide and an anti-aging agent (N-phenyl-N'-1,3- Dimethyl butyl-p-phenylenediamine (6PPD): The product name "ANTIGENE (registered trademark) 6C, manufactured by Sumitomo Chemical Co., Ltd.) was used in an amount of 1 part by weight to obtain a rubber composition. This procedure 1 was carried out by kneading at a number of revolutions of a mixer of 50 rpm 5 minutes after the introduction of various components, and the rubber temperature at this time was 160 to 170 °C.

<Program 2>

The rubber composition obtained in the procedure 1 and the N,N'-bis(4-aminophenyl) counter obtained in the production example (2-2) were blended in an open roller at 60 to 80 ° C. 1 part by weight of butylenediamine, 1 part by weight of a vulcanization accelerator (dibenzothiazole disulfide), and 1 part by weight of sulfur, a rubber composition was obtained.

Example (2-31): Manufacture of vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (2-30) was subjected to heat treatment at 170 ° C, whereby a vulcanized rubber was obtained. The obtained vulcanized rubber is excellent in anti-reversion property.

Production Example (3-1): Production of (Z)-3-(4-aminophenylaminecarbamyl)acrylic acid

Under a nitrogen atmosphere, 25.17 g (0.233 mol) of 1,4-phenylenediamine and 230 ml of tetrahydrofuran were placed in a reaction vessel. After a solution of 22.84 g (0.233 mol) of maleic anhydride dissolved in 50 ml of tetrahydrofuran was added dropwise thereto under ice cooling for about 1 hour, the mixture was stirred at room temperature overnight. After completion of the reaction, the precipitated crystals were collected by filtration, washed twice with 40 ml of tetrahydrofuran, and dried at 40 ° C for 5 hours to obtain a crude (Z)-3-(4-aminophenylaminecarbamyl) as an orange powder. ) Acrylic 46.92 g. (Z)-3-(4-Aminophenyl) 250 ml of methanol was added to 46.92 g of methacrylamide), and the mixture was stirred at 50 ° C for 1 hour, cooled, filtered, and washed twice with methanol 20 ml. The obtained crystals were dried to obtain 42.67 g of (Z)-3-(4-aminophenylaminecarbamyl)acrylic acid as a yellow-orange powder. Yield 88.8%

Production Example (3-2): Production of N,N'-bis(4-aminophenyl)cis-decylamine

In a reaction vessel, 13.85 g (67.2 mmol) of (Z)-3-(4-aminophenylaminocarbamimidyl)acrylic acid synthesized in Production Example (3-1) in a reaction vessel, and put 1, 4-phenylenediamine 6.90 g (67.2 mmol), dimethylaminopyridine 0.82 g and dimethylformamide 130 ml. 1-Ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride 12.88 g (67.2 mmol) was added thereto under ice-cooling, and stirred at room temperature overnight. After completion of the reaction, 560 ml of water was added, and the mixture was extracted four times with 500 ml of ethyl acetate. The organic layer was combined, washed with brine (500 ml), dried over sodium sulfate, and evaporated. 50 ml of chloroform was added thereto, and the mixture was concentrated under reduced pressure three times, and then, to the obtained residue, 80 ml of methanol was added, and the precipitated solid was separated by filtration. The filtrate was concentrated under reduced pressure, and then applied to a silica gel column chromatography to obtain 5.30 g of N,N'-bis(4-aminophenyl)-s-succinamine as a dark red solid. The yield was 26.6%.

¹ H-NMR (300.13 MHz, DMSO-d6) δ _ppm : 10.75 (2H, s), 7.30 (4H, d, J = 8.7 Hz), 6.52 (4H, d, J = 8.7 Hz), 6.29 (2H, s), 4.95 (4H, s)

Example (3-1): Production of rubber composition

<Program 1>

Using a Banbury mixer (600 ml of labo plastomill manufactured by Toyo Seiki), blending and blending 100 parts by weight of natural rubber (RSS #1) and HAF (manufactured by Asahi Carbon Co., Ltd., trade name "旭#70"), 45 parts by weight, 3 parts by weight of stearic acid, 5 parts by weight of zinc oxide, and an anti-aging agent (N-phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine: trade name "ANTIGENE (registered trademark) 6C" 1 part by weight of 1 part by weight of N,N'-bis(4-aminophenyl)butylammoniumamine obtained in Production Example (3-2), and a rubber composition was obtained. This procedure 1 was carried out by kneading at a number of revolutions of a mixer of 50 rpm 5 minutes after the introduction of various components, and the rubber temperature at this time was 160 to 170 °C.

<Program 2>

The rubber composition obtained by the procedure 1 and the vulcanization accelerator (N-cyclohexyl-2-benzothiazolylsulfenamide) 1 part by weight and sulfur are compounded in an open roller machine at a temperature of 60 to 80 ° C. 2 parts by weight, a rubber composition was obtained.

Example (3-2): Manufacture of vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (3-1) was subjected to a vulcanization treatment at 145 ° C to obtain a vulcanized rubber.

Example (3-3): Production of rubber composition

In place of N,N'-bis (4-amino group), commercially available 4,4'-diaminostilbene dihydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was used in the same manner as in the example (3-1). A rubber composition was obtained in the same manner as in Example (3-1) except for phenyl)cishydrylamine.

Example (3-4): Manufacture of vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (3-3) was subjected to a vulcanization treatment at 145 ° C to obtain a vulcanized rubber.

Reference example (3-1)

A rubber composition was obtained in the same manner as in Example (3-1) except that N,N'-bis(4-aminophenyl)-cis-decylamine was not used in Example (3-1).

Reference example (3-2)

The rubber composition obtained in the procedure 2 of Reference Example (3-1) was subjected to a vulcanization treatment at 145 ° C to obtain a vulcanized rubber.

The coking time and viscoelastic properties were measured as follows.

(1) Coking time

The measurement was carried out at 125 ° C according to JIS-K6300-1.

The larger the value of the coking time, the more difficult it is to cause rubber scorching, and the processing stability is good.

Test example (3-1)

The rubber composition obtained in Reference Example (3-1) was used as a control, and the coking time of the rubber composition obtained in Reference Example (3-1) was set to 100, for Examples (3-1) and Examples ( The rubber composition obtained in 3-3), the relative value of the coking time is expressed by an index, and the results are 89 and 91.

(2) Viscoelastic properties

The measurement was carried out using a viscoelastic analyzer manufactured by Ushimashima Co., Ltd.

Conditions: Temperature -5 ° C ~ 80 ° C (heating rate: 2 ° C / min) initial strain 10%, dynamic strain 2.5%, frequency 10 Hz

The vulcanized rubber obtained in Reference Example (3-2) was used as a control for the examples. (3-2) and the vulcanized rubber obtained in the example (3-4), the rate of decrease (%) of the viscoelastic property (tan δ at 60 ° C) obtained in Reference Example (3-2) was measured, and the results were respectively It is a decline rate of 33% and 17%.

Example (3-5)

The steel cord which was subjected to the brassing treatment was coated with the rubber composition obtained in the procedure 2 of Example (3-1) to obtain an endless belt. Using the obtained endless belt, a green tire was molded according to a usual production method, and the obtained green tire was heated and pressurized in a vulcanizer, whereby a vulcanized tire was obtained.

Example (3-6)

The rubber composition obtained in the procedure 2 of Example (3-1) was subjected to extrusion processing to obtain a member for a tread. Using the obtained tread member, a green tire is molded according to a usual production method, and the obtained green tire is heated and pressurized in a vulcanizer to obtain a vulcanized tire.

Example (3-7)

The rubber composition obtained in the procedure 2 of the embodiment (3-1) is subjected to extrusion processing to prepare a rubber composition having a shape corresponding to the shape of the carcass, which is attached to the top of the carcass fiber rope of the polyester. This obtains the carcass. Using the obtained carcass, a green tire is formed according to a usual production method, and the obtained green tire is heated and pressurized in a vulcanizer, whereby a vulcanized tire is obtained.

Example (3-8)

The same procedure as in Example (3-1) was carried out except that 0.2 parts by weight of N-(cyclohexylthio)-phthaliminimide (CTP) was further compounded in the procedure 2 of Example (3-1). The method obtains a rubber composition.

Example (3-9)

The rubber composition obtained in the procedure 2 of Example (3-8) was subjected to a vulcanization treatment at 145 ° C to obtain a vulcanized rubber.

Example (3-10): Production of Rubber Composition

<Program 1>

Mixing styrene with a Banbury mixer (600 ml of labo plastomill made by Toyo Seiki). Butadiene copolymer rubber SBR #1502 (manufactured by Sumitomo Chemical Co., Ltd.) 100 parts by weight, ISAF-HM (manufactured by Asahi Carbon Co., Ltd., trade name "旭#80"), 45 parts by weight, stearic acid 2 parts by weight, zinc oxide, 3 parts by weight 1 part by weight of N,N'-bis(4-aminophenyl)cisantamine, anti-aging agent (N-phenyl-N'-1,3-dimethylbutyl-p-phenylene) Amine (6PPD): The product name "ANTIGENE (registered trademark) 6C, manufactured by Sumitomo Chemical Co., Ltd.) was used in an amount of 2 parts by weight and wax ("OZOACE-0355" manufactured by Nippon Seiko Co., Ltd.) to obtain a rubber composition. This step was carried out by kneading at a number of revolutions of a mixer of 50 rpm 5 minutes after the components were charged, and the rubber temperature at this time was 160 to 175 °C.

<Program 2>

3 parts by weight of the rubber composition obtained by the procedure 1 and the vulcanization accelerator N-cyclohexyl-2-benzothiazolylsulfenamide (CBS) were mixed and kneaded in an open roller machine at a temperature of 60 to 80 ° C and 2 parts by weight of sulfur, a rubber composition was obtained.

Example (3-11): Manufacture of vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (3-10) was subjected to heat treatment at 145 ° C, whereby a vulcanized rubber was obtained. The obtained vulcanized rubber is preferably used as a tread cap.

Example (3-12): Production of rubber composition

<Program 1>

Mixing styrene with a Banbury mixer (600 ml of labo plastomill made by Toyo Seiki). 100 parts by weight of butadiene copolymer rubber SBR #1502 (manufactured by Sumitomo Chemical Co., Ltd.), 35 parts by weight of ISAF-HM (manufactured by Asahi Carbon Co., Ltd., trade name "旭#80"), 2 parts by weight of stearic acid, and 3 parts by weight of zinc oxide 1 part by weight of N,N'-bis(4-aminophenyl)cisantamine, anti-aging agent (N-phenyl-N'-1,3-dimethylbutyl-p-phenylene) Amine (6PPD): The product name "ANTIGENE (registered trademark) 6C, manufactured by Sumitomo Chemical Co., Ltd.) was used in an amount of 2 parts by weight and wax ("OZOACE-0355" manufactured by Nippon Seiko Co., Ltd.) to obtain a rubber composition. This step was carried out by kneading at a number of revolutions of a mixer of 50 rpm 5 minutes after the components were charged, and the rubber temperature at this time was 160 to 175 °C.

<Program 2>

2 parts by weight of the rubber composition obtained by the procedure 1 and the vulcanization accelerator N-cyclohexyl-2-benzothiazolylsulfenamide (CBS) were mixed and kneaded in an open roller machine at a temperature of 60 to 80 ° C. 0.5 parts by weight of a vulcanization accelerator diphenyl sulfonium (DPG), 0.8 parts by weight of a vulcanization accelerator dibenzothiazyl disulfide (MBTS), and 1 part by weight of sulfur were used to obtain a rubber composition.

Example (3-13): For the manufacture of a tread base for a vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (3-12) was subjected to heat treatment at 145 ° C, whereby a vulcanized rubber was obtained. The obtained vulcanized rubber is preferably used as the base of the tread.

Example (3-14): Production of rubber composition

<Program 1>

Using a Banbury mixer (600 ml of labo plastomill manufactured by Toyo Seiki), blending and blending 100 parts by weight of natural rubber (RSS #1) and HAF (manufactured by Asahi Carbon Co., Ltd., trade name "旭#70"), 45 parts by weight, 3 parts by weight of stearic acid, 5 parts by weight of zinc oxide, 1 part by weight of N,N'-bis(4-aminophenyl)succinimide, and aqueous cerium oxide (manufactured by TOSOH SILICA Co., Ltd.) 10 parts by weight of Nipsil (registered trademark) AQ, 2 parts by weight of anti-aging agent FR ("Antioxidant FR" manufactured by Matsubara Sangyo Co., Ltd.), 2 parts by weight of resorcin and 2 parts by weight of cobalt naphthenate, and a rubber composition was obtained. This step was carried out by kneading at a number of revolutions of a mixer of 50 rpm 5 minutes after the components were charged, and the rubber temperature at this time was 160 to 175 °C.

<Program 2>

The rubber composition obtained by the procedure 1 and the vulcanization accelerator N,N-dicyclohexyl-2-benzothiazolylsulfenamide (DCBS) 1 were mixed in an open roller machine at a temperature of 60 to 80 ° C. A rubber composition was obtained in an amount of 3 parts by weight based on parts by weight, sulfur 6 parts by weight, and methoxymethylol melamine resin ("Sumikanol 507AP" manufactured by Sumitomo Chemical Co., Ltd.).

Example (3-15): Manufacture of vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (3-14) was subjected to heat treatment at 145 ° C, whereby a vulcanized rubber was obtained. The obtained vulcanized rubber is preferably used as an endless belt.

Example (3-16): Production of rubber composition

<Program 1>

Blended with halogenated butyl rubber (Exxon Mobil) using a Banbury mixer (600 ml of labo plastomill manufactured by Toyo Seiki) 100 parts by weight of "Br-IIR2255"), 60 parts by weight of GPF, 1 part by weight of stearic acid, 3 parts by weight of zinc oxide, and N,N'-bis(4-aminophenyl)cis-decylamine 1 10 parts by weight of a part by weight and paraffin oil ("Diana Process Oil" manufactured by Idemitsu Kosan Co., Ltd.) was obtained to obtain a rubber composition. This step was carried out by kneading at a number of revolutions of a mixer of 50 rpm 5 minutes after the components were charged, and the rubber temperature at this time was 160 to 175 °C.

<Program 2>

The rubber composition obtained by the procedure 1, the anti-aging agent (condensation of aniline and acetone (TMDQ)), 1 part by weight, and the vulcanization accelerator disulfide diphenyl sulfide are blended in an open roller machine at a temperature of 60 to 80 ° C. 1 part by weight of thiazole (MBTS) and 2 parts by weight of sulfur were used to obtain a rubber composition.

Example (3-17): Manufacture of vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (3-16) was heat-treated at 145 ° C, whereby a vulcanized rubber was obtained. The obtained vulcanized rubber is preferably used as an inner liner.

Example (3-18): Production of rubber composition

<Program 1>

60 parts of natural rubber (RSS #3) and 40 parts of polybutadiene rubber ("BR150B" manufactured by Ube Industries Co., Ltd.) were blended with a Banbury mixer (a 600 ml labo plastomill manufactured by Toyo Seiki). 50 parts by weight of FEF, 2.5 parts by weight of stearic acid, 3 parts by weight of zinc oxide, 1 part by weight of N,N'-bis(4-aminophenyl)butylammonium, and an anti-aging agent (N-phenyl- N'-1,3-dimethylbutyl-p-phenylenediamine (6PPD): trade name "ANTIGENE (registered trademark) 6C" manufactured by Sumitomo Chemical Co., Ltd.) 2 parts by weight, aromatic oil (2 parts by weight of "NC-140" manufactured by Cosmo Oil Co., Ltd.) and 2 parts by weight of wax ("SUNNOC (registered trademark) WAX" manufactured by Okinawa Chemical Industry Co., Ltd.) to obtain a rubber composition. This step was carried out by kneading at a number of revolutions of a mixer of 50 rpm 5 minutes after the components were charged, and the rubber temperature at this time was 160 to 175 °C.

<Program 2>

The rubber composition obtained by the procedure 1 and the vulcanization accelerator N-t-butyl-2-benzothiazolylsulfenamide (BBS) 0.75 weight are compounded in an open roller machine at a temperature of 60 to 80 ° C. Parts and sulfur were 1.5 parts by weight to obtain a rubber composition.

Example (3-19): Manufacture of vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (3-18) was subjected to heat treatment at 145 ° C, whereby a vulcanized rubber was obtained. The obtained vulcanized rubber is preferably used as a sidewall.

Example (3-20): Production of rubber composition

<Program 1>

Using a Banbury mixer (600 ml of labo plastomill manufactured by Toyo Seiki), mix 70 parts by weight of natural rubber (TSR20) with styrene. 30 parts by weight of butadiene copolymer rubber SBR #1502 (manufactured by Sumitomo Chemical Co., Ltd.), 60 parts by weight of N339 (manufactured by Mitsubishi Chemical Corporation), 2 parts by weight of stearic acid, 5 parts by weight of zinc oxide, and treated oil (manufactured by Idemitsu Kosan Co., Ltd.) "Diana Process PS32") 7 parts by weight and 1 part by weight of N,N'-bis(4-aminophenyl)butylammoniumamine were used to obtain a rubber composition. This step is performed by mixing the number of revolutions of the mixer at 50 rpm 5 minutes after the components are put in. In practice, the rubber temperature at this time is 160 to 175 °C.

<Program 2>

The rubber composition obtained by the procedure 1 and the vulcanization accelerator N-t-butyl-2-benzothiazolylsulfenamide (BBS) 1 weight are blended in an open roller machine at a temperature of 60 to 80 ° C. Parts, sulfur 3 parts by weight, anti-aging agent (N-phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine (6PPD): trade name "ANTIGENE (registered trademark) 6C" Sumitomo Chemical Co., Ltd. 1 part by weight and an anti-aging agent (condensation of aniline and acetone (TMDQ)) (1 part by weight) to obtain a rubber composition.

Example (3-21): Manufacture of vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (3-20) was subjected to heat treatment at 145 ° C, whereby a vulcanized rubber was obtained. The obtained vulcanized rubber is preferably used as a carcass.

Example (3-22): Production of rubber composition

<Program 1>

Mixing styrene with a Banbury mixer (600 ml of labo plastomill made by Toyo Seiki). 100 parts by weight of butadiene copolymer rubber SBR #1500 (manufactured by JSR Corporation), cerium oxide (trade name: "Ultrasil (registered trademark) VN3-G" manufactured by Degussa Co., Ltd.) 78.4 parts by weight, carbon black (trade name "N- 339" manufactured by Mitsubishi Chemical Corporation) 6.4 parts by weight of a decane coupling agent (bis(3-triethoxydecylpropyl) tetrasulfide: trade name "Si-69" manufactured by Degussa Co., Ltd.) 6.4 parts by weight, treated oil ( Product name "NC-140" manufactured by Cosmo Oil Co., Ltd.) 47.6 parts by weight, anti-aging agent (N-phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine (6PPD): trade name "ANTIGENE" (registered trademark) 6C" manufactured by Sumitomo Chemical Co., Ltd.) 1.5 parts by weight, 2 parts by weight of zinc oxide, 2 parts by weight of stearic acid, and N,N'-bis(4-aminophenyl)syninamide 3 The rubber composition was obtained in parts by weight. This step is carried out by operating in a temperature range of 70 ° C to 120 ° C for 5 minutes after the components are put into operation, and mixing is performed at a rotation number of the mixer of 80 rpm, followed by 5 minutes, and the number of rotations of the mixer at 100 rpm is performed. Implemented by mixing.

<Program 2>

The rubber composition obtained by the procedure 1 and the vulcanization accelerator N-cyclohexyl-2-benzothiazolylsulfenamide (CBS) are blended in an open roller at a temperature of 30 to 80 ° C, and 1 part by weight, 1 part by weight of a vulcanization accelerator (DPG), 1.5 parts by weight of a wax (trade name "SUNNOC (registered trademark) N" manufactured by Ouchi Shinko Chemical Co., Ltd.), and 1.4 parts by weight of sulfur were obtained to obtain a rubber composition.

Example (3-23): Manufacture of vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (3-22) was subjected to heat treatment at 160 ° C, whereby a vulcanized rubber was obtained. The obtained vulcanized rubber is preferably used as a tread cap.

Example (3-24): Production of rubber composition

In addition to the solution (3-22), solution polymerization SBR ("Asaprene (registered trademark)" Asahi Kasei Chemicals Co., Ltd.) was used instead of styrene. A rubber composition was obtained in the same manner as in Example (3-22) except for butadiene copolymer rubber SBR #1500 (manufactured by JSR Corporation).

Example (3-25): Manufacture of vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (3-24) was subjected to heat treatment at 160 ° C, whereby a vulcanized rubber was obtained. The resulting vulcanized rubber as a tread The crown is preferred.

Example (3-26): Production of rubber composition

In the example (3-22), SBR #1712 (manufactured by JSR Corporation) was used instead of styrene ‧ butadiene copolymer rubber SBR #1500 (manufactured by JSR Corporation), and the amount of the treatment oil was changed to 21 parts by weight. The rubber composition was obtained in the same manner as in Example (3-22) except that the time of zinc oxide was changed to the procedure of 2.

Example (3-27): Manufacture of vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (3-26) was subjected to heat treatment at 160 ° C, whereby a vulcanized rubber was obtained. The obtained vulcanized rubber is preferably used as a tread cap.

Example (3-28): Production of rubber composition

<Program 1>

Using a Banbury mixer (600 ml of labo plastomill manufactured by Toyo Seiki), blending and blending 100 parts by weight of natural rubber (RSS #1) and HAF (manufactured by Asahi Carbon Co., Ltd., trade name "旭#70"), 45 parts by weight, 3 parts by weight of stearic acid, 5 parts by weight of zinc oxide, and 4 parts by weight of 4,4'-diaminostilbene dihydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) were used to obtain a rubber composition. This procedure 1 was carried out by kneading at a number of revolutions of a mixer of 50 rpm 5 minutes after the introduction of various components, and the rubber temperature at this time was 160 to 170 °C.

<Program 2>

The rubber composition obtained by the procedure 1 and the vulcanization accelerator (N-cyclohexyl-2-benzothiazolyl) are blended in an open roller machine at a temperature of 60 to 80 ° C. 1 part by weight of sulfoximine) and 2 parts by weight of sulfur to obtain a rubber composition.

Example (3-29): Manufacture of vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (3-28) was subjected to heat treatment at 160 ° C, whereby a vulcanized rubber was obtained. The obtained vulcanized rubber has improved viscoelastic properties and is excellent in anti-aging properties.

Example (3-30): Production of rubber composition

<Program 1>

Using a Banbury mixer (600 ml of labo plastomill manufactured by Toyo Seiki), blending and blending 100 parts by weight of natural rubber (RSS #1) and HAF (manufactured by Asahi Carbon Co., Ltd., trade name "旭#70"), 50 parts by weight, 3 parts by weight of stearic acid, 5 parts by weight of zinc oxide, and an anti-aging agent (N-phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine (6PPD): trade name "ANTIGENE (registered trademark ) 6 parts by weight of 6C Sumitomo Chemical Co., Ltd. to obtain a rubber composition. This procedure 1 was carried out by kneading at a number of revolutions of a mixer of 50 rpm 5 minutes after the introduction of various components, and the rubber temperature at this time was 160 to 170 °C.

<Program 2>

The rubber composition obtained by the procedure 1 and 4,4'-diaminostilbene dihydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and kneaded in an open roller at a temperature of 60 to 80 ° C. Parts by weight, 1 part by weight of a vulcanization accelerator (dibenzothiazole disulfide), and 1 part by weight of sulfur were used to obtain a rubber composition.

Example (3-31): Manufacture of vulcanized rubber

The rubber composition obtained in the procedure 2 of Example (3-30) was subjected to heat treatment at 170 ° C, whereby a vulcanized rubber was obtained. Anti-reversion of the obtained vulcanized rubber Excellent performance.

[Industrial availability]

According to the rubber composition of the present invention, the viscoelastic properties of the vulcanized rubber obtained from the rubber composition can be improved.

Claims (22)

A rubber composition which is one selected from the group consisting of a compound represented by the formula (I-1), a compound represented by the formula (I-2), and a compound represented by the formula (I-3). The above compound is obtained by kneading a rubber component and a filler. [In the formula (I-1), A ¹ and A ² each independently represent an alkanediyl group having 2 to 12 carbon atoms which may have a substituent, a cycloalkanediyl group having 3 to 12 carbon atoms which may have a substituent, or -B ^1- Ar-B ² - group, -CH ₂ - contained in the alkanediyl group having 2 to 12 carbon atoms may be substituted by -NH-, -O- or -S-; B ¹ and B ² are each independently represented by a single a bond or a C 2 to 6 alkanediyl group; Ar represents a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent; and R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, and a carbon number of 1 to 2; 6 alkyl, aryl group having 6 to 12 carbon atoms, hydroxyl group or alkoxy group having 1 to 6 carbon atoms, or bonded to each other to form an alkanediyl group having 1 to 12 carbon atoms; X ¹ and X ² are each independently represented - NH- or -O-]. [In the formula (I-2), A ³ and A ⁴ each independently represent an alkanediyl group having 2 to 12 carbon atoms which may have a substituent, a cycloalkyldiyl group having 3 to 12 carbon atoms which may have a substituent, or -B ^3- Ar ¹ -B ⁴ -yl, -CH ₂ - contained in the alkanediyl group having 2 to 12 carbon atoms may be substituted by -NH-, -O- or -S-; B ³ and B ⁴ are independently represented by a single bond or a C 2 to 6 alkanediyl group; Ar ¹ represents a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent; and R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, and a carbon number; An alkyl group of 1 to 6, an aryl group having 6 to 12 carbon atoms, a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms; and X ³ and X ⁴ each independently represent -NH- or -O-]. [In the formula (I-3), A ⁵ represents an alkanediyl group having 2 to 12 carbon atoms which may have a substituent, a cycloalkyldiyl group having 3 to 12 carbon atoms which may have a substituent, or ^* -B ⁵ -Ar ² -B ⁶ - group, -CH ₂ - contained in the alkyl 2 to 12 alkanediyl group may be substituted by -NH-, -O- or -S-, ^* represents a bond with X ⁵ ; B ⁵ Represents a single bond or an alkyldiyl group having 1 to 6 carbon atoms; B ⁶ represents a single bond or an alkyl 2 group having 1 to 6 carbon atoms; and Ar ² represents a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent. X ⁵ represents -CO-NH- ^* , -CO-O- ^* , -CO- ^* or a single bond, ^* represents a bonding bond with A ⁵ ; R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, An alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms, or bonded to each other to form an alkanediyl group having 1 to 12 carbon atoms. The rubber composition of claim 1, wherein R ¹ and R ² are a hydrogen atom. The rubber composition of claim 1 or 2, wherein A ¹ and A ² are each independently a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms. The rubber composition according to any one of claims 1 to 3, wherein X ¹ and X ² are -NH-. The rubber composition of claim 1, wherein R ³ and R ⁴ are a hydrogen atom. The rubber composition of claim 1 or 5, wherein A ³ and A ⁴ are each independently a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms. The rubber composition of claim 1, 5 or 6, wherein X ³ and X ⁴ are -NH-. The rubber composition of claim 1, wherein R ⁵ and R ⁶ are a hydrogen atom. The rubber composition of claim 1 or 8, wherein A ⁵ is a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent. The rubber composition of claim 1, 8 or 9, wherein X ⁵ represents a single bond, and A ⁵ represents a ^* -B ⁵ -Ar ² -B ⁶ - group (B ⁵ represents a single bond, and B ⁶ represents a single bond or a stretched alkyl group) base). The rubber composition according to any one of claims 1 to 10, wherein the rubber component is a natural rubber. The rubber composition according to any one of claims 1 to 11, which further contains a sulfur component. A vulcanized rubber obtained by subjecting the rubber composition of claim 12 to heat treatment. A tire which is processed by the rubber composition of claim 12 maker. An endless belt for a tire comprising a steel cord covered with a vulcanized rubber as claimed in claim 13. A tire carcass comprising a carcass fiber rope coated with a vulcanized rubber as claimed in claim 13. A tire wall for a tire, an inner liner for a tire, a tread crown for a tire, or a tread base for a tire, which comprises the vulcanized rubber of claim 13. A tire comprising the vulcanized rubber of claim 13. A method for improving the viscoelastic property of a vulcanized rubber, which comprises a compound represented by the formula (I-1), a compound represented by the formula (I-2), and a compound represented by the formula (I-3). a step of kneading one or more compounds of the composition group with the rubber component and the filler and the sulfur component, and a step of heat-treating the kneaded material obtained by the previous step, [In the formula (I-1), A ¹ and A ² each independently represent an alkanediyl group having 2 to 12 carbon atoms which may have a substituent, a cycloalkanediyl group having 3 to 12 carbon atoms which may have a substituent, or -B ^1- Ar-B ² - group, -CH ₂ - contained in the alkanediyl group having 2 to 12 carbon atoms may be substituted by -NH-, -O- or -S-; B ¹ and B ² are each independently represented by a single a bond or a C2 1 to 6 alkanediyl group; Ar represents a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent; and R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, and a carbon number of 1 to 2; 6 alkyl, aryl group having 6 to 12 carbon atoms, hydroxyl group or alkoxy group having 1 to 6 carbon atoms, or bonded to each other to form an alkanediyl group having 1 to 12 carbon atoms; X ¹ and X ² are each independently represented - NH- or -O-]. [In the formula (I-2), A ³ and A ⁴ each independently represent an alkanediyl group having 2 to 12 carbon atoms which may have a substituent, a cycloalkanediyl group having 3 to 12 carbon atoms which may have a substituent, or -B ^3- Ar ¹ -B ⁴ -yl, -CH ₂ - contained in the alkanediyl group having 2 to 12 carbon atoms may be substituted by -NH-, -O- or -S-; B ³ and B ⁴ are independently represented by a single bond or a C 2 to 6 alkanediyl group; Ar ¹ represents a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent; and R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, and a carbon number; An alkyl group of 1 to 6, an aryl group having 6 to 12 carbon atoms, a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms; and X ³ and X ⁴ each independently represent -NH- or -O-]. [In the formula (I-3), A ⁵ represents an alkanediyl group having 2 to 12 carbon atoms which may have a substituent, a cycloalkyldiyl group having 3 to 12 carbon atoms which may have a substituent, or ^* -B ⁵ -Ar ² -B ⁶ - group, -CH ₂ - contained in the alkyl 2 to 12 alkanediyl group may be substituted by -NH-, -O- or -S-, ^* represents a bond with X ⁵ ; B ⁵ Represents a single bond or an alkyldiyl group having 1 to 6 carbon atoms; B ⁶ represents a single bond or an alkyl 2 group having 1 to 6 carbon atoms; and Ar ² represents a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent. X ⁵ represents -CO-NH- ^* , -CO-O- ^* , -CO- ^* or a single bond, ^* represents a bonding bond with A ⁵ ; R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, An alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms, or bonded to each other to form an alkanediyl group having 1 to 12 carbon atoms. Use of one or more compounds selected from the group consisting of a compound represented by the formula (I-1), a compound represented by the formula (I-2), and a compound represented by the formula (I-3), Used to improve the viscoelastic properties of vulcanized rubber. [In the formula (I-1), A ¹ and A ² each independently represent an alkanediyl group having 2 to 12 carbon atoms which may have a substituent, a cycloalkanediyl group having 3 to 12 carbon atoms which may have a substituent, or -B ^1- Ar-B ² - group, -CH ₂ - contained in the alkanediyl group having 2 to 12 carbon atoms may be substituted by -NH-, -O- or -S-; B ¹ and B ² are each independently represented by a single a bond or a C 2 to 6 alkanediyl group; Ar represents a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent; and R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, and a carbon number of 1 to 2; 6 alkyl, aryl group having 6 to 12 carbon atoms, hydroxyl group or alkoxy group having 1 to 6 carbon atoms, or bonded to each other to form an alkanediyl group having 1 to 12 carbon atoms; X ¹ and X ² are each independently represented - NH- or -O-]. [In the formula (I-2), A ³ and A ⁴ each independently represent an alkanediyl group having 2 to 12 carbon atoms which may have a substituent, a cycloalkanediyl group having 3 to 12 carbon atoms which may have a substituent, or -B ^3- Ar ¹ -B ⁴ -yl, -CH ₂ - contained in the alkanediyl group having 2 to 12 carbon atoms may be substituted by -NH-, -O- or -S-; B ³ and B ⁴ are independently represented by a single bond or a C 2 to 6 alkanediyl group; Ar ¹ represents a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent; and R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, and a carbon number; An alkyl group of 1 to 6, an aryl group having 6 to 12 carbon atoms, a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms; and X ³ and X ⁴ each independently represent -NH- or -O-]. [In the formula (I-3), A ⁵ represents an alkanediyl group having 2 to 12 carbon atoms which may have a substituent, a cycloalkyldiyl group having 3 to 12 carbon atoms which may have a substituent, or ^* -B ⁵ -Ar ² -B ⁶ - group, -CH ₂ - contained in the alkanediyl group having 2 to 12 carbon atoms may be substituted by -NH-, -O- or -S-, ^* represents a bond with X ⁵ ; B ⁵ Represents a single bond or an alkyldiyl group having 1 to 6 carbon atoms; B ⁶ represents a single bond or an alkyl 2 group having 1 to 6 carbon atoms; and Ar ² represents a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent. X ⁵ represents -CO-NH- ^* , -CO-O- ^* , -CO- ^* or a single bond, ^* represents a bonding bond with A ⁵ ; R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, An alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms, or bonded to each other to form an alkanediyl group having 1 to 12 carbon atoms. A vulcanized rubber viscoelastic property improving agent comprising a group selected from the group consisting of a compound represented by the formula (I-1), a compound represented by the formula (I-2), and a compound represented by the formula (I-3). One or more compounds are used as active ingredients, [In the formula (I-1), A ¹ and A ² each independently represent an alkanediyl group having 2 to 12 carbon atoms which may have a substituent, a cycloalkanediyl group having 3 to 12 carbon atoms which may have a substituent, or -B ^1- Ar-B ² - group, -CH ₂ - contained in the alkanediyl group having 2 to 12 carbon atoms may be substituted by -NH-, -O- or -S-; B ¹ and B ² are each independently represented by a single a bond or a C 2 to 6 alkanediyl group; Ar represents a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent; and R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, and a carbon number of 1 to 2; 6 alkyl, aryl group having 6 to 12 carbon atoms, hydroxyl group or alkoxy group having 1 to 6 carbon atoms, or bonded to each other to form an alkanediyl group having 1 to 12 carbon atoms; X ¹ and X ² are each independently represented - NH- or -O-]. [In the formula (I-2), A ³ and A ⁴ each independently represent an alkanediyl group having 2 to 12 carbon atoms which may have a substituent, a cycloalkanediyl group having 3 to 12 carbon atoms which may have a substituent, or -B ^3- Ar ¹ -B ⁴ -yl, -CH ₂ - contained in the alkanediyl group having 2 to 12 carbon atoms may be substituted by -NH-, -O- or -S-; B ³ and B ⁴ are independently represented by a single bond or a C 2 to 6 alkanediyl group; Ar ¹ represents a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent; and R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, and a carbon number; An alkyl group of 1 to 6, an aryl group having 6 to 12 carbon atoms, a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms; and X ³ and X ⁴ each independently represent -NH- or -O-]. [In the formula (I-3), A ⁵ represents an alkanediyl group having 2 to 12 carbon atoms which may have a substituent, a cycloalkyldiyl group having 3 to 12 carbon atoms which may have a substituent, or ^* -B ⁵ -Ar ² -B ⁶ - group, -CH ₂ - contained in the alkanediyl group having 2 to 12 carbon atoms may be substituted by -NH-, -O- or -S-, ^* represents a bond with X ⁵ ; B ⁵ Represents a single bond or an alkyldiyl group having 1 to 6 carbon atoms; B ⁶ represents a single bond or an alkyl 2 group having 1 to 6 carbon atoms; and Ar ² represents a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent. ; X5 represents ^{-CO-NH- *, -CO-O-} *, -CO- * or a single bond, ^* represents a bond and A ⁵ of the junction bond; R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, C An alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms, or a bond to each other to form an alkanediyl group having 1 to 12 carbon atoms. a compound of the formula (I-1), [In the formula (I-1), A ¹ and A ² each independently represent an alkanediyl group having 2 to 12 carbon atoms which may have a substituent, a cycloalkanediyl group having 3 to 12 carbon atoms which may have a substituent, or -B ^1- Ar-B ² - group, -CH ₂ - contained in the alkanediyl group having 2 to 12 carbon atoms may be substituted by -NH-, -O- or -S-; B ¹ and B ² are each independently represented by a single a bond or a C 2 to 6 alkanediyl group; Ar represents a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent; and R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, and a carbon number of 1 to 2; 6 alkyl, aryl group having 6 to 12 carbon atoms, hydroxyl group or alkoxy group having 1 to 6 carbon atoms, or bonded to each other to form an alkanediyl group having 1 to 12 carbon atoms; X ¹ and X ² are each independently represented - NH- or -O-].