WO2018012452A1

WO2018012452A1 - Additive composition and rubber composition

Info

Publication number: WO2018012452A1
Application number: PCT/JP2017/025108
Authority: WO
Inventors: 泰生上北; 中野　貞之
Original assignee: 住友化学株式会社
Priority date: 2016-07-11
Filing date: 2017-07-10
Publication date: 2018-01-18

Abstract

An additive composition is provided which contains: a compound (C) having a base or structure (A) which can react with an olefinic double bond and a base or structure (B) which can react to or interact with carbon black; and a fatty acid metal salt.

Description

Additive composition and rubber composition

The present invention provides an additive composition capable of reducing the loss factor (tan δ) of a vulcanized rubber composition and suppressing an increase in the viscosity of the rubber composition, and the components of the additive composition, the rubber component, etc. The present invention relates to a rubber composition obtained by kneading.

In recent years, there has been a demand for improving the fuel efficiency of automobiles (ie, reducing fuel consumption) in response to environmental protection requirements. In the field of automobile tires, it is known that the fuel efficiency of automobiles is improved by reducing the loss factor of the vulcanized rubber composition used for tire manufacture.

For example, in Patent Document 1, in order to reduce the loss factor of the vulcanized rubber composition, the formula (D):

[Definition of groups in formula (D) is as described in Patent Document 1. In addition, Formula (D) is described in Patent Document 1 as Formula (I). ]
(Hereinafter sometimes abbreviated as compound (D)), a salt thereof, a solvate thereof, and a solvate of the salt thereof.

JP 2013-209605 A

As the mechanism by which the above compound (D) reduces the loss factor of the vulcanized rubber composition, for example, the olefinic double bond reacts with the olefinic double bond of the rubber component, and the amino group is carbon black. It reacts with a carboxy group present on the surface to bond a rubber component and carbon black. However, the present invention is not limited to such an estimation mechanism.

A compound (C) having a group or structure (A) capable of reacting with an olefinic double bond and a group or structure (B) capable of reacting or interacting with carbon black, such as compound (D), is described above. Thus, the loss coefficient of the vulcanized rubber composition can be reduced, but the rubber composition containing the compound (C) has a problem that its viscosity increases. The present invention has been made paying attention to such circumstances, and its purpose is to reduce the loss factor of the vulcanized rubber composition and to suppress the increase in the viscosity of the rubber composition. (I.e., an additive composition having a good balance between the effect of reducing the loss factor of the vulcanized rubber composition and the effect of suppressing the increase in viscosity of the rubber composition).

The present invention that can achieve the above object is as follows.
[1] a compound (C) having a group or structure (A) capable of reacting with an olefinic double bond, and a group or structure (B) capable of reacting or interacting with carbon black;
An additive composition containing a fatty acid metal salt.

[2] The additive composition according to the above [1], wherein the group or structure (A) is a group or structure capable of undergoing radical reaction or 1,3-dipole addition reaction with an olefinic double bond.
[3] The group or structure (A) is an olefinic double bond, an amide group, a maleimide ring, a 1H-imidazole ring, a benzoxazole ring, a benzothiazole ring, * -SSO ₃ H or a salt thereof, * -SS ^{- *, * - C≡N + -O} -, * - C≡N + -N - - *, structure represented by the formula (i), structural formula (ii) or formula, (iii) Structure represented by:

[In the above formula, * represents a bonding position. ]
The additive composition according to the above [1].

[4] The structure according to any one of [1] to [3], wherein the group or structure (B) is an unsubstituted or monosubstituted amino group, a benzene ring, a furan ring, an oxazole ring, or a 1H-benzimidazole ring. Additive composition.

[5] Compound (C) is represented by formula (I):

[In the formula (I),
R ¹ represents a C _2-12 alkanediyl group which may have one or more substituents, a C _3-10 cycloalkanediyl group which may have one or more substituents, or one or more substituents. Represents a divalent C _6-12 aromatic hydrocarbon group which may have the above-mentioned or a combination thereof.
R ² and R ³ each independently represent a hydrogen atom, a halogen atom, a hydroxy group, one or more C _1-6 alkoxy group which may have one or more substituents, or one or more substituents. Represents a good C _1-6 alkyl group, or a C _6-14 aryl group optionally having one or more substituents, or R ² and R ³ are bonded, and the carbon atom to which they are bonded; Together, they form a C _3-10 cycloalkenediyl group which may have one or more substituents.
R ⁴ is a hydroxy group, a C _1-6 alkoxy group which may have one or more substituents, a C _6-14 aryloxy group which may have one or more substituents, or —NR ^5. R ⁶ (wherein R ⁵ and R ⁶ each independently represents a hydrogen atom or a C _1-6 alkyl group optionally having one or more substituents).
X represents —NH— or —O—. ]
The additive composition according to the above [1], which is at least one selected from the group consisting of a compound represented by the formula: salt thereof, solvate thereof, and solvate of the salt thereof.
[6] The compound represented by the formula (I) is represented by the formula (II):

[In formula (II), R ¹ to R ⁴ and X are as defined above. ]
The additive composition according to [5], which is a compound represented by the formula:

[7] The additive composition according to [5] or [6] above, wherein R ¹ is a C _2-12 alkanediyl group or a divalent C _6-12 aromatic hydrocarbon group.
[8] The additive composition according to the above [5] or [6], wherein R ¹ is a C _2-12 alkanediyl group or a phenylene group.
[9] The additive composition according to [5] or [6], wherein R ¹ is a phenylene group.
[10] The additive composition according to the above [5] or [6], wherein R ¹ is a 1,4-phenylene group.

[11] The additive composition according to any one of [5] to [10], wherein R ² and R ³ are each independently a hydrogen atom or a C _1-6 alkyl group.
[12] The additive composition according to any one of [5] to [10], wherein R ² and R ³ are both hydrogen atoms.

[13] R ⁴ is a hydroxy group, a C _1-6 alkoxy group which may have one or more substituents, or a C _6-14 aryloxy group which may have one or more substituents. The additive composition according to any one of the above [5] to [12].
[14] The additive composition according to any one of [5] to [12], wherein R ⁴ is a hydroxy group or a C _1-6 alkoxy group.
[15] The additive composition according to any one of [5] to [12], wherein R ⁴ is a hydroxy group.

[16] The additive composition according to any one of [5] to [15], wherein X is —NH—.

[17] A solvent of the salt of the compound represented by the formula (I), wherein at least one selected from the group consisting of the compound represented by the formula (I), a salt thereof, a solvate thereof and a solvate of the salt thereof The additive composition according to any one of [5] to [16], which is a Japanese product.
[18] A carboxylate salt of the compound represented by formula (I), wherein at least one selected from the group consisting of the compound represented by formula (I), a salt thereof, a solvate thereof, and a solvate of the salt thereof The additive composition according to any one of [5] to [16], which is a solvate of

[19] The additive composition according to any one of [1] to [18], wherein the metal cation constituting the fatty acid metal salt is a monovalent or divalent metal cation.

[20] The additive composition according to any one of [1] to [18], wherein the metal cation constituting the fatty acid metal salt is a monovalent metal cation.
[21] The additive composition according to [20], wherein the monovalent metal cation is an alkali metal ion.
[22] The additive composition according to [21], wherein the alkali metal ion is potassium ion.

[23] The additive composition according to any one of [1] to [22], wherein the fatty acid anion constituting the fatty acid metal salt has 8 to 30 carbon atoms.
[24] The additive composition according to any one of [1] to [22], wherein the fatty acid anion constituting the fatty acid metal salt has 10 to 20 carbon atoms.
[25] The additive composition according to any one of [1] to [22], wherein the fatty acid anion constituting the fatty acid metal salt has 12 to 16 carbon atoms.

[26] The additive composition according to any one of [1] to [25], wherein the fatty acid anion constituting the fatty acid metal salt is a saturated fatty acid anion.

[27] The additive composition according to any one of [1] to [26], wherein the amount of the fatty acid metal salt is 10 to 1,000 parts by weight with respect to 100 parts by weight of the compound (C). .
[28] The additive composition according to any one of [1] to [26], wherein the amount of the fatty acid metal salt is 50 to 800 parts by weight with respect to 100 parts by weight of the compound (C).
[29] The additive composition according to any one of [1] to [26], wherein the amount of the fatty acid metal salt is 80 to 500 parts by weight with respect to 100 parts by weight of the compound (C).

[30] The additive as described in any one of [1] to [29] above, wherein the total amount of the compound (C) and the fatty acid metal salt is 50 to 100% by weight based on the total additive composition Composition.
[31] The additive according to any one of the above [1] to [29], wherein the total amount of the compound (C) and the fatty acid metal salt is 80 to 100% by weight based on the whole additive composition Composition.
[32] The additive composition according to any one of [1] to [29], comprising the compound (C) and a fatty acid metal salt.

[33] Compound (C) having a group or structure (A) capable of reacting with an olefinic double bond and a group or structure (B) capable of reacting or interacting with carbon black;
Fatty acid metal salts,
A rubber component having an olefinic double bond;
A rubber composition obtained by kneading carbon black.

[34] The rubber composition according to [33], wherein the group or structure (A) is a group or structure capable of undergoing radical reaction or 1,3-dipolar addition reaction with an olefinic double bond.
[35] The group or structure (A) is an olefinic double bond, an amide group, a maleimide ring, a 1H-imidazole ring, a benzoxazole ring, a benzothiazole ring, * -SSO ₃ H or a salt thereof, * -SS ^{- *, * - C≡N + -O} -, * - C≡N + -N - - *, structure represented by the formula (i), the structure represented by formula (ii) or the formula, The rubber composition according to [33], which has a structure represented by (iii).

[36] The structure according to any one of [33] to [35], wherein the group or structure (B) is an unsubstituted or monosubstituted amino group, a benzene ring, a furan ring, an oxazole ring, or a 1H-benzimidazole ring. Rubber composition.

[37] In the above [33], the compound (C) is at least one selected from the group consisting of the compound represented by the formula (I), a salt thereof, a solvate thereof and a solvate of the salt thereof. The rubber composition as described.
[38] The rubber composition according to [37], wherein the compound represented by the formula (I) is a compound represented by the formula (II).

[39] The rubber composition according to [37] or [38], wherein R ¹ is a C _2-12 alkanediyl group or a divalent C _6-12 aromatic hydrocarbon group.
[40] The rubber composition according to [37] or [38], wherein R ¹ is a C _2-12 alkanediyl group or a phenylene group.
[41] The rubber composition according to [37] or [38], wherein R ¹ is a phenylene group.
[42] The rubber composition according to the above [37] or [38], wherein R ¹ is a 1,4-phenylene group.

[43] The rubber composition according to any one of [37] to [42], wherein R ² and R ³ are each independently a hydrogen atom or a C _1-6 alkyl group.
[44] The rubber composition according to any one of [37] to [42], wherein R ² and R ³ are both hydrogen atoms.

[45] R ⁴ is a hydroxy group, a C _1-6 alkoxy group optionally having one or more substituents, or a C _6-14 aryloxy group optionally having one or more substituents. The rubber composition according to any one of [37] to [44].
[46] The rubber composition according to any one of [37] to [44], wherein R ⁴ is a hydroxy group or a C _1-6 alkoxy group.
[47] The rubber composition according to any one of [37] to [44], wherein R ⁴ is a hydroxy group.

[48] The rubber composition according to any one of [37] to [47], wherein X is —NH—.

[49] A solvent of the salt of the compound represented by formula (I), wherein at least one selected from the group consisting of the compound represented by formula (I), a salt thereof, a solvate thereof, and a solvate of the salt thereof The rubber composition according to any one of [37] to [48], which is a Japanese product.
[50] A carboxylate of the compound represented by the formula (I), wherein at least one selected from the group consisting of the compound represented by the formula (I), a salt thereof, a solvate thereof, and a solvate of the salt The rubber composition according to any one of [37] to [48], which is a solvate of

[51] In any one of the above [33] to [50], the amount of the compound (C) is 0.05 to 20 parts by weight with respect to 100 parts by weight of the rubber component having an olefinic double bond. The rubber composition as described.
[52] In any one of the above [33] to [50], the amount of the compound (C) is 0.1 to 10 parts by weight with respect to 100 parts by weight of the rubber component having an olefinic double bond. The rubber composition as described.
[53] In any one of the above [33] to [50], the amount of the compound (C) is 0.3 to 8 parts by weight with respect to 100 parts by weight of the rubber component having an olefinic double bond. The rubber composition as described.

[54] The rubber composition according to any one of [33] to [53], wherein the metal cation constituting the fatty acid metal salt is a monovalent or divalent metal cation.

[55] The rubber composition according to any one of [33] to [53], wherein the metal cation constituting the fatty acid metal salt is a monovalent metal cation.
[56] The rubber composition according to [55], wherein the monovalent metal cation is an alkali metal ion.
[57] The rubber composition according to [56], wherein the alkali metal ion is a potassium ion.

[58] The rubber composition according to any one of [33] to [57], wherein the fatty acid anion constituting the fatty acid metal salt has 8 to 30 carbon atoms.
[59] The rubber composition according to any one of [33] to [57], wherein the fatty acid anion constituting the fatty acid metal salt has 10 to 20 carbon atoms.
[60] The rubber composition according to any one of [33] to [57], wherein the fatty acid anion constituting the fatty acid metal salt has 12 to 16 carbon atoms.

[61] The rubber composition according to any one of [33] to [60], wherein the fatty acid anion constituting the fatty acid metal salt is a saturated fatty acid anion.

[62] The rubber composition according to any one of [33] to [61], wherein the amount of the fatty acid metal salt is 10 to 1,000 parts by weight with respect to 100 parts by weight of the compound (C).
[63] The rubber composition according to any one of [33] to [61], wherein the amount of the fatty acid metal salt is 50 to 800 parts by weight with respect to 100 parts by weight of the compound (C).
[64] The rubber composition according to any one of [33] to [61], wherein the amount of the fatty acid metal salt is 80 to 500 parts by weight with respect to 100 parts by weight of the compound (C).

[65] The rubber composition according to any one of [33] to [64], wherein the amount of carbon black is 20 to 80 parts by weight with respect to 100 parts by weight of the rubber component having an olefinic double bond. object.
[66] The rubber composition according to any one of [33] to [64], wherein the amount of carbon black is 30 to 70 parts by weight with respect to 100 parts by weight of the rubber component having an olefinic double bond. object.
[67] The rubber composition according to any one of [33] to [64], wherein the amount of carbon black is 30 to 60 parts by weight with respect to 100 parts by weight of the rubber component having an olefinic double bond. object.

[68] The rubber composition according to any one of [33] to [67], wherein the rubber component having an olefinic double bond includes a diene rubber.
[69] The rubber composition according to [68], wherein the amount of the diene rubber in the rubber component having an olefinic double bond is 50% by weight or more.
[70] The rubber composition according to [68], wherein the amount of the diene rubber in the rubber component having an olefinic double bond is 70 to 100% by weight.
[71] The rubber composition according to [68], wherein the amount of the diene rubber in the rubber component having an olefinic double bond is 80 to 100% by weight.

[72] The rubber composition according to [33] to [71], which is obtained by further kneading a sulfur component.
[73] The rubber composition according to [72], wherein the amount of the sulfur component is 0.01 to 30 parts by weight with respect to 100 parts by weight of the rubber component having an olefinic double bond.
[74] The rubber composition according to [72], wherein the amount of the sulfur component is 0.1 to 20 parts by weight with respect to 100 parts by weight of the rubber component having an olefinic double bond.
[75] The rubber composition according to [72], wherein the amount of the sulfur component is 0.1 to 10 parts by weight with respect to 100 parts by weight of the rubber component having an olefinic double bond.
[76] A vulcanized rubber composition obtained by vulcanizing the rubber composition according to any one of [72] to [75].

[77] a compound (C) having a group or structure (A) capable of reacting with an olefinic double bond and a group or structure (B) capable of reacting or interacting with carbon black;
Fatty acid metal salts,
A rubber component having an olefinic double bond;
A method for producing a rubber composition, comprising kneading carbon black.
[78] The method according to [77], further comprising kneading a sulfur component.
[79] A method for producing a vulcanized rubber composition comprising vulcanizing a rubber composition obtained by the method according to [78].

According to the present invention in which the compound (C) and the fatty acid metal salt are used in combination, the loss factor of the vulcanized rubber composition can be reduced and the increase in the viscosity of the rubber composition can be suppressed.

<Compound (C)>
The present invention is characterized by using a compound (C) having a group or structure (A) capable of reacting with an olefinic double bond and a group or structure (B) capable of reacting or interacting with carbon black. I will. Only 1 type may be used for a compound (C) and it may use 2 or more types together.

Examples of the group or structure (A) include a group or structure capable of undergoing radical reaction or 1,3-dipole addition reaction with an olefinic double bond. More specifically, examples of the group or structure (A) include an olefinic double bond, an amide group, a maleimide ring, a 1H-imidazole ring, a benzoxazole ring, a benzothiazole ring, * -SSO ₃ H or a salt thereof. , * —S—S— *, * —C≡N ⁺ —O ⁻ , * —C≡N ⁺ —N ⁻ — *, a structure represented by formula (i), a structure represented by formula (ii) Or a structure represented by formula (iii):

[In the above formula, * represents a bonding position. ]
Is mentioned. Any of the amide group, maleimide ring, 1H-imidazole ring, benzoxazole ring, and benzothiazole ring described above may be a monovalent group or a divalent group. Examples of the amide group include * —CO—NH ₂ — *, * —NHCO— *, * —CONH ₂ (in the above formula, * represents a bonding position). Examples of the maleimide ring include a 1-maleimidyl group. Examples of the 1H-imidazole ring include a 1-imidazolyl group. Examples of the benzoxazole ring include a benzoxazolyl group. Examples of the benzothiazole ring include a benzothiazolyl group.

Examples of the group or structure (B) include an unsubstituted or monosubstituted amino group (preferably an unsubstituted amino group), a benzene ring, a furan ring, an oxazole ring, or a 1H-benzimidazole ring. Any of the benzene ring, furan ring, oxazole ring and 1H-benzimidazole ring described above may be a monovalent group or a divalent group. Examples of the benzene ring include a phenyl group and a 1,4-phenylene group. Examples of the furan ring include 2-furyl group and 3-furyl group. Examples of the oxazole ring include a 2-oxazolyl group. Examples of the 1H-benzimidazole ring include a 2-benzimidazolyl group. These can react with the carboxy group of carbon black, or can interact with the aromatic ring of carbon black by π-π.

Specific examples of the compound (C) include the following compounds. However, the present invention is not limited to these compounds [In the following formula, A represents O, S or NH, m represents an integer of 1 to 6, n represents an integer of 1 to 6, and x represents 1 to Represents an integer of 4].

Compound (C) is preferably the formula (I):

Or a salt thereof, a solvate thereof, and a solvate of the salt thereof. Hereinafter, the “compound represented by the formula (I)” may be abbreviated as “compound (I)”. Similarly, compounds represented by other formulas may be abbreviated. “At least one selected from the group consisting of a compound represented by the formula (I), a salt thereof, a solvate thereof and a solvate of the salt” may be abbreviated as “compound (I) etc.”. is there.

R ¹ in the formula (I) is a C _2-12 alkanediyl group _optionally having one or more substituents, and a C _3-10 cycloalkanediyl group _optionally having one or more substituents. It represents a divalent C _6-12 aromatic hydrocarbon group which may have one or more substituents, or a combination thereof.

In the present specification, “C _xy ” means that the number of carbon atoms is x or more and y or less (x, y: integer).

In the present specification, the alkanediyl group includes both a linear alkanediyl group and a branched alkanediyl group. In the present specification, examples of the “C _2-12 alkanediyl group” include an ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, propylene group, 1-methyltrimethylene group, 2-methyl group. Trimethylene, 1-ethyltrimethylene, 2-ethyltrimethylene, 1-propyltrimethylene, 2-propyltrimethylene, 1-methyltetramethylene, 2-methyltetramethylene, 1-ethyltetra Methylene group, 2-ethyltetramethylene group, 1-propyltetramethylene group, 2-propyltetramethylene group, 1-methylpentamethylene group, 2-methylpentamethylene group, 3-methylpentamethylene group, 1-ethylpentamethylene group Group, 2-ethylpentamethylene group, 3-ethylpentamethylene group, 1-propyl Rupentamethylene group, 2-propylpentamethylene group, 3-propylpentamethylene group, 1-methylhexamethylene group, 2-methylhexamethylene group, 3-methylhexamethylene group, 1-ethylhexamethylene group, 2-ethyl Examples include a hexamethylene group, a 3-ethylhexamethylene group, a 1-propylhexamethylene group, a 2-propylhexamethylene group, and a 3-propylhexamethylene group.

Examples of the substituent that the C _2-12 alkanediyl group may have include, for example, a halogen atom, a C _1-6 alkoxy group, a C _1-6 alkoxy-carbonyl group, a C _1-7 acyl group, a C _{1 1- 7} acyl-oxy group, C _6-14 aryl group _optionally having one or more substituents. In addition, description of a halogen atom etc. is mentioned later.

In the present specification, examples of the “C _3-10 cycloalkanediyl group” include cyclopropane-1,2-diyl group, cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane -1,4-diyl group, cycloheptane-1,4-diyl group, cyclooctane-1,5-diyl group, cyclononane-1,5-diyl group, and cyclodecane-1,6-diyl group.

As the substituent that the C _3-10 cycloalkanediyl group may have, for example, a halogen atom, a C _1-6 alkyl group, a C _1-6 alkoxy group, a C _1-6 alkoxy-carbonyl group, C _{1 A -7} acyl group, a C _1-7 acyl-oxy group, and a C _6-14 aryl group _optionally having one or more substituents.

In the present specification, examples of the “divalent C _6-12 aromatic hydrocarbon group” include a phenylene group (eg, 1,4-phenylene group), a naphthylene group (eg, 1,4-naphthylene group, 1 , 5-naphthylene group, 2,6-naphthylene group, 2,7-naphthylene group) and biphenyldiyl group (eg, 1,1′-biphenyl-4,4′-diyl group).

Examples of the substituent that the divalent C _6-12 aromatic hydrocarbon group may have include a halogen atom, a C _1-6 alkyl group, a C _1-6 alkoxy group, and a C _1-6 alkoxy-carbonyl group. Group, C _1-7 acyl group, C _1-7 acyl-oxy group, C _6-14 aryl group, sulfo group. The sulfo group is a group represented by —SO ₃ H.

R ¹ is preferably a C _2-12 alkanediyl group or a divalent C _6-12 aromatic hydrocarbon group, more preferably a C _2-12 alkanediyl group or a phenylene group, still more preferably a phenylene group. Particularly preferred is a 1,4-phenylene group.

R ² and R ^{3 in} formula (I) are each independently a hydrogen atom, a halogen atom, a hydroxy group, an optionally substituted C _1-6 alkoxy group, or one or more substituents. Represents a C _1-6 alkyl group optionally having C 1, or a C _6-14 aryl group optionally having one or more substituents, or R ² and R ³ are bonded and they are bonded Together with the carbon atom to form a C _3-10 cycloalkenediyl group which may have one or more substituents.

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

In the present specification, the alkoxy group includes both a linear alkoxy group and a branched alkoxy group. In the present specification, examples of the “C _1-6 alkoxy group” include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, and a pentyloxy group. And hexyloxy group.

Examples of the substituent that the C _1-6 alkoxy group may have include, for example, a halogen atom, a C _1-6 alkoxy group, a C _1-6 alkoxy-carbonyl group, a C _1-7 acyl group, and a C _1-7. An acyl-oxy group, and a C _6-14 aryl group which may have one or more substituents.

In the present specification, the alkyl group includes both a linear alkyl group and a branched alkyl group. In the present specification, examples of the “C _1-6 alkyl group” include a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, s-butyl group, t-butyl group, 2 -Methylbutyl group, 2-ethylbutyl group, 3-methylbutyl group, 3-ethylbutyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group.

Examples of the substituent that the C _1-6 alkyl group may have include, for example, a halogen atom, a C _1-6 alkoxy group, a C _1-6 alkoxy-carbonyl group, a C _1-7 acyl group, a C _1-7 An acyl-oxy group, and a C _6-14 aryl group which may have one or more substituents.

In the present specification, examples of the “C _6-14 aryl group” include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, and a 9-anthryl group.

Examples of the substituent that the C _6-14 aryl group may have include, for example, a halogen atom, a C _1-6 alkyl group, a C _1-6 alkoxy group, a C _1-6 alkoxy-carbonyl group, and a C _1-7. Examples include an acyl group, a C _1-7 acyl-oxy group, a C _6-14 aryl group, and a sulfo group.

In the present specification, examples of the “C _1-7 acyl group” include a formyl group, a C _1-6 alkyl-carbonyl group (eg, acetyl group, pivaloyl group), and a benzoyl group.

In the present specification, examples of the “C _1-6 alkoxy group” contained in the C _1-6 alkoxy-carbonyl group and the “C _1-7 acyl group” contained in the C _1-7 acyl-oxy group include, for example, Can be mentioned.

Examples of the “C _3-10 cycloalkenediyl group formed by combining R ² and R ³ together with the carbon atom to which they are bonded” include a cyclopropene-1,2-diyl group, Cyclobutene-1,2-diyl group, cyclopentene-1,2-diyl group, cyclohexene-1,2-diyl group, cycloheptene-1,2-diyl group, cyclooctene-1,2-diyl group, cyclononene-1, Examples thereof include 2-diyl group and cyclodecene-1,2-diyl group.

Examples of the substituent that the C _3-10 cycloalkenediyl group may have include a halogen atom, a C _1-6 alkyl group, a C _1-6 alkoxy group, a C _1-6 alkoxy-carbonyl group, and a C _{1 A -7} acyl group, a C _1-7 acyl-oxy group, and a C _6-14 aryl group _optionally having one or more substituents.

R ² and R ³ are each independently preferably a hydrogen atom or a C _1-6 alkyl group, more preferably a hydrogen atom.

^{R 4} in formula (I), hydroxy groups (-OH), one or more substituents a _{C 1-6} alkoxy group optionally having one or more may have a substituent group _{C 6 -14} aryloxy group, or -NR ⁵ R ⁶ (wherein R ⁵ and R ⁶ are each independently a hydrogen atom or a C _1-6 alkyl group optionally having one or more substituents) Represents).

In the present specification, examples of the “C _6-14 aryl group” contained in the C _6-14 aryloxy group include those described above.

R ⁴ is preferably a hydroxy group, a C _1-6 alkoxy group optionally having one or more substituents, or a C _6-14 aryloxy group optionally having one or more substituents. More preferably a hydroxy group or a C _1-6 alkoxy group, and still more preferably a hydroxy group.

X in the formula (I) represents —NH— or —O—. X is preferably —NH—.

Compound (I) is preferably represented by the formula (II):

[In the formula (II), R ¹ to R ⁴ and X are as defined above. ]
It is a compound represented by these.

The salt of compound (I) includes (a) an amine salt formed by —NH ₂ of compound (I) and another acid, and (b) —NH— of compound (I) when X is —NH—. Examples include amine salts formed by-and other acids, and (c) carboxylates formed by -COOH of compound (I) and other bases when R ⁴ is a hydroxy group. The other acid that forms the amine salt of (a) and (b) may be either an organic acid or an inorganic acid, and the base that forms the carboxylate salt of (c) is an organic base or an inorganic base. Either is acceptable. The salt of compound (I) is preferably a carboxylate, more preferably at least one selected from the group consisting of an alkali metal carboxylate and an alkaline earth metal carboxylate, and more preferably an alkali carboxylate A metal salt, particularly preferably a sodium carboxylate.

The solvent that forms the solvate of compound (I) and the solvate of the salt of compound (I) may be water or an organic solvent (for example, methanol). The solvent forming the solvate is preferably water or methanol, more preferably water.

Compound (I) or the like is preferably a solvate of a salt of compound (I), more preferably a solvate of a carboxylate salt of compound (I), and more preferably a carboxylic acid of compound (I). At least one selected from the group consisting of hydrates of alkali metal salts and hydrates of carboxylic acid alkaline earth metal salts of compound (I), particularly preferably water of sodium salt of carboxylic acid of compound (I) It is a Japanese product.

Specific examples of compound (I) or a salt thereof are shown below.

Compound (I) and the like can be produced by the method described in Patent Document 1 or a method according to the method.

<Fatty acid metal salt>
One feature of the present invention is that a fatty acid metal salt is used. By the combined use of the compound (C) and the fatty acid metal salt, it is possible to achieve both reduction in the loss factor of the vulcanized rubber composition and suppression of increase in the viscosity of the rubber composition. Only one type of fatty acid metal salt may be used, or two or more types may be used in combination.

Examples of the metal cation constituting the fatty acid metal salt include a monovalent metal cation and a divalent metal cation. Examples of monovalent metal cations include alkali metal ions (eg, Li ⁺ , Na ⁺ , K ⁺ ) and the like. Examples of the divalent metal cation include alkaline earth metal ions (eg, Mg ²⁺ , Ca ²⁺ ), zinc ions (Zn ²⁺ ) and the like.

Among the fatty acid metal salts, the loss factor of the vulcanized rubber composition can be further reduced by using a salt of a fatty acid anion and a monovalent metal cation together with the compound (C). Accordingly, the metal cation constituting the fatty acid metal salt is preferably a monovalent metal cation, more preferably an alkali metal ion, and still more preferably a potassium ion (K ⁺ ).

The fatty acid anion constituting the fatty acid metal salt may be a saturated fatty acid anion or an unsaturated fatty acid anion. This anion is preferably a saturated fatty acid anion.

Examples of saturated fatty acids include caprylic acid (8 carbon atoms), pelargonic acid (9 carbon atoms), capric acid (10 carbon atoms), lauric acid (12 carbon atoms), myristic acid (14 carbon atoms), pentadecylic acid ( 15 carbon atoms, palmitic acid (16 carbon atoms), margaric acid (17 carbon atoms), stearic acid (18 carbon atoms), tuberculostearic acid (19 carbon atoms), arachidic acid (20 carbon atoms), behenic acid ( Examples thereof include 22 carbon atoms, lignoceric acid (24 carbon atoms), serotic acid (26 carbon atoms), montanic acid (28 carbon atoms), and mellic acid (30 carbon atoms).

Examples of unsaturated fatty acids include palmitoleic acid (16 carbon atoms), oleic acid (18 carbon atoms), linoleic acid (18 carbon atoms), eleostearic acid (18 carbon atoms), arachidonic acid (20 carbon atoms), etc. Is mentioned.

From the viewpoint of reducing the loss factor of the vulcanized rubber composition, the number of carbon atoms of the fatty acid anion constituting the fatty acid metal salt is preferably 8-30, more preferably 10-20, and still more preferably 12-16. It is.

The fatty acid anion constituting the fatty acid metal salt is preferably a C _8-30 saturated fatty acid anion, more preferably a C _10-20 saturated fatty acid anion, and still more preferably a C _12-16 saturated fatty acid anion.

The fatty acid metal salt is preferably a salt of a C _8-30 saturated fatty acid anion and a monovalent metal cation, more preferably a salt of a C _10-20 saturated fatty acid anion and an alkali metal ion, still more preferably C _12-16 saturated. It is a salt of a fatty acid anion and a potassium ion.

<Additive composition>
The additive composition of the present invention may contain another additive different from the compound (C) and the fatty acid metal salt. The total amount of the compound (C) and the fatty acid metal salt is preferably 50 to 100% by weight, more preferably 80 to 100% by weight, based on the whole additive composition of the present invention. The additive composition of the present invention is more preferably composed of the compound (C) and a fatty acid metal salt.

The amount of the fatty acid metal salt is preferably 10 to 1,000 parts by weight, more preferably 50 to 800 parts by weight, and still more preferably 80 to 500 parts by weight with respect to 100 parts by weight of the compound (C).

<Rubber composition, vulcanized rubber composition, and production method thereof>
The present invention provides a rubber composition obtained by kneading the above-mentioned compound (C), a fatty acid metal salt, a rubber component having an olefinic double bond, and carbon black, and a method for producing the same. The present invention also provides a rubber composition (hereinafter referred to as “sulfur”) obtained by kneading the above-mentioned compound (C), a fatty acid metal salt, a rubber component having an olefinic double bond, carbon black, and a sulfur component. A rubber composition containing a component "), and a method for producing the same. The present invention also provides a vulcanized rubber composition obtained by vulcanizing a rubber composition containing a sulfur component, and a method for producing the same.

The above-mentioned compound (C) may react with a rubber component having an olefinic double bond during kneading to form another compound. Moreover, the above-mentioned compound (C) decomposes during kneading, and this decomposition product may react with a rubber component having an olefinic double bond to form another compound. However, with current techniques for analyzing solid rubber compositions, it is not possible, or approximately practical, to directly identify the compounds that may be formed in the rubber composition by their structure or properties. Not right. Therefore, in the present specification and claims, the rubber composition of the present invention is obtained by kneading the above-mentioned compound (C), a fatty acid metal salt, a rubber component having an olefinic double bond, and carbon black. Specified. The same applies to the vulcanized rubber composition.

The amount of the compound (C) is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and still more preferably 0.1 to 100 parts by weight of the rubber component having an olefinic double bond. 3 to 8 parts by weight.

Rubber components having an olefinic double bond include natural rubber (NR) and modified natural rubber (eg, epoxidized natural rubber, deproteinized natural rubber); polyisoprene rubber (IR), styrene-butadiene copolymer rubber (SBR). ), Polybutadiene rubber (BR), acrylonitrile / butadiene copolymer rubber (NBR), isoprene / isobutylene copolymer rubber (IIR), ethylene / propylene / diene copolymer rubber (EPDM) and the like. . Only 1 type may be used for the rubber component which has an olefinic double bond, and 2 or more types may be used together.

The rubber component having an olefinic double bond preferably contains a diene rubber. Here, the diene rubber means a rubber made from a diene monomer having a conjugated double bond. Examples of the diene rubber include natural rubber, modified natural rubber, polyisoprene rubber, chloroprene rubber, styrene / butadiene copolymer rubber, polybutadiene rubber, and nitrile rubber. The diene rubber is preferably highly unsaturated, and more preferably natural rubber. It is also effective to use natural rubber in combination with another rubber (for example, styrene / butadiene copolymer rubber or polybutadiene rubber).

When a diene rubber (especially natural rubber) is used, the amount of the diene rubber in the rubber component having an olefinic double bond is preferably 50% by weight or more, more preferably 70 to 100% by weight, even more preferably. Is 80 to 100% by weight.

Examples of natural rubber include natural rubber of grades such as RSS # 1, RSS # 3, TSR20, and SIR20. Examples of the epoxidized natural rubber include those having a degree of epoxidation of 10 to 60 mol% (for example, ENR25 and ENR50 manufactured by Kumphuran Gasley). As the deproteinized natural rubber, a deproteinized natural rubber having a total nitrogen content of 0.3% by weight or less is preferable. Other modified natural rubbers include, for example, polar groups obtained by reacting natural rubber with 4-vinylpyridine, N, N-dialkylaminoethyl acrylate (for example, N, N-diethylaminoethyl acrylate), 2-hydroxy acrylate, etc. Modified natural rubber.

Examples of the SBR include emulsion polymerization SBR and solution polymerization SBR described in pages 210 to 211 of “Rubber Industry Handbook <Fourth Edition>” edited by the Japan Rubber Association. Among these, solution polymerization SBR is preferable for the rubber composition for treads.

Examples of the solution polymerization SBR include a modified solution polymerization SBR obtained by modification with a modifying agent and having at least one element of nitrogen, tin and silicon at the molecular end. Examples of the modifier include lactam compounds, amide compounds, urea compounds, N, N-dialkylacrylamide compounds, isocyanate compounds, imide compounds, silane compounds having an alkoxy group, aminosilane compounds, tin compounds and silane compounds having an alkoxy group. And a combined modifier of an alkyl acrylamide compound and a silane compound having an alkoxy group. These modifiers may be used alone or in combination. Specific examples of the modified solution polymerization SBR include solution polymerization SBR and JSR in which molecular ends are modified using 4,4′-bis (dialkylamino) benzophenone such as “Nipol (registered trademark) NS116” manufactured by Nippon Zeon Co., Ltd. Examples thereof include solution polymerization SBR in which molecular ends are modified using a tin halide compound such as “SL574” manufactured by the company, and silane-modified solution polymerization SBR such as “E10” and “E15” manufactured by Asahi Kasei.

Also, oil-extended SBR in which oil such as process oil or aroma oil is added to emulsion polymerization SBR and solution polymerization SBR is also preferable for the rubber composition for tread.

The BR may be either a solution polymerization BR having a low vinyl content or a solution polymerization BR having a high vinyl content, but a solution polymerization BR having a high vinyl content is preferred. A modified solution polymerization BR having at least one element of nitrogen, tin, or silicon at the molecular end obtained by modification with a modifier is particularly preferred. Examples of the modifier include 4,4′-bis (dialkylamino) benzophenone, tin halide compound, lactam compound, amide compound, urea compound, N, N-dialkylacrylamide compound, isocyanate compound, imide compound, and alkoxy group. Examples thereof include a silane compound having an alkoxy group (for example, a trialkoxysilane compound), an aminosilane compound, a tin compound and a silane compound having an alkoxy group, and a combined modifier having an alkylacrylamide compound and an silane compound having an alkoxy group. These modifiers may be used alone or in combination. Examples of the modified solution polymerization BR include tin-modified BR such as “Nipol (registered trademark) BR 1250H” manufactured by Nippon Zeon.

BR can be preferably used for a rubber composition for a tread and a rubber composition for a sidewall. BR may be used in a blend with SBR and / or natural rubber (NR). In the rubber composition for a tread, in the rubber component having an olefinic double bond, for example, the amount of SBR and / or NR is 60 to 100% by weight, and the amount of BR is 0 to 40% by weight. In the rubber composition for a sidewall, in the rubber component having an olefinic double bond, preferably, the amount of SBR and / or NR is 10 to 70% by weight, and the amount of BR is 90 to 30% by weight. More preferably, the amount of NR is 40 to 60% by weight and the amount of BR is 60 to 40% by weight. For the rubber composition for a tread and the rubber composition for a sidewall, a blend of modified SBR and non-modified SBR, a blend of modified BR and non-modified BR, and the like can be preferably used.

When the rubber composition is used for tire treads, for example, in passenger car tires, the rubber component having an olefinic double bond uses SBR, which is excellent in wear resistance and hysteresis loss reduction performance, as a base material. In tires, a higher strength NR is optionally used as a base material together with SBR, and it is possible to blend these base materials with BR as necessary to obtain a tread having excellent wear resistance, fatigue resistance, and rebound resilience. Since it is obtained, it is preferable.

When rubber composition is used for tire sidewall, NR and SBR are blended for passenger car tires, or NR and BR are blended, and NR and BR are blended for truck and bus tires. It is preferable to be used because bending resistance and crack growth resistance are obtained.

When the rubber composition is used for a tire belt, use of NR and / or IR as a rubber component having an olefinic double bond can provide high elasticity and good adhesion to reinforcing fibers. Therefore, it is preferable.

When the rubber composition is used as an inner liner of a tire, it is difficult to use a blend of IIR and SBR and NR or a blend of IIR and NR as a rubber component having an olefinic double bond. It is preferable because permeability and bending resistance can be obtained.

Examples of the carbon black include those described on page 494 of “Rubber Industry Handbook <Fourth Edition>” edited by the Japan Rubber Association. Carbon black may use only 1 type and may use 2 or more types together. As carbon black, HAF (High Ablation Furnace), SAF (Super Abrasion Furnace), ISAF (Intermediate SAF), ISAF-HM (Intermediate SAF-HighFurgence), FEF (FastEurFastGurP). SRF (Semi-Reinforcing Furnace) is preferable.

The amount of carbon black is preferably 20 to 80 parts by weight, more preferably 30 to 70 parts by weight, and further preferably 30 to 60 parts by weight with respect to 100 parts by weight of the rubber component having an olefinic double bond.

Examples of the sulfur component include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, highly dispersible sulfur, morpholine disulfide, and tetramethylthiuram disulfide. Usually, powdered sulfur is preferable, and insoluble sulfur is preferable when the rubber composition is used for manufacturing a tire member having a large amount of sulfur such as a belt member.

The amount of the sulfur component is preferably 0.01-30 parts by weight, more preferably 0.1-20 parts by weight, still more preferably 0.1-0.1 parts by weight, relative to 100 parts by weight of the rubber component having an olefinic double bond. 10 parts by weight.

In the present invention, in addition to the compound (C), fatty acid metal salt, rubber component having an olefinic double bond, carbon black, and sulfur component, other components known in the rubber field may be used. Other components include, for example, fillers other than carbon black, compounds capable of binding to silica, vulcanization accelerators, vulcanization accelerators, resins, viscoelasticity improvers, anti-aging agents, oils, waxes, and crackers. Agents, retarders, compounds having an oxyethylene unit, and catalysts (such as cobalt naphthenate). As for another component, all may use only 1 type and may use 2 or more types together.

Examples of fillers other than carbon black include silica (for example, hydrous silica), aluminum hydroxide, bituminous coal pulverized material, talc, clay (particularly, calcined clay), and titanium oxide.

Examples of the silica include silica having a CTAB specific surface area of 50 to 180 m ² / g and silica having a nitrogen adsorption specific surface area of 50 to 300 m ² / g. Examples of commercially available products of silica include “Nipsil (registered trademark) AQ” and “Nipsil (registered trademark) AQ-N” manufactured by Tosoh Silica Co., Ltd., “Ultrasil (registered trademark) VN3” and “Ultrasil” manufactured by Degussa. (Registered trademark) VN3-G "," Ultrasil (registered trademark) 360 "," Ultrasil (registered trademark) 7000 "," Zeosil (registered trademark) 115GR "," Zeosil (registered trademark) 1115MP "manufactured by Rhodia, “Zeosil (registered trademark) 1205MP”, “Zeosil (registered trademark) Z85MP” are mentioned. (I) silica having a pH of 6 to 8, (ii) silica containing 0.2 to 1.5% by weight of sodium, (iii) true spherical silica having a roundness of 1 to 1.3, (iv) ) Silicone oil (eg, dimethyl silicone oil), organosilicon compound containing ethoxysilyl group, silica surface-treated with alcohol (eg, ethanol, polyethylene glycol), etc. (v) two or more different nitrogen adsorption specific surface areas Mixtures of silica with can be used as fillers. When the rubber composition is used in a passenger car tread, the amount of silica is preferably in the range of 10 to 120 parts by weight with respect to 100 parts by weight of the rubber component having an olefinic double bond. When silica is blended, the silica / carbon black weight ratio is preferably 0.7 / 1 to 1 / 0.1.

Examples of the aluminum hydroxide include aluminum hydroxide having a nitrogen adsorption specific surface area of 5 to 250 m ² / g and a DOP oil supply amount of 50 to 100 ml / 100 g.

The average particle size of the bituminous coal pulverized product is usually 0.1 mm or less, preferably 0.05 mm or less, more preferably 0.01 mm or less. Even if a bituminous coal pulverized product having an average particle size exceeding 0.1 mm is used, the hysteresis loss of the rubber composition may not be sufficiently reduced, and the fuel efficiency may not be sufficiently improved. Further, when the rubber composition is used as an inner liner composition, the air permeation resistance of the composition may not be sufficiently improved even when a bituminous coal pulverized product having an average particle size exceeding 0.1 mm is used. is there.

The lower limit of the average particle diameter of the bituminous coal pulverized product is not particularly limited, but is preferably 0.001 mm or more. If it is less than 0.001 mm, the cost tends to increase. The average particle size of the bituminous coal pulverized product is a mass-based average particle size calculated from a particle size distribution measured according to JIS Z 8815-1994.

The specific gravity of the bituminous coal pulverized product is preferably 1.6 or less, more preferably 1.5 or less, and even more preferably 1.3 or less. When a bituminous coal pulverized product having a specific gravity exceeding 1.6 is used, the specific gravity of the entire rubber composition increases, and there is a possibility that the fuel efficiency of the tire cannot be sufficiently improved. The specific gravity of the pulverized bituminous coal is preferably 0.5 or more, and more preferably 1.0 or more. If a bituminous coal pulverized product having a specific gravity of less than 0.5 is used, workability during kneading may be deteriorated.

When using a bituminous coal pulverized product, the amount is usually 5 parts by weight or more, preferably 10 parts by weight or more, and usually 70 parts by weight or less, preferably 100 parts by weight of the rubber component having an olefinic double bond. Is 60 parts by weight or less. If this amount is less than 5 parts by weight, the effect of the pulverized bituminous coal may not be sufficiently obtained, and if it exceeds 70 parts by weight, the workability during kneading may be deteriorated.

When silica is used as the filler, it is preferable to use a compound capable of binding to silica such as a silane coupling agent. Examples of the compound include bis (3-triethoxysilylpropyl) tetrasulfide (eg, “Si-69” manufactured by Degussa), bis (3-triethoxysilylpropyl) disulfide (eg, “Si— 75 "), bis (3-diethoxymethylsilylpropyl) tetrasulfide, bis (3-diethoxymethylsilylpropyl) disulfide, 3-octanoylthiopropyltriethoxysilane (also known as" octanethioic acid S- [3- ( Triethoxysilyl) propyl] ester ", for example," NXT silane "manufactured by General Electronic Silicons), octanethioic acid S- [3-{(2-methyl-1,3-propanedialkoxy) ethoxysilyl} propyl] ester , Octanethioic acid S- [3-{(2-methyl-1,3 Propane dialkoxy) methylsilyl} propyl] ester, methyltrimethoxysilane, methyltriethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (methoxyethoxy) silane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, 3-methacryloxy Propyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyl Liethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-isocyanato Mention may be made of propyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane. Among these, bis (3-triethoxysilylpropyl) tetrasulfide (eg “Si-69” manufactured by Degussa), bis (3-triethoxysilylpropyl) disulfide (eg “Si-75” manufactured by Degussa) ), 3-octanoylthiopropyltriethoxysilane (for example, “NXT silane” manufactured by General Electronic Silicons) is preferable.

The addition timing of the compound capable of binding to silica is not particularly limited, but it is preferably blended with a rubber component having an olefinic double bond at the same time as silica. When silica and a compound capable of binding to silica are used, the amount of the compound capable of binding to silica is preferably 2 to 10 parts by weight, more preferably 7 to 9 parts by weight with respect to 100 parts by weight of silica. When a compound capable of binding to silica is blended, the blending temperature is preferably 80 to 200 ° C, more preferably 110 to 180 ° C.

When silica is used as a filler, in addition to compounds capable of binding to silica, monohydric alcohols such as ethanol, butanol and octanol; ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, pentaerythritol, poly It is also preferable to use polyhydric alcohols such as ether polyols; N-alkylamines; amino acids; liquid polybutadienes whose molecular ends are carboxy-modified or amine-modified.

Examples of vulcanization accelerators include thiazole-based vulcanization accelerators described in pages 412 to 413 of Rubber Industry Handbook <Fourth Edition> (issued by the Japan Rubber Association on January 20, 1994), Examples thereof include phenamide vulcanization accelerators and guanidine vulcanization accelerators.

Specific examples of the vulcanization accelerator include N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), N-tert-butyl-2-benzothiazolylsulfenamide (BBS), and N, N-dicyclohexene. Xyl-2-benzothiazolylsulfenamide (DCBS), 2-mercaptobenzothiazole (MBT), dibenzothiazyl disulfide (MBTS), and diphenylguanidine (DPG).

When only carbon black is used as the filler, N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), N-tert-butyl-2-benzothiazolylsulfenamide (BBS) are used as vulcanization accelerators. ), N, N-dicyclohexyl-2-benzothiazolylsulfenamide (DCBS) or dibenzothiazyl disulfide (MBTS) and diphenylguanidine (DPG) are preferably used in combination. When silica and carbon black are used in combination as fillers, N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), N-tert-butyl-2-benzothiazolylsulfene as vulcanization accelerators It is preferable to use either amide (BBS), N, N-dicyclohexyl-2-benzothiazolylsulfenamide (DCBS) or dibenzothiazyl disulfide (MBTS) and diphenylguanidine (DPG).

The ratio of the sulfur component to the vulcanization accelerator is not particularly limited, but the weight ratio of the sulfur component / vulcanization accelerator is preferably 1/10 to 10/1, more preferably 1/5 to 5/1, A preferred range is 1/2 to 2/1. In addition, in a rubber member mainly composed of natural rubber, EV vulcanization, which is a method of improving heat resistance, in which the ratio of sulfur component / vulcanization accelerator is 1 or less, is preferably used in applications that particularly require improvement in heat resistance. It is done.

Examples of the vulcanization accelerating aid include zinc oxide, stearic acid, citraconimide compound, alkylphenol / sulfur chloride condensate, organic thiosulfate compound, and formula (III):
R ¹⁶ —S—S—R ¹⁷ —S—S—R ¹⁸ (III)
(Wherein R ¹⁷ represents a C _2-10 alkanediyl group, and R ¹⁶ and R ¹⁸ each independently represents a monovalent organic group containing a nitrogen atom.)
The compound represented by these is mentioned. In addition, in this invention, zinc oxide is included in the concept of a vulcanization | cure acceleration | stimulation adjuvant, and is not included in the concept of the above-mentioned filler.

As the vulcanization acceleration aid, zinc oxide, stearic acid, and citraconic imide compounds are preferable, and zinc oxide and stearic acid are more preferable.

When zinc oxide is used, the amount is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 15 parts by weight, still more preferably 100 parts by weight of the rubber component having an olefinic double bond. Is 0.1 to 10 parts by weight. When stearic acid is used, the amount is preferably 0.01 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, still more preferably 100 parts by weight of the rubber component having an olefinic double bond. Is 0.1 to 5 parts by weight.

As the citraconimide compound, biscitraconimides are preferable because they are thermally stable and have excellent dispersibility in a rubber component having an olefinic double bond. Specifically, 1,2-biscitraconimidomethylbenzene, 1,3-biscitraconimidomethylbenzene, 1,4-biscitraconimidomethylbenzene, 1,6-biscitraconimidomethylbenzene, 2,3-bis Citraconimidomethyltoluene, 2,4-biscitraconimidomethyltoluene, 2,5-biscitraconimidomethyltoluene, 2,6-biscitraconimidomethyltoluene, 1,2-biscitraconimidoethylbenzene, 1,3-biscitracon Imidoethylbenzene, 1,4-biscitraconimidoethylbenzene, 1,6-biscitraconimidoethylbenzene, 2,3-biscitraconimidoethyltoluene, 2,4-biscitraconimidoethyltoluene, 2,5-biscitraconimidoethyltoluene Emissions, such as 2,6-biscitraconimide ethyltoluene and the like.

Among citraconic imide compounds, a vulcanized rubber composition that is particularly thermally stable, particularly excellent in dispersibility in a rubber component having an olefinic double bond, and having high hardness (Hs) can be obtained ( For the reason of (reversion control), 1,3-biscitraconimidomethylbenzene represented by the following formula is preferable.

Since a vulcanized rubber composition having high hardness (Hs) can be obtained as a vulcanization acceleration aid, the formula (IV):

[Wherein n is an integer of 0 to 10, each X is independently an integer of 2 to 4, and each R ¹⁹ is independently a C _5-12 alkyl group. ]
It is preferable to use an alkylphenol-sulfur chloride condensate represented by

N is preferably an integer of 1 to 9 because the dispersibility of the alkylphenol / sulfur chloride condensate (IV) in the rubber component having an olefinic double bond is good.

When X exceeds 4, the alkylphenol-sulfur chloride condensate (IV) tends to become thermally unstable. When X is 1, the sulfur content (sulfur in the alkylphenol-sulfur chloride condensate (IV)) Less weight). X is preferably 2 for the reason that high hardness can be expressed efficiently (reversion suppression).

R ¹⁹ is a C _5-12 alkyl group. R ¹⁹ is preferably a C _6-9 alkyl group because the dispersibility of the alkylphenol / sulfur chloride condensate (IV) in the rubber component having an olefinic double bond is good.

As a specific example of the alkylphenol / sulfur chloride condensate (IV), n is 0 to 10, X is 2, R ¹⁹ is an octyl group, and the sulfur content is 24% by weight. The tack roll V200 is mentioned.

As a vulcanization acceleration aid, a vulcanized rubber composition having high hardness (Hs) can be obtained (reversion suppression).
HO ₃ S—S— (CH ₂ ) _k —S—SO ₃ H (V)
[Wherein k is an integer of 3 to 10. ]
It is preferable to use a salt of an organic thiosulfate compound represented by the formula (hereinafter sometimes referred to as “organic thiosulfate compound salt (V)”). An organic thiosulfate compound salt (V) containing crystal water may be used. Examples of the organic thiosulfate compound salt (V) include lithium salt, potassium salt, sodium salt, magnesium salt, calcium salt, barium salt, zinc salt, nickel salt, cobalt salt, etc., potassium salt, sodium salt Is preferred.

K is an integer of 3 to 10, preferably an integer of 3 to 6. When k is 2 or less, there is a tendency that sufficient heat fatigue resistance cannot be obtained. When k is 11 or more, the effect of improving the heat fatigue resistance by the organic thiosulfate compound salt (V) may not be sufficiently obtained. .

The organic thiosulfate compound salt (V) is preferably a sodium salt monohydrate or a sodium salt dihydrate from the viewpoint of being stable at normal temperature and pressure, and obtained from sodium thiosulfate from the viewpoint of cost. The organic thiosulfate compound salt (V) is more preferable, and sodium 1,6-hexamethylenedithiosulfate dihydrate represented by the following formula is more preferable.

Disperse well in the rubber component having an olefinic double bond and, when used in combination with alkylphenol / sulfur chloride condensate (IV), inserted in the middle of -S _X -crosslink of alkylphenol / sulfur chloride condensate (IV) Because it is possible to form a hybrid bridge with the alkylphenol-sulfur chloride condensate (IV):
R ¹⁶ —S—S—R ¹⁷ —S—S—R ¹⁸ (III)
(Wherein R ¹⁷ represents a C _2-10 alkanediyl group, and R ¹⁶ and R ¹⁸ each independently represents a monovalent organic group containing a nitrogen atom.)
It is preferable to use the compound represented by these as a vulcanization | cure acceleration | stimulation adjuvant with alkylphenol and sulfur chloride condensate (IV).

R ¹⁷ is a C _2-10 alkanediyl group, preferably a C _4-8 alkanediyl group, and more preferably a linear C _4-8 alkanediyl group. R ¹⁷ is preferably linear. When the carbon number of R ¹⁷ is 1 or less, thermal stability may be poor. If the carbon number of R ¹⁷ is 11 or more, the distance between the polymers via the vulcanization accelerating aid becomes long, and the effect of adding the vulcanization accelerating aid may not be obtained.

R ¹⁶ and R ¹⁸ are each independently a monovalent organic group containing a nitrogen atom. As the monovalent organic group containing a nitrogen atom, those containing at least one aromatic ring are preferred, and those containing an aromatic ring and a ═N—C (═S) — group (thiocarbamoyl group) are more preferred. R ¹⁶ and R ¹⁸ may be the same or different, but are preferably the same for reasons such as ease of production.

Examples of the compound (III) include 1,2-bis (dibenzylthiocarbamoyldithio) ethane, 1,3-bis (dibenzylthiocarbamoyldithio) propane, 1,4-bis (dibenzylthiocarbamoyldithio) butane 1,5-bis (dibenzylthiocarbamoyldithio) pentane, 1,6-bis (dibenzylthiocarbamoyldithio) hexane, 1,7-bis (dibenzylthiocarbamoyldithio) heptane, 1,8-bis (di Examples include benzylthiocarbamoyldithio) octane, 1,9-bis (dibenzylthiocarbamoyldithio) nonane, 1,10-bis (dibenzylthiocarbamoyldithio) decane. Of these, 1,6-bis (dibenzylthiocarbamoyldithio) hexane is preferred because it is thermally stable and has excellent dispersibility in a rubber component having an olefinic double bond.

Examples of commercially available products of compound (III) include VULCUREN TRIAL PRODUCT KA9188 and VULCUREN VP KA9188 (1,6-bis (dibenzylthiocarbamoyldithio) hexane) manufactured by Bayer.

The rubber composition may contain an organic compound such as resorcinol, a resin such as a resorcinol resin, a modified resorcinol resin, a cresol resin, a modified cresol resin, a phenol resin, and a modified phenol resin. By including resorcinol and these resins, the elongation at break and the complex elastic modulus of the vulcanized rubber composition can be improved. Moreover, when using a rubber composition for manufacture of the rubber product which contacts a code | cord | chord, adhesiveness with a code | cord | chord can be improved by including resorcinol and resin.

Examples of resorcinol include resorcinol manufactured by Sumitomo Chemical Co., Ltd. Examples of the resorcinol resin include resorcinol / formaldehyde condensate. Examples of the modified resorcinol resin include those obtained by alkylating a part of the resorcinol resin repeating unit. Specifically, Penacolite resins B-18-S and B-20 manufactured by India Spec, Sumikanol 620 manufactured by Taoka Chemical Industries, R-6 manufactured by Uniroyal, SRF1501 manufactured by Schenectady Chemical, Ash Examples include Arofine 7209 manufactured by Land.

Examples of the cresol resin include a cresol / formaldehyde condensate. Examples of the modified cresol resin include those obtained by modifying the terminal methyl group of the cresol resin to a hydroxy group, and those obtained by alkylating some of the repeating units of the cresol resin. Specifically, Sumikanol 610 manufactured by Taoka Chemical Industry Co., Ltd., PR-X11061 manufactured by Sumitomo Bakelite Co., Ltd., and the like can be given.

Examples of phenolic resins include phenol / formaldehyde condensates. Examples of modified phenolic resins include resins obtained by modifying phenolic resins with cashew oil, tall oil, linseed oil, various animal and vegetable oils, unsaturated fatty acids, rosin, alkylbenzene resins, aniline, melamine, and the like.

Examples of other resins include methoxylated methylol melamine resins such as “SUMIKANOL 507AP” manufactured by Sumitomo Chemical Co., Ltd .; Coumarone resin NG4 (softening point 81-100 ° C.) manufactured by Nippon Steel Chemical Co., Ltd. Coumarone-indene resin such as “Process Resin AC5” (softening point 75 ° C.); Terpene resin such as terpene resin, terpene / phenol resin, and aromatic modified terpene resin; “Nicanol® A70” manufactured by Mitsubishi Gas Chemical Company ”(Softening point 70 to 90 ° C.) and the like; hydrogenated rosin derivatives; novolac alkylphenol resins; resol alkylphenol resins; C5 petroleum resins; liquid polybutadiene.

Examples of the viscoelasticity improver include N, N′-bis (2-methyl-2-nitropropyl) -1,6-hexanediamine (for example, “Sumifine (registered trademark) 1162” manufactured by Sumitomo Chemical Co., Ltd.), Dithiouracil compounds described in JP-A-63-23942, “Tactrol (registered trademark) AP”, “Tactrol (registered trademark) V-200” manufactured by Taoka Chemical Co., Ltd., alkylphenols described in JP-A-2009-138148, Sulfur chloride condensate, bis (3-triethoxysilylpropyl) tetrasulfide (eg “Si-69” manufactured by Degussa), bis (3-triethoxysilylpropyl) disulfide (eg “Si-75” manufactured by Degussa) ), Bis (3-diethoxymethylsilylpropyl) tetrasulfide, bis (3-diethoxymethylsilylpropyl) Pyr) disulfide, octanethioic acid S- [3- (triethoxysilyl) propyl] ester, octanethioic acid S- [3-{(2-methyl-1,3-propanedialkoxy) ethoxysilyl} propyl] ester, octanethioic acid S- [3-{(2-methyl-1,3-propanedialkoxy) methylsilyl} propyl] ester, methyltrimethoxysilane, methyltriethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, Ethyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (methoxyethoxy) sila , Phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, (3-glycidoxypropyl) trimethoxysilane, (3-glycine Sidoxypropyl) triethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane , 3-isocyana Topropyltriethoxysilane, 1,6-bis (dibenzylthiocarbamoyldithio) hexane (for example, “KA9188” manufactured by Bayer), 1,6-hexamethylenedithiosulfate disodium salt dihydrate, 1,3- Bis (citraconimidomethyl) benzene (for example, “Parkalink 900” manufactured by Flexis), 1-benzoyl-2-phenylhydrazide, 1-hydroxy-N ′-(1-methylethylidene) -2-naphthoic acid hydrazide, 3 -Hydroxy-N ′-(1-methylethylidene) -2-naphthoic acid hydrazide, 1-hydroxy-N ′-(1-methylpropylidene) -2-naphthoic acid hydrazide described in JP-A-2004-91505, 3 -Hydroxy-N ′-(1-methylpropylidene) -2-naphthoic acid hydrazide, 1 Hydroxy-N ′-(1,3-dimethylbutylidene) -2-naphthoic acid hydrazide, 3-hydroxy-N ′-(1,3-dimethylbutylidene) -2-naphthoic acid hydrazide, 1-hydroxy-N ′ Carboxylic acid hydrazide derivatives such as-(2-furylmethylene) -2-naphthoic acid hydrazide, 3-hydroxy-N '-(2-furylmethylene) -2-naphthoic acid hydrazide, and the like described in JP 2000-190704 A -Hydroxy-N '-(1,3-dimethylbutylidene) -2-naphthoic acid hydrazide, 3-hydroxy-N'-(1,3-diphenylethylidene) -2-naphthoic acid hydrazide, 3-hydroxy-N ' -(1-methylethylidene) -2-naphthoic acid hydrazide, bismercaptooxadi described in JP-A-2006-328310 Tetrazole compounds, pyrithione salt compounds described in JP-2009-40898, include cobalt hydroxide compounds described in JP-A No. 2006-249361.

Among them, N, N′-bis (2-methyl-2-nitropropyl) -1,6-hexanediamine (for example, “Sumifine® 1162” manufactured by Sumitomo Chemical Co., Ltd.), bis (3-triethoxysilyl) Propyl) tetrasulfide (eg “Si-69” manufactured by Degussa), bis (3-triethoxysilylpropyl) disulfide (eg “Si-75” manufactured by Degussa), 1,6-bis (dibenzylthiocarbamoyl) Dithio) hexane (for example, “KA9188” manufactured by Bayer), hexamethylene bisthiosulfate disodium salt dihydrate, 1,3-bis (citraconimidomethyl) benzene (for example, “Parkalink 900” manufactured by Flexis) "Tacchiroll (registered trademark) AP", "Tacchiroll (registered trademark) V-20" manufactured by Taoka Chemical Industries, Ltd. "It is preferable.

Examples of the anti-aging agent include those described on pages 436 to 443 of “Rubber Industry Handbook <Fourth Edition>” edited by the Japan Rubber Association. Anti-aging agents include N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine (abbreviation “6PPD”, for example, “Antigen (registered trademark) 6C” manufactured by Sumitomo Chemical), reaction of aniline and acetone. Products (abbreviated as “TMDQ”), poly (2,2,4-trimethyl-1,2-) dihydroquinoline) (for example, “Antioxidant FR” manufactured by Matsubara Sangyo Co., Ltd.), synthetic wax (paraffin wax, etc.), plant A wax is preferably used.

When an anti-aging agent is used, the amount thereof is preferably 0.01 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, more preferably 100 parts by weight of the rubber component having an olefinic double bond. The amount is preferably 0.1 to 5 parts by weight.

Examples of the oil include process oil and vegetable oil. Examples of the process oil include paraffinic process oil, naphthenic process oil, and aromatic process oil. Examples of commercially available products include aromatic oil (“NC-140” manufactured by Cosmo Oil Co., Ltd.) and process oil (“Diana Process PS32” manufactured by Idemitsu Kosan Co., Ltd.).

Examples of the wax include “Sannok (registered trademark) wax” manufactured by Ouchi Shinsei Chemical Co., Ltd. and “OZOACE-0355” manufactured by Nippon Seiwa Co., Ltd.

The peptizer is not particularly limited as long as it is usually used in the rubber field. For example, it is described in pages 446 to 449 of “Rubber Industry Handbook <Fourth Edition>” edited by the Japan Rubber Association. And aromatic mercaptan peptizers, aromatic disulfide peptizers, and aromatic mercaptan metal salt peptizers. Of these, dixylyl disulfide and o, o'-dibenzamide diphenyl disulfide ("Noctizer SS" manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.) are preferable. Only one type of peptizer may be used, or two or more types may be used in combination.

The amount of peptizer is not particularly limited, but is preferably 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight based on 100 parts by weight of the rubber component having an olefinic double bond. Part is more preferred.

Examples of the retarder include phthalic anhydride, benzoic acid, salicylic acid, N-nitrosodiphenylamine, N- (cyclohexylthio) phthalimide (CTP), sulfonamide derivatives, diphenylurea, bis (tridecyl) pentaerythritol diphosphite, and the like. (Cyclohexylthio) phthalimide (CTP) is preferably used.

The amount of the retarder is not particularly limited, but is preferably 0.01 to 1 part by weight, and 0.05 to 0.5 part by weight with respect to 100 parts by weight of the rubber component having an olefinic double bond. More preferred.

In the present invention, the formula: —O— (CH ₂ —CH ₂ —O) _q —H [wherein q is an integer of 1 or more. You may use the compound which has an oxyethylene unit which has a structure represented by this. Here, in the above formula, q is preferably 2 or more, and more preferably 3 or more. Moreover, q is preferably 16 or less, and more preferably 14 or less. When q is 17 or more, compatibility with a rubber component having an olefinic double bond and reinforcing properties tend to be lowered.

The position of the oxyethylene unit in the compound having an oxyethylene unit may be a main chain, a terminal, or a side chain. Of the compounds having oxyethylene units, a compound having oxyethylene units at least in the side chain is preferred from the viewpoint of sustaining the effect of preventing static electricity accumulation on the obtained tire surface and reducing electric resistance.

Examples of the compound having an oxyethylene unit in the main chain include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, monoethylene glycol, diethylene glycol, triethylene glycol, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene polyoxypropylene Examples thereof include alkyl ethers, polyoxyethylene alkylamines, polyoxyethylene styrenated alkyl ethers, and polyoxyethylene alkyl amides.

When using a compound having an oxyethylene unit at least in the side chain, the number of oxyethylene units is preferably 4 or more, more preferably 8 or more per 100 carbon atoms constituting the main chain. When the number of oxyethylene units is 3 or less, the electrical resistance tends to increase. The number of oxyethylene units is preferably 12 or less, and more preferably 10 or less. When the number of oxyethylene units is 13 or more, the compatibility with the rubber component having an olefinic double bond and the reinforcing property tend to be lowered.

When using a compound having an oxyethylene unit at least in the side chain, the main chain is preferably composed mainly of polyethylene, polypropylene or polystyrene.

The rubber composition of the present invention comprises the above compound (C), a fatty acid metal salt, a rubber component having an olefinic double bond (hereinafter sometimes abbreviated as “rubber component”), carbon black, and, if necessary, It can be produced by kneading other components (for example, a vulcanization accelerator).

In addition to the above components, the rubber composition obtained by further kneading the sulfur component is first a step of kneading the rubber component and carbon black or the like (hereinafter sometimes abbreviated as “step 1”), and then a step. It is preferable to produce the rubber composition obtained in 1 through a step of kneading the rubber composition and the sulfur component (hereinafter sometimes abbreviated as “step 2”). Further, a pre-kneading step of kneading the rubber component may be provided before the step 1 (that is, kneading the rubber component with carbon black or the like) to facilitate processing of the rubber component.

In the production of a rubber composition containing a sulfur component, the total amount of the compound (C) and the fatty acid metal salt may be kneaded with a rubber component or the like in either the preliminary kneading step, step 1 or step 2, The compound (C) and the fatty acid metal salt may be divided and kneaded with a rubber component or the like in at least two steps of the preliminary kneading step to step 2.

When blending zinc oxide, it is preferable to knead with a rubber component or the like in step 1. When a vulcanization accelerator is blended, it is preferably kneaded with a rubber component or the like in step 2. When blending a peptizer, it is preferable to knead with a rubber component or the like in step 1. When providing the preliminary kneading step, it is preferable to knead the entire amount of the peptizer in the preliminary kneading step or to separate the peptizer and knead the rubber component in both the preliminary kneading step and step 1. .

For the kneading in Step 1, for example, an internal mixer including a Banbury mixer, an open kneader, a pressure kneader, an extruder, an injection molding machine, or the like can be used. The discharge temperature of the rubber composition after kneading in step 1 is preferably 200 ° C. or less, more preferably 120 to 180 ° C.

For kneading in step 2, for example, an open roll, a calendar, or the like can be used. The kneading temperature in Step 2 (the temperature of the rubber composition being kneaded) is preferably 60 to 120 ° C.

A vulcanized rubber composition can be produced by vulcanizing a rubber composition containing the above-described sulfur component. You may manufacture a vulcanized rubber composition by processing the rubber composition containing the above-mentioned sulfur component into a specific shape and then vulcanizing it.

The vulcanization temperature is preferably 120 to 180 ° C. A person skilled in the art can appropriately set the vulcanization time according to the composition of the rubber composition. Vulcanization is usually carried out at normal pressure or under pressure.

The rubber composition and vulcanized rubber composition of the present invention are useful for producing various products. As a product obtained from the rubber composition and the vulcanized rubber composition, a vulcanized tire and a tire member are preferable. Examples of the tire member include a tire belt member including the vulcanized rubber composition of the present invention and a steel cord, a tire carcass member including the vulcanized rubber composition of the present invention and a carcass fiber cord, and a tire sidewall member. , A tire inner liner member, a tire cap tread member, or a tire under tread member.

The vulcanized tire is manufactured by first manufacturing a tire member, combining these to manufacture a raw tire, and vulcanizing the raw tire. The tire manufactured using the rubber composition of the present invention has a low loss factor and can achieve low fuel consumption.

The vulcanized rubber composition of the present invention can be used not only for the tire applications described above but also as various anti-vibration rubbers. Examples of such anti-vibration rubbers include anti-vibration rubbers for automobiles such as engine mounts, strut mounts, bushes, and exhaust hangers. The anti-vibration rubber can be manufactured by first processing a rubber composition containing a sulfur component into a predetermined shape and then vulcanizing it.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by the following examples, and appropriate modifications are made within a range that can meet the above and the following purposes. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention. In the following examples and comparative examples, “parts” means “parts by weight” unless otherwise specified.

Example 1
<Step 1>
Using a Banbury mixer (600 ml Labo Plast Mill manufactured by Toyo Seiki), 100 parts of natural rubber (RSS # 1), 45 parts of carbon black (N220, ISAF), 3 parts of stearic acid, 5 parts of zinc oxide, anti-aging agent (N -Phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine, trade name "Antigen (registered trademark) 6C", manufactured by Sumitomo Chemical Co., Ltd.) 1 part, (2Z) -4-[(4-aminophenyl ) Amino] -4-oxo-2-butenoic acid sodium dihydrate (1 type of compound (C)) and 1 part of potassium palmitate were kneaded and mixed to obtain a rubber composition. In this step, the components were put into a Banbury mixer and then kneaded for 5 minutes at a rotation speed of 50 rpm. The rubber temperature at that time was 160 to 170 ° C.
<Process 2>
The rubber composition obtained in the step 1, 1 part of a vulcanization accelerator (N-cyclohexyl-2-benzothiazolylsulfenamide) and 2 parts of sulfur at a temperature of 60 to 80 ° C. in an open roll machine. The rubber composition was obtained by kneading and blending.
<Manufacture of vulcanized rubber>
The rubber composition obtained in step 2 was vulcanized at 145 ° C. to obtain a vulcanized rubber composition.

Example 2
A rubber composition and a vulcanized rubber composition were obtained in the same manner as in Example 1 except that the amount of potassium palmitate was changed from 1 part to 1.4 parts in Step 1.

Example 3
A rubber composition and a vulcanized rubber composition were obtained in the same manner as in Example 1 except that the blending amount of potassium palmitate in Step 1 was changed from 1 part to 1.6 parts.

Example 4
A rubber composition and a vulcanized rubber composition were obtained in the same manner as in Example 1 except that the blending amount of potassium palmitate in Step 1 was changed from 1 part to 1.8 parts.

Example 5
A rubber composition and a vulcanized rubber composition were obtained in the same manner as in Example 1 except that the blending amount of potassium palmitate in Step 1 was changed from 1 part to 2 parts.

Example 6
A rubber composition and a vulcanized rubber composition were obtained in the same manner as in Example 1 except that 1 part of calcium palmitate was added in place of 1 part of potassium palmitate in Step 1.

Example 7
A rubber composition and a vulcanized rubber composition were obtained in the same manner as in Example 1 except that 2 parts of calcium palmitate was blended in place of 1 part of potassium palmitate in Step 1.

Example 8
A rubber composition and a vulcanized rubber composition were obtained in the same manner as in Example 1 except that 4 parts of calcium palmitate was added in place of 1 part of potassium palmitate in Step 1.

Example 9
A rubber composition and a vulcanized rubber composition were obtained in the same manner as in Example 1 except that 2 parts of magnesium stearate was blended in place of 1 part of potassium palmitate in Step 1.

Example 10
A rubber composition and a vulcanized rubber composition were obtained in the same manner as in Example 1 except that 2 parts of zinc stearate was added in place of 1 part of potassium palmitate in Step 1.

Example 11
A rubber composition and a vulcanized rubber composition were obtained in the same manner as in Example 1 except that 2 parts of potassium laurate was added in place of 1 part of potassium palmitate in Step 1.

Comparative Example 1
A rubber composition and a vulcanized rubber composition were obtained in the same manner as in Example 1 except that potassium palmitate was not blended in Step 1.

Compound Mooney viscosity and viscoelastic properties were measured as follows.
(1) Compound Mooney Viscosity The compound Mooney viscosity of the rubber composition was measured at 125 ° C. in accordance with JIS-K6300-1.
The smaller the value of the compound Mooney viscosity is, the less rubber scorch occurs and the better the processing stability of the rubber composition.

The relative value of the compound Mooney viscosity of the rubber composition obtained in any of Examples 1 to 11 with respect to the compound Mooney viscosity of the rubber composition obtained in Comparative Example 1 (= 100 × obtained in any of Examples 1 to 11) Compound Mooney viscosity of the rubber composition / Compound Mooney viscosity of the rubber composition obtained in Comparative Example 1) was calculated. The results are shown in Table 1. The lower the relative value, the better the effect of suppressing the increase in viscosity of the rubber composition.

(2) Viscoelastic properties The viscoelastic properties (tan δ at 60 ° C.) of the vulcanized rubber composition were measured using a dynamic viscoelasticity measuring device, iplexer 500N, manufactured by GABO.
Conditions: temperature 60 ° C., initial strain 10%, dynamic strain 0-2.5%, frequency 10 Hz

Relative value of the viscoelastic property of the rubber composition obtained in any of Examples 1 to 11 with respect to the viscoelastic property (tan δ at 60 ° C.) of the rubber composition obtained in Comparative Example 1 (= 100 × Example 1) The viscoelastic properties of the rubber composition obtained in any of 11 to 11 / viscoelastic properties of the rubber composition obtained in Comparative Example 1) were calculated. The results are shown in Table 1. The lower the relative value, the better the effect of reducing the loss factor (tan δ) of the vulcanized rubber composition.

As shown in Table 1, compound (C) (ie, (2Z) -4-[(4-aminophenyl) amino] -4-oxo- is used as an additive for reducing the loss factor of the vulcanized rubber composition. In Examples 1 to 11 in which the compound (C) and the fatty acid metal salt are used in combination, the compound Mooney viscosity of the rubber composition is reduced compared to Comparative Example 1 in which only 2-butenoate dihydrate is used. ing. As described above, the combined use of the compound (C) and the fatty acid metal salt can suppress an increase in the viscosity of the rubber composition while maintaining a low loss factor (tan δ) of the vulcanized rubber composition.

Further, in Examples 1 to 5 using potassium palmitate and Example 11 using potassium laurate, not only the compound Mooney viscosity of the rubber composition but also the vulcanized rubber composition was compared with Comparative Example 1. The loss factor (tan δ) also decreases.

The additive composition of the present invention is useful as an additive capable of reducing the loss factor of the vulcanized rubber composition and suppressing the increase in viscosity of the rubber composition.

This application is based on Japanese Patent Application No. 2016-137129 filed in Japan, the contents of which are incorporated in full herein.

Claims

A compound (C) having a group or structure (A) capable of reacting with an olefinic double bond and a group or structure (B) capable of reacting or interacting with carbon black;
Fatty acid metal salts,
A rubber component having an olefinic double bond;
A rubber composition obtained by kneading carbon black.
The rubber composition according to claim 1, wherein the group or structure (A) is a group or structure capable of undergoing radical reaction or 1,3-dipole addition reaction with an olefinic double bond.
The group or structure (A) is an olefinic double bond, an amide group, a maleimide ring, a 1H-imidazole ring, a benzoxazole ring, a benzothiazole ring, * -SSO 3 H or a salt thereof, * —S—S— *, * —C≡N + —O − , * —C≡N + —N − — *, a structure represented by formula (i), a structure represented by formula (ii), or a formula (iii) Structure:

[In the above formula, * represents a bonding position. ]
The rubber composition according to claim 1, wherein
The rubber composition according to any one of claims 1 to 3, wherein the group or structure (B) is an unsubstituted or monosubstituted amino group, a benzene ring, a furan ring, an oxazole ring, or a 1H-benzimidazole ring.
Compound (C) is represented by formula (I):

[In the formula (I),
R 1 represents a C 2-12 alkanediyl group which may have one or more substituents, a C 3-10 cycloalkanediyl group which may have one or more substituents, or one or more substituents. Represents a divalent C 6-12 aromatic hydrocarbon group which may have the above-mentioned or a combination thereof.
R 2 and R 3 each independently represent a hydrogen atom, a halogen atom, a hydroxy group, one or more C 1-6 alkoxy group which may have one or more substituents, or one or more substituents. Represents a good C 1-6 alkyl group, or a C 6-14 aryl group optionally having one or more substituents, or R 2 and R 3 are bonded, and the carbon atom to which they are bonded; Together, they form a C 3-10 cycloalkenediyl group which may have one or more substituents.
R 4 is a hydroxy group, a C 1-6 alkoxy group which may have one or more substituents, a C 6-14 aryloxy group which may have one or more substituents, or —NR 5. R 6 (wherein R 5 and R 6 each independently represents a hydrogen atom or a C 1-6 alkyl group optionally having one or more substituents).
X represents —NH— or —O—. ]
The rubber composition according to claim 1, wherein the rubber composition is at least one selected from the group consisting of a compound represented by the formula:
The compound represented by formula (I) is represented by formula (II):

[In formula (II), R 1 to R 4 and X are as defined above. ]
The rubber composition according to claim 5, which is a compound represented by the formula:
The rubber composition according to claim 5 or 6, wherein R 1 is a phenylene group.
The rubber composition according to any one of claims 5 to 7, wherein R 2 and R 3 are both hydrogen atoms.
R 4 is a hydroxy group, a C 1-6 alkoxy group which may have one or more substituents, or a C 6-14 aryloxy group which may have one or more substituents. The rubber composition according to any one of 5 to 8.
The rubber composition according to any one of claims 5 to 8, wherein R 4 is a hydroxy group.
The rubber composition according to any one of claims 5 to 10, wherein X is -NH-.
At least one selected from the group consisting of a compound represented by formula (I), a salt thereof, a solvate thereof and a solvate of the salt is a solvate of a salt of the compound represented by formula (I) The rubber composition according to any one of claims 5 to 11.
The rubber composition according to any one of claims 1 to 12, wherein the metal cation constituting the fatty acid metal salt is a monovalent or divalent metal cation.
The rubber composition according to any one of claims 1 to 12, wherein the metal cation constituting the fatty acid metal salt is a monovalent metal cation.
The rubber composition according to any one of claims 1 to 14, wherein the fatty acid anion constituting the fatty acid metal salt has 8 to 30 carbon atoms.
The rubber composition according to any one of claims 1 to 15, which is obtained by further kneading a sulfur component.
A vulcanized rubber composition obtained by vulcanizing the rubber composition according to claim 16.
A compound (C) having a group or structure (A) capable of reacting with an olefinic double bond and a group or structure (B) capable of reacting or interacting with carbon black;
An additive composition containing a fatty acid metal salt.