WO2016186155A1 - Process for producing rubber composition - Google Patents

Abstract

The present invention provides a process for producing a rubber composition that contains no sulfur ingredient, the process comprising: step 1 in which at least one substance selected from the group consisting of compounds represented by formula (I), salts thereof, and solvates thereof and solvates of the salts, a rubber ingredient, and carbon black are kneaded to prepare a kneaded mixture; step 2 in which the obtained kneaded mixtue is cooled to prepare a cooled kneaded mixture; and step 3 in which the obtained cooled kneaded mixture is kneaded. (The definitions of the groups in formula (I) are as described in the description.)

Description

Method for producing rubber composition

The present invention relates to a method for producing a rubber composition.

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 (tan δ) of the vulcanized rubber composition used for tire manufacture.

In Patent Document 1, in order to reduce the loss factor (tan δ) of the vulcanized rubber composition, the formula (A):

[Definition of the group in the formula (A) is as described in Patent Document 1. The formula (A) is described as the formula (I) in Patent Document 1. ]
And the use of at least one of the salt, the solvate thereof, and the solvate of the salt thereof. As the compound represented by the formula (A), a salt thereof, a solvate thereof, and a solvate of the salt, in the example of Patent Document 1, (2Z) -4-[(4-aminophenyl) amino]- Sodium 4-oxo-2-butenoate dihydrate is used.

In Patent Document 2, in order to reduce the loss factor (tan δ) of the vulcanized rubber composition, the formula (B):

[Definition of the group in the formula (B) is as described in Patent Document 2. The formula (B) is described as the formula (I) in Patent Document 2. ]
It is described that the compound represented by these is used. In the examples of Patent Document 2, sodium (2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoate is used as the compound represented by the formula (B).

JP 2013-209605 A JP 2014-95014 A

Compounds as described in Patent Documents 1 and 2 above, salts thereof, solvates thereof, and solvates of salts thereof (for example, (2Z) -4-[(4-aminophenyl) amino] -4 -Sodium oxo-2-butenoate and its dihydrate) are effective in reducing the loss factor (tan δ) of the vulcanized rubber composition. However, when such a compound is used, there is a problem that the viscosity of the rubber composition increases and the processability decreases.

The present invention has been made paying attention to the circumstances as described above, and is selected from the group consisting of a compound represented by the following formula (I), a salt thereof, a solvate thereof, and a solvate of the salt. It is to suppress an increase in the viscosity of the rubber composition due to the use of at least one.

The present invention that can achieve the above object is as follows.

[1] A method for producing a rubber composition containing no sulfur component,
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 represents 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.
X represents —NH— or —O—. ]
Step 1 for preparing a kneaded product by kneading 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, a rubber component, and carbon black;
Step 2 for preparing the cooled kneaded product by subjecting the obtained kneaded product to a cooling operation, and Step 3 for kneading the obtained cooled kneaded product
Manufacturing method.

[2] The production method according to [1], wherein in step 2, the kneaded product is cooled to 120 ° C. or lower.
[3] The production method according to [1], wherein in step 2, the kneaded product is cooled to 100 ° C. or lower.
[4] The production method according to [1], wherein in step 2, the kneaded product is cooled to 80 ° C. or lower.

[5] The production method according to any one of [1] to [4], wherein the temperature of the kneaded product after cooling in step 2 is 0 ° C. or higher.
[6] The production method according to any one of [1] to [4], wherein the temperature of the kneaded product after cooling in Step 2 is 5 ° C. or higher.

[7] The manufacturing method according to any one of [1] to [6], wherein the cooling operation in step 2 includes processing the kneaded material into a sheet shape or a board shape.

[8] The production method according to [7], wherein the kneaded material processed into a sheet or board has a thickness of 1 to 500 mm.
[9] The production method according to [7], wherein the kneaded material processed into a sheet shape or a board shape has a thickness of 1 to 400 mm.
[10] The production method according to [7], wherein the kneaded material processed into a sheet or board has a thickness of 1 to 100 mm.

[11] The production method according to any one of [1] to [10], wherein the kneading in step 1 is performed for 1 minute or more at a rotation speed of 5 rpm or more.

[12] The production method according to [11], wherein the kneading rotation speed in step 1 is 10 rpm or more.
[13] The production method according to [11], wherein the rotational speed of kneading in step 1 is 10 to 100 rpm.
[14] The production method according to [11], wherein the rotational speed of kneading in step 1 is 10 to 90 rpm.

[15] The production method according to any one of [11] to [14], wherein the kneading time in step 1 is 1 to 10 minutes.
[16] The production method according to any one of [11] to [14], wherein the kneading time in step 1 is 2 to 8 minutes.

[17] The production method according to any one of [1] to [16], wherein the apparatus set temperature at the start of kneading in step 1 is 100 to 180 ° C.
[18] The production method according to any one of [1] to [16], wherein the apparatus setting temperature at the start of kneading in step 1 is 120 to 180 ° C.
[19] The production method according to any one of [1] to [16], wherein the apparatus set temperature at the start of kneading in step 1 is 140 to 180 ° C.
[20] The production method according to any one of [1] to [16], wherein the apparatus set temperature at the start of kneading in step 1 is 150 to 170 ° C.

[21] The production method according to any one of [1] to [20], wherein the discharge temperature of the kneaded product after kneading in step 1 is 150 ° C. or higher.
[22] The production method according to any one of [1] to [20], wherein the discharge temperature of the kneaded product after kneading in step 1 is 155 to 200 ° C.
[23] The production method according to any one of [1] to [20], wherein the discharge temperature of the kneaded product after kneading in step 1 is 160 to 185 ° C.

[24] The production method according to any one of [1] to [23], wherein the kneading in the step 3 is performed by changing a rotation speed.

[25] The production method according to [24], wherein the rotational speed of the first kneading in step 3 is 40 to 100 rpm.
[26] The production method according to [24], wherein the rotational speed of the first kneading in step 3 is 45 to 90 rpm.
[27] The production method according to [24], wherein the rotational speed of the first kneading in the step 3 is 46 to 80 rpm.

[28] The production method according to any one of [24] to [27], wherein the initial kneading time in step 3 is 0.5 to 10 minutes.
[29] The production method according to any one of [24] to [27], wherein the initial kneading time in step 3 is 0.5 to 8 minutes.
[30] The production method according to any one of [24] to [27], wherein the initial kneading time in step 3 is 0.5 to 6 minutes.

[31] The production method according to any one of [1] to [30], wherein the apparatus set temperature at the start of kneading in step 3 is 100 to 180 ° C.
[32] The production method according to any one of [1] to [30], wherein the apparatus set temperature at the start of kneading in step 3 is 120 to 170 ° C.
[33] The production method according to any one of [1] to [30], wherein the apparatus set temperature at the start of kneading in step 3 is 140 to 170 ° C.

[34] The production method according to any one of [1] to [33], wherein the discharge temperature of the kneaded material after kneading in step 3 is 100 to 180 ° C.
[35] The production method according to any one of [1] to [33], wherein the discharge temperature of the kneaded material after kneading in step 3 is 100 to 175 ° C.
[36] The production method according to any one of [1] to [33], wherein the discharge temperature of the kneaded product after kneading in step 3 is 100 to 170 ° C.

[37] The rubber composition to be produced contains at least one total amount selected from the group consisting of the compound represented by formula (I), a salt thereof, a solvate thereof, and a solvate of the salt. The production method according to any one of [1] to [36], wherein the amount is 0.01 to 100 parts by weight per 100 parts by weight of the rubber component.
[38] The rubber composition to be produced contains at least one total amount selected from the group consisting of the compound represented by formula (I), a salt thereof, a solvate thereof, and a solvate of the salt. The production method according to any one of [1] to [36], wherein the amount is 0.01 to 20 parts by weight per 100 parts by weight of the rubber component.
[39] The rubber composition to be produced contains at least one total amount selected from the group consisting of the compound represented by formula (I), a salt thereof, a solvate thereof, and a solvate of the salt The production method according to any one of [1] to [36], wherein the amount is 0.1 to 10 parts by weight per 100 parts by weight of the rubber component.

[40] The production according to any one of [1] to [39], wherein the amount of carbon black used is 20 to 80 parts by weight per 100 parts by weight of the rubber component contained in the rubber composition to be produced. Method.
[41] The production according to any one of [1] to [39], wherein the amount of carbon black used is 30 to 70 parts by weight per 100 parts by weight of the rubber component contained in the produced rubber composition. Method.
[42] The production according to any one of [1] to [39], wherein the amount of carbon black used is 30 to 60 parts by weight per 100 parts by weight of the rubber component contained in the produced rubber composition. Method.

[43] The total amount of at least one total selected from the group consisting of the compound represented by formula (I), a salt thereof, a solvate thereof, and a solvate of the salt and the total amount of carbon black are kneaded in Step 1 The production method according to any one of [1] to [42].

[44] Any one of [1] to [5] above, wherein the rubber composition to be produced contains an anti-aging agent, and the total amount of the anti-aging agent and the cooled kneaded product obtained in step 2 are kneaded in step 3. The manufacturing method as described in one.

[45] The production method according to the above [44], wherein the amount of the anti-aging agent used is 0.01 to 15 parts by weight per 100 parts by weight of the rubber component contained in the rubber composition to be produced.
[46] The production method according to [44], wherein the amount of the anti-aging agent used is 0.1 to 10 parts by weight per 100 parts by weight of the rubber component contained in the rubber composition to be produced.
[47] The production method according to [44], wherein the amount of the anti-aging agent used is 0.1 to 5 parts by weight per 100 parts by weight of the rubber component contained in the rubber composition to be produced.

[48] The compound represented by the formula (I) is represented by the formula (II):

[In the formula (II), R ¹ to R ⁴ and X are as defined above. ]
The production method according to any one of [1] to [47], which is a compound represented by the formula:

[49] The production method according to any one of [1] to [48], wherein R ¹ is a C _2-12 alkanediyl group or a divalent C _6-12 aromatic hydrocarbon group.
[50] The production method according to any one of [1] to [48], wherein R ¹ is a C _2-12 alkanediyl group or a phenylene group.
[51] The production method according to any one of [1] to [48], wherein R ¹ is a phenylene group.
[52] The production method according to any one of [1] to [48], wherein R ¹ is a 1,4-phenylene group.

[53] The production method according to any one of [1] to [52], wherein R ² and R ³ are each independently a hydrogen atom or a C _1-6 alkyl group.
[54] The production method according to any one of [1] to [52], wherein R ² and R ³ are hydrogen atoms.

[55] The production method according to any one of [1] to [54], wherein R ⁴ is a hydroxy group or a C _1-6 alkoxy group.
[56] The production method according to any one of [1] to [54], wherein R ⁴ is a hydroxy group.

[57] The production method according to any one of [1] to [56], wherein X is -NH-.

[58] The 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 production method according to any one of [1] to [57], which is a Japanese product.
[59] 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 thereof The production method according to any one of [1] to [57], which is a solvate of
[60] 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 is an alkali carboxylate of the compound represented by the formula (I) Any one of the above [1] to [57], which is at least one selected from the group consisting of hydrates of metal salts and hydrates of alkaline earth metal carboxylates of the compounds represented by formula (I) The manufacturing method as described in one.
[61] Sodium 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 thereof The production method according to any one of [1] to [57], which is a salt hydrate.

[62] The production method according to any one of [1] to [61], wherein 50% by weight or more of the rubber component is a diene rubber.
[63] The production method according to any one of [1] to [61], wherein 70 to 100% by weight of the rubber component is a diene rubber.
[64] The production method according to any one of [1] to [61], wherein 80 to 100% by weight of the rubber component is a diene rubber.

[65] A method for producing a rubber composition containing a sulfur component, wherein the rubber composition obtained by the production method according to any one of [1] to [64] and a sulfur component are kneaded. Manufacturing method.

[66] The production method according to [65], wherein the amount of the sulfur component used is 0.01 to 30 parts by weight per 100 parts by weight of the rubber component contained in the rubber composition to be produced.
[67] The production method according to [65], wherein the amount of the sulfur component used is 0.1 to 20 parts by weight per 100 parts by weight of the rubber component contained in the rubber composition to be produced.
[68] The production method according to [65], wherein the amount of the sulfur component used is 0.1 to 10 parts by weight per 100 parts by weight of the rubber component contained in the rubber composition to be produced.

[69] A rubber composition containing no sulfur component, obtained by the production method according to any one of [1] to [64].
[70] A rubber composition containing a sulfur component, obtained by the production method according to any one of [65] to [68].
[71] A vulcanized rubber composition obtained by vulcanizing the rubber composition containing the sulfur component according to [70].

[72] A vulcanized tire including the vulcanized rubber composition according to [71].
[73] A tire belt member comprising the vulcanized rubber composition according to [71] and a steel cord.
[74] A tire carcass member comprising the vulcanized rubber composition according to [71] and a carcass fiber cord.
[75] A tire member comprising the vulcanized rubber composition according to [71].
[76] The tire member according to [75], which is a tire sidewall member, a tire inner liner member, a tire cap tread member, or a tire undertread member.

[77] A method for producing a vulcanized rubber composition, comprising vulcanizing a rubber composition containing a sulfur component obtained by the production method according to any one of [65] to [68] .

According to the present invention, the viscosity of the rubber composition is increased by using 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. Can be suppressed.

<Ingredients>
First, components that can be used in the present invention will be described.

(1) Compound represented by formula (I), etc. The present invention provides a compound of formula (I):

Or at least one selected from the group consisting of a salt, a solvate thereof, and a solvate of the salt thereof. In the present specification, 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 a C _1-6 alkoxy group, a C _1-6 alkoxy-carbonyl group, a C _1-7 acyl group, and a C _1-7 acyl- Examples thereof include an oxy group and a C _6-14 aryl group which may have one or more substituents. The explanation of the C _1-6 alkoxy group will be given 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.

Examples of the substituent that the C _3-10 cycloalkanediyl group may have include a C _1-6 alkyl group, a C _1-6 alkoxy group, a C _1-6 alkoxy-carbonyl group, and a C _1-7 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” 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, for example, a C _1-6 alkyl group, a C _1-6 alkoxy group, a C _1-6 alkoxy-carbonyl group, C _Examples thereof include a _1-7 acyl group, a C _1-7 acyl-oxy group, a C _6-14 aryl group, and a 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 a C _1-6 alkoxy group, a C _1-6 alkoxy-carbonyl group, a C _1-7 acyl group, and a C _1-7 acyl-oxy group. 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 a C _1-6 alkoxy group, a C _1-6 alkoxy-carbonyl group, a C _1-7 acyl group, and a C _1-7 acyl-oxy group. 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 C _1-6 alkyl group, a C _1-6 alkoxy group, a C _1-6 alkoxy-carbonyl group, a C _1-7 acyl group, _Examples thereof include 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 C _1-6 alkyl group, a C _1-6 alkoxy group, a C _1-6 alkoxy-carbonyl group, and a C _1-7 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) is a hydroxy group (—OH), a C _1-6 alkoxy group optionally having one or more substituents, or a C optionally having one or more substituents. Represents a _6-14 aryloxy group.

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 or a C _1-6 alkoxy group, 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.

The amount of compound (I) and the like used (that is, at least one total amount selected from the group consisting of the compound represented by formula (I), a salt thereof, a solvate thereof and a solvate of the salt) The amount is preferably 0.01 to 100 parts by weight, more preferably 0.01 to 20 parts by weight, still more preferably 0.1 to 10 parts by weight per 100 parts by weight of the rubber component contained in the rubber composition produced in the present invention. Part.

(2) Rubber component As the rubber component, natural rubber (NR) and modified natural rubber (for example, epoxidized natural rubber, deproteinized natural rubber); polyisoprene rubber (IR), styrene / butadiene copolymer rubber (SBR), Various synthetic rubbers such as polybutadiene rubber (BR), acrylonitrile / butadiene copolymer rubber (NBR), isoprene / isobutylene copolymer rubber (IIR), ethylene / propylene / diene copolymer rubber (EPDM), halogenated butyl rubber (HR), etc. Is illustrated. Only 1 type may be used for a rubber component and it may use 2 or more types together.

The rubber component 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 is preferably 50% by weight or more, more preferably 70 to 100% by weight, still more preferably 80 to 100% by weight. is there.

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 Guthrie). 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 (eg, N, N, -diethylaminoethyl acrylate), 2-hydroxy acrylate, and the like. Modified natural rubber containing

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, for example, the amount of SBR and / or NR in the rubber component is 60 to 100% by weight, and the amount of BR is 0 to 40% by weight. In the rubber composition for a sidewall, the amount of SBR and / or NR in the rubber component is preferably 10 to 70% by weight, the amount of BR is 90 to 30% by weight, and 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 produced in the present invention is used for tire treads, for example, in passenger car tires, SBR, which is excellent in wear resistance and hysteresis loss reduction performance, is used as a base material in rubber components, and in truck and bus tires. Higher strength NR is optionally used as a base material together with SBR, and these base materials can be blended with BR as necessary to obtain a tread excellent in wear resistance, fatigue resistance and impact resilience. Therefore, it is preferable.

When the rubber composition produced in the present invention is used for a tire sidewall, NR and SBR are blended in a passenger car tire, or NR and BR are blended, and NR in a truck / bus tire. It is preferable to use a blend of BR and BR since bending resistance and crack growth resistance can be obtained.

When the rubber composition produced in the present invention is used for a tire belt, it is preferable to use NR and / or IR as a rubber component because a high elastic modulus and good adhesion to reinforcing fibers can be obtained. .

When the rubber composition produced in the present invention is used as an inner liner of a tire, it is preferable to blend IIR, SBR, and NR as a rubber component, or blend IIR and NR. And bending resistance is preferable.

(3) Carbon Black 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. Examples of carbon black include HAF (High Absorption Furnace), SAF (Super Abrasion Furnace), ISAF (Intermediate SAF), ISAF-HM (Intermediate SAF-High Fur, and FEF (Fast East Fur, FAS ), SRF (Semi-Reinforcing Furnace) is preferable.

The amount of carbon black used is preferably 20 to 80 parts by weight, more preferably 30 to 70 parts by weight, still more preferably 30 to 60 parts by weight per 100 parts by weight of the rubber component contained in the rubber composition produced in the present invention. Part.

(4) Sulfur component Examples of the sulfur component include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur, morpholine disulfide, and tetramethylthiuram disulfide. Usually, powdered sulfur is preferred, and insoluble sulfur is preferred when the rubber composition produced in the present invention is used for producing tire members having a large amount of sulfur such as belt members.

The amount of the sulfur component used is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 20 parts by weight, still more preferably 100 parts by weight of the rubber component contained in the rubber composition produced in the present invention. 0.1 to 10 parts by weight.

(5) Other components In the present invention, other components known in the rubber field may be used in addition to the above-mentioned compound (I) and the like, rubber components, carbon black, and sulfur components. Other components include fillers other than carbon black, compounds capable of binding to silica, vulcanization accelerators, vulcanization accelerators, resins, viscoelasticity improvers, anti-aging agents, oils, waxes, peptizers, Examples thereof include a retarder, a compound having an oxyethylene unit, and a catalyst (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 silica products include “Nipsil (registered trademark) AQ” and “Nipsil (registered trademark) AQ-N” manufactured by Tosoh Silica Co., Ltd., “Ultrazil (registered trademark) VN3” and “Ultrazil” 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” may be 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 produced in the present invention is used for a passenger car tread, the amount of silica used is preferably in the range of 10 to 120 parts by weight per 100 parts by weight of the rubber component contained in the rubber composition produced in the present invention. 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 produced in the present invention is used as a composition for an inner liner, even if a bituminous coal pulverized product having an average particle size of more than 0.1 mm is used, the air permeability of the composition is sufficient. May not be improved.

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 the 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 per 100 parts by weight of the rubber component contained in the rubber composition produced in the present invention. Hereinafter, it is preferably 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 the rubber component 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 per 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 thereof is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 15 parts by weight, per 100 parts by weight of the rubber component contained in the rubber composition produced in the present invention. More preferably, it 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, per 100 parts by weight of the rubber component contained in the rubber composition produced in the present invention. More preferably, it 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 the rubber component. 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 the citraconimide compounds, it is particularly stable thermally, particularly excellent in dispersibility in the rubber component, and can provide a vulcanized rubber composition having high hardness (Hs) (reversion control). 1,3-biscitraconimidomethylbenzene represented by the following formula is preferred.

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, X is an integer of 2 to 4, and R ¹⁹ is 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 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 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 ) _m —S—SO ₃ H (V)
[Wherein, m 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.

M is an integer of 3 to 10, preferably an integer of 3 to 6. When m is 2 or less, there is a tendency that sufficient heat fatigue resistance cannot be obtained. When m 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 and, when used in combination with alkylphenol / sulfur chloride condensate (IV), it is inserted in the middle of -S _X -crosslinking of alkylphenol / sulfur chloride condensate (IV) to condense alkylphenol / sulfur chloride Because it is possible to form a hybrid bridge with the product (IV), the 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.)
It is preferable to use the compound represented by these as a vulcanization | cure acceleration | stimulation adjuvant.

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 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 the rubber component.

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., manufactured by Kobe Oil 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.) A wax is preferably used.

When an anti-aging agent is used, the amount is preferably 0.01 to 15 parts by weight, more preferably 0.1 to 10 parts by weight per 100 parts by weight of the rubber component contained in the rubber composition produced in the present invention. Parts, more 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 used is not particularly limited, but is preferably 0.01 to 1 part by weight, preferably 0.05 to 0, per 100 parts by weight of the rubber component contained in the rubber composition produced in the present invention. More preferably, 5 parts by weight.

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 used is not particularly limited, but is preferably 0.01 to 1 part by weight, preferably 0.05 to 0.5 parts by weight per 100 parts by weight of the rubber component contained in the rubber composition produced in the present invention. Part is 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, the compatibility with the rubber component and the reinforcing property tend to decrease.

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 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.

<Step 1>
The production method of the present invention includes step 1 of preparing a kneaded product by kneading compound (I) and the like, a rubber component, and carbon black. The rubber component and carbon black such as compound (I) may all be kneaded in the total amount used in step 1, and they are divided and part of them is kneaded in step 1, and then The remaining kneaded product and the cooled kneaded product obtained in step 2 may be kneaded in step 3. However, in order to sufficiently exhibit the effect of reducing the loss factor (tan δ) due to the compound (I) or the like, it is preferable to knead the entire amount of the compound (I) and the like and carbon black in step 1 in order to sufficiently exhibit the effect of reducing the loss factor (tan δ). .

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 rotational speed of kneading in step 1 is preferably 5 rpm or more, more preferably 10 rpm or more, further preferably 10 to 100 rpm, and particularly preferably 10 to 90 rpm. The kneading time in step 1 is preferably 1 minute or more, more preferably 1 to 10 minutes, and further preferably 2 to 8 minutes. In step 1, the kneading may be continued by first kneading at a low rotation speed (for example, 10 rpm) and then increasing the rotation speed (for example, 50 rpm). The apparatus set temperature at the start of kneading in step 1 is preferably 100 to 180 ° C., more preferably 120 to 180 ° C., still more preferably 140 to 180 ° C., and particularly preferably 150 to 170 ° C. The discharge temperature of the kneaded product after kneading in step 1 is preferably 150 ° C. or higher, more preferably 155 to 200 ° C., and further preferably 160 to 185 ° C.

<Step 2>
The production method of the present invention includes step 2 of preparing the cooled kneaded product by subjecting the obtained kneaded product to a cooling operation. In step 2, the kneaded product is preferably cooled to 120 ° C. or lower, more preferably 100 ° C. or lower, and still more preferably 80 ° C. or lower. The temperature lower limit of the kneaded product after cooling is not particularly limited, but the temperature of the kneaded product after cooling is preferably 0 ° C. or higher, more preferably 5 ° C. or higher.

Examples of the cooling operation include (i) forced cooling of the kneaded product (for example, water cooling or forced air cooling), and (ii) processing the kneaded product into a sheet or board using, for example, an open roll. (The kneaded product is cooled when it comes into contact with an open roll or the like), (iii) After the kneaded product is processed into a sheet or board, the sheet or board kneaded product is forcibly cooled or allowed to cool. And the like. In order to efficiently and uniformly cool the kneaded material, it is preferable that the cooling operation includes processing the kneaded material into a sheet shape or a board shape. The thickness of the kneaded material processed into a sheet or board is preferably 1 to 500 mm, more preferably 1 to 400 mm, and still more preferably 1 to 100 mm.

The cooling operation in the present invention does not include that the obtained kneaded product is simply left to stand and the temperature is naturally lowered (ie, allowed to cool) without performing the above-described operation. In paragraph [0057] of Patent Document 2, first, the rubber component, carbon black, and compound I described in Patent Document 2 (ie, (2Z) -4-[(4-aminophenyl) amino] -4 -Oxo-2-butenoate) is kneaded with a Banbury mixer (first kneading) and discharged to prepare a master batch, and then the master batch and other components are kneaded with a Banbury mixer (second kneading). That is, two-stage kneading is described. However, Patent Document 2 does not describe performing a cooling operation on the master batch obtained by the first kneading.

<Step 3>
The manufacturing method of this invention includes the process 3 which knead | mixes the obtained cooling kneaded material. In the production method of the present invention, the kneaded product containing the rubber component and carbon black, such as compound (I), is once cooled, and the resulting kneaded kneaded product is kneaded to shear the rubber component (low rubber component). As a result, it is presumed that the increase in viscosity of the rubber composition due to the compound (I) or the like is suppressed. However, the present invention is not limited to such estimation.

For the kneading in step 3, for example, an internal mixer including a Banbury mixer, an open kneader, a pressure kneader, an extruder, and an injection molding machine can be used.

It is preferable to perform the kneading in the step 3 by changing the rotation speed. In order to sufficiently shear the rubber component, the rotational speed of the initial kneading in the step 3 is preferably 40 to 100 rpm, more preferably 45 to 90 rpm, and further preferably 46 to 80 rpm. Preferably it is 0.5 to 10 minutes, more preferably 0.5 to 8 minutes, and still more preferably 0.5 to 6 minutes. After first kneading at such a rotational speed and sufficiently shearing the rubber component, the rotational speed is decreased (for example, 10 rpm) to sufficiently knead the rubber component and other components. Alternatively, the rotational speed may be increased again (for example, 50 rpm) and kneading may be performed. The apparatus set temperature at the start of kneading in step 3 is preferably 100 to 180 ° C, more preferably 120 to 170 ° C, and still more preferably 140 to 170 ° C. The cooled and kneaded product obtained in step 2 is charged into the kneading apparatus while maintaining the temperature after cooling, and heated after the start of kneading in step 3. The discharge temperature of the kneaded product after kneading in step 3 is preferably 100 to 180 ° C, more preferably 100 to 175 ° C, and still more preferably 100 to 170 ° C.

<Kneading process of sulfur component>
The present invention also provides a production method including kneading the rubber composition obtained as described above and a sulfur component. For kneading the sulfur component, for example, an open roll, a calendar, or the like can be used. The kneading temperature of the sulfur component (temperature of the rubber composition being kneaded) is preferably 60 to 120 ° C.

<Vulcanization process>
A vulcanized rubber composition can be produced by vulcanizing a rubber composition containing a sulfur component. 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.

<Other processes>
In the production method of the present invention, other steps may be performed in addition to the steps 1 to 3, the kneading step of the sulfur component and the vulcanization step. As another process, the mastication process of the rubber component before the process 1 etc. are mentioned, for example.

<Kneading of other ingredients>
The above-described kneading of the other components may be performed in any one of step 1, step 3 and other steps (for example, a kneading step). However, when the anti-aging agent is kneaded with the rubber component or the like in the step 1 or the previous kneading step, the anti-aging agent in the kneaded product acts on the compound (I) or the like in the step 1, and the compound (I) or the like In some cases, the effect of reducing tan δ is weakened. In order to avoid such adverse effects, when producing a rubber composition containing an anti-aging agent, it is preferable to knead the entire amount of the anti-aging agent with the cooled kneaded product obtained in step 2 in step 3.

When using a vulcanization accelerator, it is preferable to knead the entire amount in the kneading step of the sulfur component, that is, kneading the sulfur component and the vulcanization accelerator together with the rubber composition. Further, the components other than the antioxidant and the vulcanization accelerator are preferably kneaded with the rubber component or the like before the sulfur component kneading step, that is, in either the mastication step, step 1 or step 3. . Components other than the anti-aging agent and the vulcanization accelerator may be divided and kneaded with a rubber component or the like in two or more steps of the mastication step, step 1 and step 3.

<Rubber composition>
The present invention also provides a rubber composition containing no sulfur component, a rubber composition containing a sulfur component, and a vulcanized rubber composition obtained by the above-described production method.

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 coefficient (tan δ) 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.

Hereinafter, the present invention will be described more specifically with reference to examples and the like. 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 also possible to implement them, and they are all included in the technical scope of the present invention. “Parts” described in the following examples and the like means “parts by weight”.

1. Ingredients The ingredients used in the following examples and the like are as follows.
・ NR: Natural rubber (RSS # 1)
CB1: Carbon black HAF (Asahi Carbon Co., Ltd., trade name “Asahi # 70”)
CB2: Carbon Black ISAF (Asahi Carbon Co., Ltd., trade name “Asahi # 80”)
CB3: Carbon black FEF (Asahi Carbon Co., Ltd., trade name “Asahi # 60”)
Compound (I-1): (2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoate sodium dihydrate Zinc oxide (ZnO)
・ Stearic acid: “Lunac S20” manufactured by Kao Corporation
Anti-aging agent: “Antigen (registered trademark) 6C” (N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine) manufactured by Sumitomo Chemical Co., Ltd.
- sulfur content: powdery sulfur _(S 8)
・ Vulcanization accelerator: N-cyclohexyl-2-benzothiazolylsulfenamide

2. Operation in Examples The rubber composition containing no sulfur component, the rubber composition containing the sulfur component, and the vulcanized rubber composition of the example were manufactured as follows. In the following, step 1 in the present invention is referred to as “non-pro first step”, step 2 as “cooling step”, step 3 as “non-pro second step”, and sulfur component kneading step as “pro”. Step ".

<Non-pro first step>
The natural rubber was put into a pressure kneader (TD1-5MDX manufactured by Toshin Co., Ltd.) whose apparatus set temperature at the start of kneading was 155 ° C., and then kneaded for 2 minutes at a rotation speed of 50 rpm. To this, components other than the rubber component were added in the amounts shown in Tables 1 to 5 below, and kneading was performed at the rotational speeds and times shown in Tables 1 to 5 below, and the kneaded product was discharged. The discharge temperatures are shown in Tables 1 to 5 below.

<Cooling process>
The kneaded product obtained in the first step of non-pro was processed into a sheet having a thickness of 3 to 5 mm using an open roll (laboratory mill manufactured by Kansai Roll Co., Ltd.) having a set temperature of 50 ° C. The sheet-like kneaded material was allowed to cool in an air atmosphere at room temperature until the temperature after cooling shown in 1 to 5 was reached.

<Non-pro second step>
The rubber composition obtained in the above cooling process is put into a pressure kneader (TD1-5MDX manufactured by Toshin Co., Ltd.) whose apparatus set temperature at the start of kneading is 155 ° C., and sheared for 1 minute at a rotation speed of 50 rpm. Then, the components are added in the amounts shown in Tables 1 to 5 below, and kneaded for 1 minute at a rotational speed of 10 rpm and further for 1 minute at a rotational speed of 50 rpm, to obtain a rubber composition containing no sulfur component. It was. The discharge temperatures are shown in Tables 1 to 5 below.

<Pro process>
The rubber composition obtained in the second step of non-pro is kneaded with the vulcanization accelerator and the sulfur component in the amounts shown in Tables 1 to 5 below at a temperature of 60 to 80 ° C. with an open roll, and the sulfur component A rubber composition containing was obtained.

<Vulcanization process>
Using a vulcanizing press, the vulcanization temperature was set to 145 ° C., and the vulcanization time was 90% vulcanization time (tc (90)) obtained by rheometer measurement according to JIS K 6300-2. A vulcanized rubber composition was obtained by vulcanizing the rubber composition obtained by the pro process at a value obtained by adding 5 minutes to the value.

3. Operation in Comparative Examples and Reference Examples Rubber compositions containing no sulfur component, rubber compositions containing sulfur components, and vulcanized rubber compositions of Comparative Examples and Reference Examples were produced as follows. In the following, a process for producing a rubber composition not containing a sulfur component is referred to as a “non-pro first process”, and a process for producing a rubber composition containing a sulfur component is referred to as a “pro process”.

<Non-pro first step>
The natural rubber was put into a pressure kneader (TD1-5MDX manufactured by Toshin Co., Ltd.) whose apparatus set temperature at the start of kneading was 155 ° C., and then kneaded for 2 minutes at a rotation speed of 50 rpm. To this, components other than the rubber component were added in the amounts shown in Tables 1 to 5 below, and kneading was performed at the rotational speeds and times shown in Tables 1 to 5 below, and the kneaded product was discharged. The discharge temperatures are shown in Tables 1 to 5 below.

<Pro process>
The rubber composition obtained by the first step of non-pro is kneaded with the vulcanization accelerator and the sulfur component in the amounts shown in Tables 1 to 5 below at a temperature of 60 to 80 ° C. with an open roll, and the sulfur component A rubber composition containing was obtained.

<Vulcanization process>
Using a vulcanizing press, the vulcanization temperature was set to 145 ° C, and the vulcanization time was added to the value of tc (90) obtained by rheometer measurement in accordance with JIS K 6300-2 by 5 minutes. By setting the time and vulcanizing the rubber composition obtained by the pro process, a vulcanized rubber composition was obtained.

4). Characterization <Relative value of viscosity>
In accordance with JIS-K6300-1, the Mooney viscosity of the rubber compositions containing sulfur components obtained in Examples, Comparative Examples and Reference Examples was measured at 125 ° C.

From the Mooney viscosity of the rubber composition of Reference Example not using Compound (I-1) and the Mooney viscosity of the rubber composition of Examples or Comparative Examples using Compound (I-1), Formula (1):
Relative value of viscosity = (Mooney viscosity of rubber composition of Example or Comparative Example) / (Mooney viscosity of rubber composition of Reference Example) (1)
Was used to calculate the relative value of the viscosity. The results are shown in Tables 1 to 5 below.

<Relative value of tan δ>
Using the viscoelasticity analyzer manufactured by Ueshima Seisakusho Co., Ltd. under the following conditions, the viscoelastic properties of the vulcanized rubber compositions obtained in Examples, Comparative Examples and Reference Examples were measured, and their loss coefficients at 60 ° C. (Tan δ) was determined.
Measurement temperature: -5 ℃ -80 ℃
Temperature increase rate: 2 ° C / min Initial strain: 10%
Dynamic strain: 2.5%
Frequency: 10Hz

From the tan δ of the rubber composition of the reference example not using the compound (I-1) and the tan δ of the vulcanized rubber composition of the example or comparative example using the compound (I-1), the formula (2):
Relative value of tan δ = (tan δ of the vulcanized rubber composition of Example or Comparative Example) / (tan δ of the vulcanized rubber composition of Reference Example) (2)
Was used to calculate the relative value of tan δ. The results are shown in Tables 1 to 5 below.

Examples 1 to 4, Comparative Examples 1 and 2, and Reference Examples 1 and 2
The rubber compositions and vulcanized rubber compositions of Examples 1 to 4, Comparative Examples 1 and 2, and Reference Examples 1 and 2 were produced using the above-described operations and the components and conditions shown in Table 1 below. The relative viscosity values and the relative tan δ values of Examples 1 and 2 and Comparative Example 1 shown in Table 1 below are the Mooney of the rubber composition of Reference Example 1 in Formula (1) and Formula (2), respectively. The viscosity and the tan δ value of the vulcanized rubber composition were calculated, and the relative viscosity values and the relative tan δ values of Examples 3 and 4 and Comparative Example 2 were calculated using the equations (1) and (2), respectively. The value was calculated using the Mooney viscosity of the rubber composition of Reference Example 2 and the value of tan δ of the vulcanized rubber composition.

As shown in Table 1 above, in Comparative Examples 1 and 2 in which a rubber composition containing no sulfur component was produced in only one kneading step (non-pro first step), the relative value of the viscosity was greater than 1. It was. This shows that the viscosity of the rubber composition is increased by using compound (I-1) only in the conventional one-stage kneading process.

On the other hand, in Examples 1 to 4 in which a rubber composition containing no sulfur component was produced in a two-stage kneading process (non-pro first process and non-pro second process), the relative value of the viscosity was less than 1. It was. As described above, in Examples 1 to 4 in which the two-stage kneading process is performed, not only the viscosity increase of the rubber composition due to the use of the compound (I-1) is suppressed, but also the compound (I-1) is used. The viscosity of the rubber composition could be reduced more than in Reference Examples 1 and 2.

Surprisingly, the relative value of tan δ in Examples 1 and 2 was lower than that in Comparative Example 1, and the relative value of tan δ in Examples 3 and 4 was lower than that in Comparative Example 2. Thus, by performing the two-stage kneading step, not only the increase in viscosity but also tan δ could be further reduced.

Examples 5 to 7, Comparative Example 3, and Reference Example 3
The rubber compositions and vulcanized rubber compositions of Examples 5 to 7, Comparative Example 3, and Reference Example 3 were produced by the above operation and the components and conditions shown in Table 2 below. The relative viscosity values and the relative tan δ values of Examples 5 to 7 and Comparative Example 3 shown in Table 2 below are the Mooney values of the rubber composition of Reference Example 3 in Formula (1) and Formula (2), respectively. The viscosity and tan δ value of the vulcanized rubber composition were used for calculation.

In Examples 5 to 7, kneading was carried out at 50 rpm for 1 to 3 minutes after kneading at 10 rpm for 2 minutes in the non-pro first step. Even in Example 5 in which kneading was performed at 10 rpm for 2 minutes and at 50 rpm for 1 minute in the non-pro first step, the relative value of the viscosity was 1, and the increase and decrease in viscosity could be suppressed. From this result, it is estimated that the suppression of the increase in viscosity is caused by performing the second step of non-pro after cooling.

Examples 8 to 15, Comparative Examples 4 and 5, and Reference Examples 4 and 5
The rubber compositions and vulcanized rubber compositions of Examples 8 to 15, Comparative Examples 4 and 5, and Reference Examples 4 and 5 were produced using the above-described operations and the components and conditions shown in Table 3 below. The relative values of the viscosity and the tan δ of Examples 8 to 12 and Comparative Example 4 shown in Table 3 below are the Mooney of the rubber composition of Reference Example 4 in Formula (1) and Formula (2), respectively. The viscosity and the tan δ value of the vulcanized rubber composition were calculated, and the relative viscosity values and the tan δ values of Examples 13 to 15 and Comparative Example 5 were calculated using the formulas (1) and (2), respectively. The value was calculated using the Mooney viscosity of the rubber composition of Reference Example 5 and the tan δ value of the vulcanized rubber composition.

The effect of kneading other components (zinc oxide, stearic acid, anti-aging agent) in the first step of non-pro was examined. The relative values of the viscosity of Examples 9 to 12, 14 and 15 in which zinc oxide, stearic acid or an antioxidant is kneaded in the first step of non-pro are about 1 or less than 1, and these other components are Even if kneaded in the first step of pro, an increase in viscosity can be suppressed. However, in Examples 11, 12, and 15 in which the anti-aging agent was kneaded in the first step of non-pro, the relative value of tan δ was larger than in the other examples. It is presumed that the effect of reducing tan δ of compound (I-1) is weakened by kneading the antioxidant in the first step of non-pro. Therefore, when the anti-aging agent is used, the total amount of the anti-aging agent is not used in the non-pro first step (ie, step 3 of the present invention) but in the non-pro second step (ie, step 3 of the present invention). It is preferable to knead the cooled kneaded product.

Examples 16 to 21, Comparative Examples 6 to 8, and Reference Examples 6 to 8
The rubber compositions and vulcanized rubber compositions of Examples 16 to 21, Comparative Examples 6 to 8, and Reference Examples 6 to 8 were produced using the above-described operations and the components and conditions shown in Table 4 below. The relative values of viscosity and tan δ of Examples 16 and 17 and Comparative Example 6 shown in Table 4 below are the Mooney of the rubber composition of Reference Example 6 in Formula (1) and Formula (2), respectively. The viscosity and the tan δ value of the vulcanized rubber composition were calculated, and the relative viscosity values and the relative tan δ values of Examples 18 and 19 and Comparative Example 7 were calculated using the equations (1) and (2), respectively. In Example 2, the Mooney viscosity of the rubber composition of Reference Example 7 and the tan δ value of the vulcanized rubber composition were calculated, and the relative values of the viscosity and tan δ of Examples 20 and 21 and Comparative Example 8 were In the formulas (1) and (2), the Mooney viscosity of the rubber composition of Reference Example 8 and the tan δ value of the vulcanized rubber composition were used.

In any of Examples 16 to 21 in which the type of carbon black was changed, the relative value of viscosity and the relative value of tan δ were smaller than those of the comparative example. From these results, it can be seen that according to the production method of the present invention, it is possible to suppress an increase in viscosity due to the compound (I) and to reduce tan δ regardless of the type of carbon black.

Examples 22 and 23, Comparative Examples 9 and 10, and Reference Example 9
The rubber compositions and vulcanized rubber compositions of Examples 22 and 23, Comparative Examples 9 and 10, and Reference Example 9 were produced using the above-described operations and the components and conditions shown in Table 5 below. The relative viscosity values and the relative tan δ values of Examples 22 and 23 and Comparative Examples 9 and 10 shown in Table 5 below are the rubber composition of Reference Example 9 in Formula (1) and Formula (2), respectively. The Mooney viscosity and the tan δ value of the vulcanized rubber composition were used for calculation.

Also in Examples 22 and 23 in which the addition amount of compound (I-1) was changed, the relative value of viscosity and the relative value of tan δ were smaller than those of the comparative example. From these results, it can be seen that according to the production method of the present invention, increase in viscosity can be suppressed and tan δ can be reduced regardless of the amount of compound (I-1) added.

Production Example 1
A 500-mL reaction vessel purged with nitrogen was charged with 1.65 g (15.3 mmol) of p-phenylenediamine and 180 mL of tetrahydrofuran, and the reaction vessel was kept at 0 to 5 ° C.
While maintaining this reaction vessel at 0 to 5 ° C., 5.51 g (51.0 mmol) of p-phenylenediamine was added thereto, and then 5.00 g (51.0 mmol) of maleic anhydride was dissolved in 7.5 mL of tetrahydrofuran. The resulting solution was added dropwise over 30 minutes. The above-described operation of adding p-phenylenediamine and the operation of dropwise addition of a maleic anhydride tetrahydrofuran solution were repeated a total of 6 times.
After completion of the sixth dropwise addition of maleic anhydride in tetrahydrofuran, the resulting mixture was stirred at 20-25 ° C. for an additional 2 hours. Thereafter, the obtained reaction solution was concentrated to dryness to obtain crude crystals. This crude crystal was confirmed by NMR measurement to have (2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoic acid as the main component. Yield: 94.3%.

Production Example 2
A 500 mL reaction vessel purged with nitrogen was charged with 10 mL of tetrahydrofuran, and the reaction vessel was kept at 0 to 5 ° C.
While maintaining this reaction vessel at 0 to 5 ° C., 30.0 g (305.9 mmol) of maleic anhydride was dissolved in 45 mL of tetrahydrofuran, and 34.7 g (321.2 mmol) of p-phenylenediamine. Was dissolved in 30 mL of methanol and added dropwise in parallel over 2 hours. After completion of the dropwise addition, the resulting mixture was kept at 0-5 ° C. and further stirred for 2 hours. Thereafter, the obtained reaction solution was concentrated to dryness to obtain crude crystals. This crude crystal was confirmed by NMR measurement to have (2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoic acid as the main component. Yield: 92.6%.

According to the production method of the present invention, an increase in the viscosity of the rubber composition due to the use of compound (I) or the like can be suppressed. The rubber composition obtained by the production method of the present invention is useful for production of various products (for example, vulcanized tires and tire members).

This application is based on Japanese Patent Application No. 2015-102549 filed in Japan, the contents of which are incorporated in full herein.

Claims (23)

1. A method for producing a rubber composition containing no sulfur component,
   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 represents 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.
   X represents —NH— or —O—. ]
   Step 1 for preparing a kneaded product by kneading 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, a rubber component, and carbon black;
   Step 2 for preparing the cooled kneaded product by subjecting the obtained kneaded product to a cooling operation, and Step 3 for kneading the obtained cooled kneaded product
   Manufacturing method.
2. The manufacturing method of Claim 1 which cools a kneaded material to 120 degrees C or less in the process 2.
3. The manufacturing method according to claim 1 or 2, wherein the cooling operation in step 2 includes processing the kneaded material into a sheet shape or a board shape.
4. The production method according to any one of claims 1 to 3, wherein the kneading in step 1 is performed at a rotation speed of 10 rpm or more for 1 minute or more.
5. The production method according to any one of claims 1 to 4, wherein a discharge temperature of the kneaded material after kneading in step 1 is 150 ° C or higher.
6. The production according to any one of claims 1 to 5, wherein the rubber composition to be produced contains an anti-aging agent, and the total amount of the anti-aging agent and the cooled kneaded product obtained in step 2 are kneaded in step 3. Method.
7. The compound represented by formula (I) is represented by formula (II):
   

   

   
   [In the formula (II), R ¹ to R ⁴ and X are as defined above. ]
   The production method according to any one of claims 1 to 6, which is a compound represented by the formula:
8. The production method according to any one of claims 1 to 7, wherein R ¹ is a phenylene group.
9. The production method according to any one of claims 1 to 8, wherein R ² and R ³ are hydrogen atoms.
10. The production method according to any one of claims 1 to 9, wherein R ⁴ is a hydroxy group.
11. The production method according to any one of claims 1 to 10, wherein X is -NH-.
12. 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 production method according to any one of claims 1 to 11.
13. The production method according to any one of claims 1 to 12, wherein 50% by weight or more of the rubber component is a diene rubber.
14. A method for producing a rubber composition containing a sulfur component, the method comprising kneading a rubber composition obtained by the production method according to any one of claims 1 to 13 and a sulfur component. .
15. A rubber composition containing no sulfur component, obtained by the production method according to any one of claims 1 to 13.
16. A rubber composition containing a sulfur component obtained by the production method according to claim 14.
17. A vulcanized rubber composition obtained by vulcanizing the rubber composition containing the sulfur component according to claim 16.
18. A vulcanized tire comprising the vulcanized rubber composition according to claim 17.
19. A tire belt member comprising the vulcanized rubber composition according to claim 17 and a steel cord.
20. A tire carcass member comprising the vulcanized rubber composition according to claim 17 and a carcass fiber cord.
21. A tire member comprising the vulcanized rubber composition according to claim 17.
22. The tire member according to claim 21, which is a tire sidewall member, a tire inner liner member, a tire cap tread member, or a tire undertread member.
23. A method for producing a vulcanized rubber composition, comprising vulcanizing a rubber composition containing a sulfur component obtained by the production method according to claim 14.