JP2014084312A - Compound for improving viscoelastic properties of vulcanized rubber, and rubber composition including the compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound which can improve viscoelastic properties of a vulcanized rubber, and a rubber composition including the compound.SOLUTION: This invention provides a compound represented by the formula (I) or a hydrate thereof, and a rubber composition including the compound or hydrate thereof and a rubber component.

Description

  The present invention relates to a compound useful for improving viscoelastic properties of a vulcanized rubber used for producing a rubber product such as a tire or a hydrate thereof, and the compound or a hydrate thereof and a rubber component. The present invention relates to a rubber composition comprising

  In recent years, there has been a demand for improvement in fuel consumption (that is, reduction in fuel consumption) of automobiles due to a demand for environmental protection. In the field of tires for automobiles, it is known that the fuel efficiency of automobiles is improved by improving the viscoelastic properties of vulcanized rubber used in tire manufacture (Introduction to Rubber Technology, edited by the Japan Rubber Association). "See Maruzen, page 124).

  The subject of this invention is providing the rubber composition containing the compound which can improve the viscoelastic property of vulcanized rubber used in order to manufacture rubber products, such as a tire, and the said compound.

  The present invention includes the following inventions.

で表される化合物又はその水和物。 [1] Formula (I):

Or a hydrate thereof.

[2] A rubber composition comprising the compound according to [1] or a hydrate thereof and a rubber component.

[3] 100 parts by weight of diene rubber,
0.1 to 10 parts by weight of the compound according to the above [1] or a hydrate thereof,
Resorcinol, resorcinol resin, modified resorcinol resin, cresol resin, modified cresol resin, phenol resin, and at least one compound selected from the group consisting of modified phenol resin (methylene acceptor), 0.1 to 5 parts by weight and hexa At least one compound (methylene donor) selected from the group consisting of a partial condensate of methoxymethylol melamine, a partial condensate of hexamethylol melamine pentamethyl ether, and hexamethylenetetramine, containing 0.1 to 5 parts by weight A rubber composition.

[4] 100 parts by weight of a diene rubber,
0.1 to 10 parts by weight of the compound according to the above [1] or a hydrate thereof,
A rubber composition comprising 0.1 to 5 parts by weight of at least one vulcanization accelerator auxiliary selected from the group consisting of alkylphenol / sulfur chloride condensates and organic thiosulfate compounds.

[5] A rubber component containing 20 to 90 parts by weight of natural rubber and / or isoprene rubber and 10 to 80% by weight of butadiene rubber containing 1,2-syndiotactic polybutadiene crystals, 100 parts by weight,
0.1 to 10 parts by weight of the compound according to the above [1] or a hydrate thereof,
A rubber composition comprising

[6] 100 parts by weight of a diene rubber,
0.1 to 10 parts by weight of the compound according to the above [1] or a hydrate thereof,
A rubber composition comprising 5 to 70 parts by weight of a pulverized bituminous coal having an average particle size of 0.1 mm or less.

[7] 100 parts by weight of a diene rubber,
0.1 to 10 parts by weight of the compound according to the above [1] or a hydrate thereof,
A rubber composition comprising 5 to 100 parts by weight of carbon black having a DBP (dibutyl phthalate) oil absorption of 5 to 300 ml / 100 g.

[8] A rubber component containing 50 to 100 parts by weight of butyl rubber and / or halogenated butyl rubber and 0 to 50% by weight of natural rubber and / or isoprene rubber, 100 parts by weight,
0.1 to 10 parts by weight of the compound according to the above [1] or a hydrate thereof,
A rubber composition comprising 5 to 100 parts by weight of carbon black having a CTAB surface area of 20 to 60 m ² / g and a particle diameter of 40 to 100 nm.

[9] Emulsion polymerization styrene butadiene rubber and / or solution polymerization styrene butadiene rubber 100 parts by weight,
0.1 to 10 parts by weight of the compound according to the above [1] or a hydrate thereof,
A rubber composition comprising silica having a CTAB surface area of 60 to 180 m ² / g, a nitrogen adsorption specific surface area of 50 to 300 m ² / g, and 5 to 150 parts by weight.

[10] A rubber composition comprising natural rubber, the compound according to the above [1] or a hydrate thereof, and carbon black,
The content of natural rubber in 100% by weight of the rubber component is 50% by weight or more, and the content of the compound or hydrate thereof according to [1] in the rubber composition is in the rubber composition. The rubber composition for tires which is 0.3 to 10 parts by weight with respect to 100% by weight of the total content of carbon black and silica.

[11] A rubber composition for tires comprising natural rubber, the compound or hydrate thereof according to [1] above, and carbon black and / or silica.

[12] A natural rubber, the compound according to [1] or a hydrate thereof, and carbon black,
The content of natural rubber in 100% by weight of rubber component is 80% by weight or more,
A rubber composition for tires, wherein the total content of the compound according to [1] or a hydrate thereof is 0.5 to 10 parts by weight with respect to 100 parts by weight of the total of carbon black and silica.

[13] A natural rubber, the compound according to the above [1] or a hydrate thereof, and carbon black,
The content of natural rubber in 100% by weight of the rubber component is 20% by weight or more, and the rubber component contains butadiene rubber,
A rubber composition for tires, wherein the total content of the compound according to [1] above or a hydrate thereof is 0.15 to 14 parts by weight with respect to 100 parts by weight of the total of carbon black and silica.

[14] A natural rubber, the compound according to [1] or a hydrate thereof, and carbon black,
The content of natural rubber in 100% by weight of rubber component is 80% by weight or more,
A rubber composition for tires, wherein the total content of the compound according to [1] or a hydrate thereof is 0.3 to 10 parts by weight with respect to 100 parts by weight of the total of carbon black and silica.

[15] A natural rubber, the compound according to the above [1] or a hydrate thereof, and carbon black,
The content of natural rubber in 100% by weight of the rubber component is 30% by weight or more, and the rubber component includes butadiene rubber,
A rubber composition for tires, wherein the total content of the compound according to [1] or a hydrate thereof is 0.18 to 11 parts by weight with respect to 100 parts by weight of carbon black and silica in total.

[16] A rubber composition for tires comprising a rubber component containing natural rubber and butadiene rubber, the compound according to the above [1] or a hydrate thereof, and carbon black.

[17] A rubber component containing natural rubber and a butadiene rubber synthesized using a rare earth element-based catalyst, the compound according to the above [1] or a hydrate thereof, carbon black, and a formula: R ⁵ -S —S—A—S—S—R ^{6 wherein} A is an alkylene group having 2 to 10 carbon atoms, R ⁵ and R ⁶ are the same or different and each represents a monovalent organic group containing a nitrogen atom. The rubber composition for tires containing the compound represented by this.

  According to the present invention, it is possible to improve fuel efficiency in rubber products such as automobile tires by improving the viscoelastic properties of vulcanized rubber. In the present specification, “improving viscoelastic properties” includes, for example, modifying a loss factor (tan δ) of vulcanized rubber, as will be described later.

で表される化合物（以下、「化合物（Ｉ）」という。）又は化合物（Ｉ）の水和物、並びに化合物（Ｉ）又はその水和物とゴム成分とを含んでなるゴム組成物である。 Embodiments of the present invention will be described below.
The present invention relates to a compound of formula (I):

Or a hydrate of compound (I), and a rubber composition comprising compound (I) or a hydrate thereof and a rubber component. .

<Method for Producing Compound (I)>
For example, the compound (I) of the present invention produces a compound having a hydroxy group by carrying out the reactions shown in the formula (a), the formula (b) and the formula (c), and performs a salt formation reaction on the compound. Can be manufactured. Examples of the salt forming reaction include a reaction of subjecting the compound having a hydroxy group to metal chloride using a metal salt (Na hydroxide, Na carbonate, Na hydrogen carbonate, etc.).

<Method for Producing Compound (I) Hydrate>
The hydrate of the compound (I) of the present invention produces a compound having a hydroxy group, for example, by the reaction shown in the formula (a), the formula (b) and the formula (c). It can be produced by carrying out a salt formation reaction in a mixed solvent of solvents or by producing a compound (I) and then performing repulping or recrystallization with an aqueous solvent.

  The rubber composition of the present invention can be obtained by, for example, kneading the compound (I) of the present invention or a hydrate thereof and a rubber component.

  The rubber composition of the present invention contains compound (I) or a hydrate thereof in an amount of preferably 0.1 to 10 parts by weight, more preferably 0.3 to 3 parts by weight per 100 parts by weight of the rubber component. . The rubber composition of the present invention may contain compound (I) or a hydrate thereof alone or both of compound (I) and a hydrate thereof.

<Rubber component>
Examples of the rubber component contained in the rubber composition of the present invention include natural rubber (NR), epoxidized natural rubber, deproteinized natural rubber, modified natural rubber (HPNR) having a phosphorus content of 200 ppm or less, and other modifications. In addition to natural rubber, polyisoprene rubber (IR), styrene / butadiene copolymer rubber (SBR), polybutadiene rubber (BR), acrylonitrile / butadiene copolymer rubber (NBR), isoprene / isobutylene copolymer rubber (IIR), ethylene Examples include various synthetic rubbers such as propylene-diene copolymer rubber (EPDM), halogenated butyl rubber (HR), styrene isoprene butadiene rubber (SIBR), and chloroprene rubber (CR). These rubbers may be used alone or in combination of two or more. It is preferable to use a highly unsaturated rubber such as natural rubber, styrene / butadiene copolymer rubber or polybutadiene rubber, and it is more preferable to use natural rubber. It is also effective to combine several types of rubber components such as a combination of natural rubber and styrene / butadiene copolymer rubber or a combination of natural rubber and polybutadiene rubber depending on the desired application.

  Examples of natural rubber include natural rubber of grades such as RSS # 1, RSS # 3, TSR20, SIR20 and the like. As the epoxidized natural rubber, for example, those having a degree of epoxidation of 10 to 60 mol% such as ENR25 and ENR50 manufactured by Kumpoulan Guthrie are preferable. As the deproteinized natural rubber, a deproteinized natural rubber having a total nitrogen content of 0.3% by weight or less is preferable. The modified natural rubber contains a polar group obtained by reacting natural rubber with 4-vinylpyridine, N, N, -dialkylaminoethyl acrylate (for example, N, N, -diethylaminoethyl acrylate), 2-hydroxyacrylate or the like in advance. It is preferable to use a modified natural rubber. Isoprene rubbers such as NR and IR are preferred because good elongation at break and durability can be obtained.

  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. In particular, solution-polymerized SBR is preferably used as a rubber composition for treads, and further, molecular terminals using 4,4′-bis- (dialkylamino) benzophenone such as “Nippol (registered trademark) NS116” manufactured by Nippon Zeon Co., Ltd. -Polymerized SBR modified with styrene, solution-polymerized SBR modified with molecular halides using tin halide compounds such as "SL574" manufactured by JSR, and commercial products of silane-modified solution-polymerized SBR such as "E10" and "E15" manufactured by Asahi Kasei Or a lactam compound, an amide compound, a urea compound, an N, N-dialkylacrylamide compound, an isocyanate compound, an imide compound, a silane compound having an alkoxy group (trialkoxysilane compound, etc.), or an aminosilane compound. Or a silane compound having a tin compound and an alkoxy group, Two or more of the different compounds described above, such as an alkyl acrylamide compound and an alkoxy group-containing silane compound, are obtained by modifying the molecular ends, respectively, and nitrogen, tin, or silicon at the molecular ends, or Solution polymerization SBR having these plural elements is particularly preferably used. Further, oil-added SBR in which oil such as post-polymerization process oil or aroma oil is added to emulsion polymerization SBR and solution polymerization SBR is also preferable. The rubber composition of the present invention containing solution polymerization SBR and / or emulsion polymerization SBR is particularly preferably used as a rubber composition for treads.

  Examples of BR include solution polymerization BR such as high cis BR having 90% or more of cis 1,4 bond and low cis BR having cis bond of around 35%. It is preferred to use a low cis BR with a high vinyl content. Furthermore, tin-modified BR such as “Nipol (registered trademark) BR 1250H” manufactured by Nippon Zeon, 4,4′-bis- (dialkylamino) benzophenone, tin halide compound, lactam compound, amide compound, urea compound, N , N-dialkylacrylamide compounds, isocyanate compounds, imide compounds, silane compounds having an alkoxy group (trialkoxysilane compounds, etc.), aminosilane compounds alone, or a silane compound having a tin compound and an alkoxy group In addition, two or more of the different compounds described above, such as an alkylacrylamide compound and an alkoxy group-containing silane compound, are used, and each of the molecular ends obtained by modifying the molecular ends is nitrogen, tin, or silicon, or Solution polymerization BR having these multiple elements , Particularly preferably used. The rubber composition of the present invention containing these BRs can be preferably used as a rubber composition for a tread or a rubber composition for a sidewall. In addition, for example, BR1220 manufactured by Nippon Zeon Co., Ltd., BR with high cis content such as BR150B manufactured by Ube Industries, Ltd., 1,2-syndiotactic such as VCR412, VCR617 manufactured by Ube Industries, Ltd. BR that is common in the tire industry, such as BR containing polybutadiene crystals (SPB), can be used. The BR containing SPB is not simply a dispersion of crystals in the SPB-containing BR, but is chemically bonded to the SPB-containing BR and dispersed in a non-oriented manner. In addition, it is preferable that the generation and propagation of cracks tend to be suppressed by dispersing. In addition, tin-modified butadiene rubber (tin-modified BR) modified with a tin compound can also be used. BR is usually used by blending with SBR and / or natural rubber.

［式中、Ｒ^１及びＲ^２は、同一若しくは異なって、水素原子、分岐若しくは非分岐のアルキル基、分岐若しくは非分岐のアリール基、分岐若しくは非分岐のアルコキシ基、分岐若しくは非分岐のシリルオキシ基、分岐若しくは非分岐のアセタール基、カルボキシル基、メルカプト基又はこれらの誘導体を示す。Ａ’は、分岐若しくは非分岐のアルキレン基、分岐若しくは非分岐のアリーレン基又はこれらの誘導体を示す。］
で表される化合物と有機アルカリ金属化合物を反応させて得られる化学種である。
このようなジエン系重合体としては、例えば国際公開第２０１２／０５７３０８号に記載されているようなジエン系重合体が挙げられる。 The rubber composition of the present invention includes the following (A) and (B):
(A) an active conjugated diene-based polymer having an alkali metal terminal obtained by polymerizing a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer in the presence of (C) below,
(B) a modifying agent having a functional group,
It may contain a modified diene polymer obtained by reacting. Here, (C) is the following formula:

[Wherein R ¹ and R ² are the same or different and each represents a hydrogen atom, a branched or unbranched alkyl group, a branched or unbranched aryl group, a branched or unbranched alkoxy group, a branched or unbranched silyloxy group. Represents a branched or unbranched acetal group, carboxyl group, mercapto group or derivatives thereof. A ′ represents a branched or unbranched alkylene group, a branched or unbranched arylene group, or a derivative thereof. ]
Is a chemical species obtained by reacting a compound represented by the formula with an organic alkali metal compound.
Examples of such a diene polymer include a diene polymer as described in International Publication No. 2012/057308.

［式中、Ｘ^１、Ｘ^２及びＸ^３は、それぞれ独立に、下式（ｇ）：

〔式中、Ｒ^３及びＲ^４は、それぞれ独立に、炭素原子数が１〜６のヒドロカルビル基、炭素原子数が１〜６の置換ヒドロカルビル基、シリル基又は置換シリル基を表し、Ｒ^３及びＲ^４は結合して窒素原子と共に環構造を形成していてもよい。〕
で表される基、水酸基、ヒドロカルビル基又は置換ヒドロカルビル基を表し、Ｘ^１、Ｘ^２及びＸ^３の少なくとも１つが、上に示す式（ｇ）で表される基又は水酸基である。］
で表される構成単位とを有する共役ジエン系重合体であって、重合体の少なくとも一端が変性されてなる共役ジエン系重合体を含んでよい。
このような共役ジエン系重合体としては、例えば特開２０１２−１４０５９５号に記載されているような共役ジエン系重合体が挙げられる。 The rubber composition of the present invention comprises a structural unit and a formula based on a conjugated diene:

[Wherein, X ¹ , X ² and X ³ each independently represent the following formula (g):

Wherein, R ³ and R ⁴ are each independently a hydrocarbyl group having 1 to 6 carbon atoms, carbon atoms represent a 1-6 substituted hydrocarbyl group, a silyl group or a substituted silyl group, R ³ and R ⁴ may be bonded to form a ring structure with the nitrogen atom. ]
Represents a group, a hydroxyl group, a hydrocarbyl group or a substituted hydrocarbyl group, and at least one of X ¹ , X ² and X ³ is a group or a hydroxyl group represented by the formula (g) shown above. ]
And a conjugated diene polymer having at least one end modified with a conjugated diene polymer.
As such a conjugated diene polymer, for example, a conjugated diene polymer as described in JP 2012-140595 A can be mentioned.

  The rubber composition of the present invention may contain the above various rubber components and can be used for various applications. For example, when the rubber composition of the present invention is used for tire applications, the tire is required to have various performances such as high speed resistance and dry / wet grip properties in addition to low fuel consumption. In order to achieve these performances, various rubbers are selected according to the performance required for each of the members constituting the tire and blended with the compound (I) of the present invention or a hydrate thereof. The rubber composition of the present invention can be prepared.

  When the rubber composition of the present invention is used for tire treads, for example, in passenger car tires, SBR having excellent wear resistance and high hysteresis is used as a base material as a rubber component, while truck and bus tires have higher strength. It is preferable to use NR arbitrarily as a base material together with SBR, and blend BR with each to obtain wear resistance, fatigue resistance, and impact resilience. It is more excellent that the rubber composition of the present invention contains SBR and / or NR in a blend ratio of 60 to 100% by weight with respect to the total rubber weight, and BR in a blend ratio of 40 to 0% by weight with respect to the total rubber weight. Since the said characteristic is acquired, it is preferable.

  When the rubber composition of 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 of the present invention is used for tire sidewalls, NR and SBR are blended in passenger car tires, or NR and BR are blended, and NR and BR in truck and bus tires. Is preferably used as a rubber component because bending resistance and resistance to crack growth are obtained. It is more excellent that the rubber composition of the present invention contains SBR and / or NR in a blend ratio of 10 to 70% by weight with respect to the total rubber weight and BR in a blend ratio of 90 to 30% by weight with respect to the total rubber weight. Since the said characteristic is acquired, it is preferable and it is more preferable to contain NR in the blend ratio of 40 to 60 weight% with respect to the total rubber weight, and BR to 60 to 40 weight% with respect to the total rubber weight.

  When the rubber composition of the present invention is used as an inner liner of a tire, blending IIR, SBR and NR as rubber components or blending IIR and NR as a rubber component may result in gas resistance and resistance. Since flexibility is obtained, it is preferable.

  In addition to compound (I) or a hydrate thereof and a rubber component, the rubber composition of the present invention includes a filler, a sulfur component, a vulcanization accelerator, a vulcanization acceleration aid, zinc oxide, a resin, and improved viscoelastic properties. An agent or the like may be included.

<Filler>
The rubber composition of the present invention may contain fillers commonly used in the rubber field such as carbon black, silica, talc, clay, aluminum hydroxide, titanium oxide, bitumious coal and the like.

  Examples of the carbon black include those described in page 494 of “Rubber Industry Handbook <Fourth Edition>” edited by the Japan Rubber Association. HAF (High Abrasion Furnace), SAF (Super Abrasion Furnace), ISAF (Intermediate SAF), ISAF-HM (Intermediate SAF-High Modulus), FEF (Fast Extrusion Furnace), MAF, GPF (General Purpose Furnace), SRF (Semi Carbon black such as -Reinforcing Furnace) is preferred.

When using the rubber composition of the present invention for a tread of a tire, CTAB surface area 40~250m ² / g, nitrogen adsorption specific surface area 20 to 200 m ² / g, it is carbon black having a particle diameter 10~50nm Preferably, It is more preferable to use carbon black having a CTAB surface area of 70 to 180 m ² / g. Examples thereof include those of N110, N220, N234, N299, N326, N330, N330T, N339, N343, and N351 in the ASTM standard. It is also preferable to use surface-treated carbon black in which 0.1 to 50% by weight of silica is adhered to the surface of carbon black. Furthermore, it is also effective to combine a plurality of fillers such as a combination of carbon black and silica. When the rubber composition of the present invention is used for tire treads, it is preferable to use carbon black alone or to use both carbon black and silica.

When the rubber composition of the present invention is used for tire carcass and sidewalls, it is preferable to use carbon black having a CTAB surface area of 20 to 60 m ² / g and a particle diameter of 40 to 100 nm. Examples of such carbon black include N330, N339, N343, N351, N550, N568, N582, N630, N642, N660, N662, N754, N762 and the like in the ASTM standard.

  Although the usage-amount of this filler is not specifically limited, It is preferable that it is the range of 5-100 weight part with respect to 100 weight part of rubber components. When only carbon black is used as a filler, the amount is preferably 30 to 80 parts by weight, and when used in combination with silica in a tread member application, the amount is preferably 5 to 50 parts by weight.

As silica, for example, it is preferable to use silica having a CTAB specific surface area of 50 to 180 m ² / g or a nitrogen adsorption specific surface area of 50 to 300 m ² / g. Examples of these include “AQ” and “AQ-N” manufactured by Tosoh Silica Co., Ltd., “Ultrasil (registered trademark) VN3”, “Ultrasil (registered trademark) VN3-G” manufactured by Degussa, “Ultrasil (registered trademark) 360”, “Ultrasil (registered trademark) 7000”, “Zeosil (registered trademark) 115GR”, “Zeosil (registered trademark) 1115MP”, “Zeosil (registered trademark) 1205MP” manufactured by Rhodia, Commercial products such as “Zeosil (registered trademark) Z85MP” and “Nip Seal (registered trademark) AQ” manufactured by Nippon Silica Co., Ltd. Silica having a pH of 6 to 8, silica containing 0.2 to 1.5% by weight of sodium, true spherical silica having a roundness of 1 to 1.3, silicone oil such as dimethyl silicone oil, and ethoxysilyl group It is also preferable to use an organosilicon compound, silica treated with an alcohol such as ethanol or polyethylene glycol, or silica having two or more different nitrogen adsorption specific surface areas.

  When silica is used as the filler, bis (3-triethoxysilylpropyl) tetrasulfide (“Si-69” manufactured by Degussa), bis (3-triethoxysilylpropyl) disulfide (“Si-75 manufactured by Degussa) ), Bis (3-diethoxymethylsilylpropyl) tetrasulfide, bis (3-diethoxymethylsilylpropyl) disulfide, octanethioic acid S- [3- (triethoxysilyl) propyl] ester (manufactured by General Electronic Silicones) "NXT silane"), octanethioic acid S- [3-{(2-methyl-1,3-propanedialkoxy) ethoxysilyl} propyl] ester and octanethioic acid S- [3-{(2-methyl-1,3 -Propanedialkoxy) methylsilyl} propyl] ester phenyl Ethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (methoxyethoxy) silane, 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-glycidoxypropyl) triethoxysilane, 2 -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane It is preferable to add a compound having a functional group such as silicon or an element such as silicon that can be bonded to silica, such as one or more silane coupling agents selected from the group consisting of bis (3-triethoxy Silylpropyl) tetrasulfide (Degussa “Si-69”), bis 3-triethoxysilylpropyl) disulfide (manufactured by Degussa, "Si-75"), 3-octanoylthiopropyl aminopropyltriethoxysilane (General Electronic Silicon Inc. Ltd. "NXT silane") it is particularly preferred. Although the addition time of these compounds is not particularly limited, it is preferably blended with rubber at the same time as silica. These blending amounts are preferably 2 to 10% by weight, more preferably 7 to 9% by weight, based on silica. When the above silane coupling agent or the like is blended in the rubber composition of the present invention, it is preferably blended at a temperature in the range of 80 to 200 ° C, more preferably in the range of 110 to 180 ° C.

  In the case of using silica as a filler, in addition to silica, an element such as silicon capable of binding to silica or a compound having a functional group such as alkoxysilane, monohydric alcohol such as ethanol, butanol, octanol, ethylene glycol, Diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, pentaerythritol, polyether polyols and other dihydric or higher alcohols, N-alkylamines, amino acids, liquid polybutadienes whose molecular ends are carboxyl-modified or amine-modified, etc. Is also preferable.

  The rubber composition of the present invention may contain bituminous coal as a pulverized product. Bituminous coal includes general coal. 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. If it exceeds 0.1 mm, the hysteresis loss of the rubber composition may not be sufficiently reduced, and the fuel efficiency may not be sufficiently improved. Moreover, when using the composition of this invention as a composition for inner learners, air permeation resistance may not fully be improved. Although the minimum of the average particle diameter of a bituminous coal ground material is not specifically limited, Preferably it is 0.001 mm or more. If it is less than 0.001 mm, the cost tends to increase. The average particle size of the pulverized bituminous coal 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 pulverized bituminous coal is preferably 1.6 or less, more preferably 1.5 or less, and even more preferably 1.3 or less. When it exceeds 1.6, the specific gravity of the whole 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 it is less than 0.5, the workability during kneading may be deteriorated.

  The content of the bituminous coal pulverized product is usually 5 parts by weight or more, preferably 10 parts by weight or more with respect to 100 parts by weight of the rubber component. When the amount is less than 5 parts by weight, there may be a case where a sufficient effect due to the blended bituminous coal is not obtained. The content of the bituminous coal pulverized product is usually 70 parts by weight or less, preferably 60 parts by weight or less. If it exceeds 70 parts by weight, the workability during kneading may be deteriorated.

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 rubber composition of the present invention may contain two or more fillers.

  The amount of the filler used is not particularly limited, but silica is preferably used in the rubber composition for a tread for passenger cars, and the range of 10 to 120 parts by weight per 100 parts by weight of the rubber component is preferable. Moreover, when mix | blending a silica, it is preferable to mix | blend 5-50 weight part of carbon black, and the blend ratio of silica / carbon black is especially preferable 0.7 / 1-1 / 0.1.

<Sulfur component>
Examples of the sulfur component include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur. Usually, powdered sulfur is preferred, and insoluble sulfur is preferred when used for tire members having a large amount of sulfur such as belt members.

<Vulcanization accelerator>
Examples of the vulcanization accelerator include thiazole vulcanization accelerators and sulfenamides described on pages 412 to 413 of Rubber Industry Handbook <Fourth Edition> (issued by the Japan Rubber Association on January 20, 1994). And guanidine vulcanization accelerators. Specifically, for example, N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), N-tert-butyl-2-benzothiazolylsulfenamide (BBS), N, N-dicyclohexyl-2 -Benzothiazolylsulfenamide (DCBS), 2-mercaptobenzothiazole (MBT), dibenzothiazyl disulfide (MBTS), diphenylguanidine (DPG).

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

  The ratio of sulfur to the vulcanization accelerator is not particularly limited, but the rubber composition of the present invention can contain sulfur and vulcanization accelerator in the range of sulfur / vulcanization accelerator = 2/1 to 1/2 by weight ratio. It is preferable to include. Further, EV vulcanization in which the ratio of sulfur / vulcanization accelerator, which is a method for improving heat resistance in rubber members mainly composed of natural rubber, is 1 or less is used in the present invention in applications that particularly require improvement in heat resistance. Preferably used.

<Vulcanization acceleration aid>
Examples of the vulcanization accelerating auxiliary agent include a citraconimide compound, an alkylphenol / sulfur chloride condensate, an organic thiosulfate compound, and the following general formula R ⁵ —S—S—A—S—S—R ⁶
(In the formula, A represents an alkylene group having 2 to 10 carbon atoms, and R ⁵ and R ⁶ each independently represents a monovalent organic group containing a nitrogen atom.)
The compound etc. which are represented by these are mentioned.

  It is preferable to use a citraconimide compound as a vulcanization acceleration auxiliary because it does not affect the scorch time.

  As the citraconimide compound, biscitraconimides are preferable because they are thermally stable and have excellent dispersibility in rubber. 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 them, 1,3-biscitracone is particularly stable because it is thermally stable, particularly excellent in dispersibility in rubber, and a rubber composition having high hardness (Hs) can be obtained (reversion control). Imidomethylbenzene is preferred.

1,3-biscitraconimidomethylbenzene is represented by the following chemical formula.

  As a vulcanization acceleration aid, it is preferable to use an alkylphenol / sulfur chloride condensate because a rubber composition having higher hardness (Hs) can be obtained.

（式中、ｎは０又は１〜１０の整数であり、Ｘは２〜４の整数であり、Ｒは炭素数５〜１２のアルキル基である。） The alkylphenol / sulfur chloride condensate is represented by the following chemical formula.

(In the formula, n is 0 or an integer of 1 to 10, X is an integer of 2 to 4, and R is an alkyl group having 5 to 12 carbon atoms.)

  For the reason that the dispersibility of the alkylphenol / sulfur chloride condensate in rubber is good, n is preferably 0 or an integer of 1 to 10, more preferably an integer of 1 to 9.

  X is preferably an integer of 2 to 4 and more preferably 2 because X can exhibit high hardness efficiently (reversion suppression). Moreover, when X exceeds 4, it tends to become thermally unstable. When X is 1, the sulfur content (sulfur weight) in the alkylphenol-sulfur chloride condensate is small.

  R is preferably an alkyl group having 5 to 12 carbon atoms, and more preferably an alkyl group having 6 to 9 carbon atoms, because the dispersibility of the alkylphenol / sulfur chloride condensate in rubber is good. .

As a specific example of the alkylphenol / sulfur chloride condensate, n is 0-10, X is 2, R is a C ₈ H ₁₇ alkyl group, and the sulfur content is 24% by weight, manufactured by Taoka Chemical Co., Ltd. A tack roll V200 is exemplified.

The following general formula: MO ₃ SS— (CH ₂ ) _m —S—SO ₃ M [where _m is the reason why high hardness (Hs) can be obtained as a vulcanization acceleration aid (reversion suppression). Is an integer from 3 to 10, and M is lithium, potassium, sodium, magnesium, calcium, barium, zinc, nickel or cobalt. The compound is hydrophilic and may contain crystal water. It is preferable to use an organic thiosulfate compound represented by the formula:

  m is preferably an integer of 3 to 10, and more preferably an integer of 3 to 6. When m is 2 or less, sufficient heat fatigue resistance tends to be not obtained, and when m is 11 or more, the effect of improving heat fatigue resistance tends to be small although the molecular weight increases. M is preferably lithium, potassium, sodium, magnesium, calcium, barium, zinc, nickel or cobalt, and preferably potassium or sodium. Moreover, the said compound may contain crystal water in the molecule | numerator.

  Specific examples of the organic thiosulfate compound include sodium salt monohydrate, sodium salt dihydrate and the like from the property that the hydrate is stable at normal temperature and normal pressure. For economic reasons such as (NaCl) being inexpensive, a derivative from sodium thiosulfate, such as sodium 1,6-hexamethylenedithiosulfate dihydrate, is preferred.

  1,6-hexamethylenedithiosulfate sodium dihydrate is represented by the following chemical formula.

In addition to the above three types, the vulcanization acceleration aid is well dispersed in the rubber and can be supplied with sulfur, or inserted in the middle of the -Sx-crosslink of the alkylphenol / sulfur chloride condensate. For the reason that it is possible to form a hybrid bridge with a sulfur chloride condensate, the following general formula: R ⁵ —S—S—A—S—S—R ⁶ [wherein A is a carbon number of 2 to 10] It is preferable to use a compound represented by the following formula: R ⁵ and R ⁶ each independently represents a monovalent organic group containing a nitrogen atom.

  A is preferably an alkylene group. Examples of the alkylene group include linear, branched, and cyclic groups, and there is no particular limitation, and any can be used, but a linear alkylene group is preferable.

2-10 are preferable and, as for carbon number of A, 4-8 are more preferable. When the carbon number of A is 1 or less, the thermal stability is poor, and the merit obtained from the SS bond may not be obtained. Further, in the 11 or more carbon atoms of A, the distance between the through vulcanization acceleration auxiliary polymer becomes a length of more than S ₈ tether, vulcanization acceleration auxiliary is -S x _- substituted with In some cases, it is difficult to replace, the crosslinking does not proceed, and the effect of adding the vulcanization acceleration aid may not be obtained. Here, _x in -S _x- means an integer of 8 or less (that is, 1 to 8).

Examples of the alkylene group (A) satisfying the above conditions include ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, decamethylene group and the like. Among them, the alkylene group (A) is smoothly substituted because —S _x — (x = 2 to 8) is smoothly substituted for sulfur crosslinking between polymers via a vulcanization accelerating auxiliary agent and is thermally stable. Is preferably a hexamethylene group.

R ⁵ and R ⁶ are each preferably a monovalent organic group containing a nitrogen atom, more preferably an aromatic ring containing at least one, and a carbon atom bonded to a dithio group = N—C (= Those containing a linking group represented by S)-are more preferred.

R ⁵ and R ⁶ may be the same or different from each other, but are preferably the same for reasons such as ease of production.

  Examples of the compound satisfying the above conditions include 1,2-bis (N, N′-dibenzylthiocarbamoyldithio) ethane, 1,3-bis (N, N′-dibenzylthiocarbamoyldithio) propane, 1, 4-bis (N, N′-dibenzylthiocarbamoyldithio) butane, 1,5-bis (N, N′-dibenzylthiocarbamoyldithio) pentane, 1,6-bis (N, N′-dibenzylthio) Carbamoyldithio) hexane, 1,7-bis (N, N′-dibenzylthiocarbamoyldithio) heptane, 1,8-bis (N, N′-dibenzylthiocarbamoyldithio) octane, 1,9-bis (N , N′-dibenzylthiocarbamoyldithio) nonane, 1,10-bis (N, N′-dibenzylthiocarbamoyldithio) decane and the like. Of these, 1,6-bis (N, N′-dibenzylthiocarbamoyldithio) hexane is preferred because it is thermally stable and has excellent dispersibility in rubber.

The following general formula: R ⁵ —S—S—A—S—S—R ⁶ [wherein A is an alkylene group having 2 to 10 carbon atoms, R ⁵ and R ⁶ each independently include a nitrogen atom 1 Examples of the commercially available compounds represented by the formula: ) Hexane).

Among the four types of vulcanization accelerators described above, since sulfur is not contained in the molecular structure, it is thermally stable, and the initial vulcanization rate is excessively increased without releasing sulfur during crosslinking. 1,3-biscitraconimidomethylbenzene is preferred because it does not rapidly reach the target. In addition, due to the effects of the benzene ring and the C ₈ H ₁₇ branched chain (alkyl group), dispersibility in the rubber composition is good, sulfur can be released, and ultra-high hardness (Hs) is obtained. For this reason, alkylphenol / sulfur chloride condensates are preferred.

<Resin>
The rubber composition of the present invention may contain a resin such as resorcinol, resorcinol resin (condensate), modified resorcinol resin (condensate), cresol resin, modified cresol resin, phenol resin, and modified phenol resin. By including resorcinol and at least one of these resins, elongation at break and complex elastic modulus can be improved. Moreover, when using the rubber composition of this invention as a rubber product which contacts a code | cord | chord, adhesiveness with a code | cord | chord can be improved by including these resin.

  Specific examples of resorcinol include resorcinol from 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 Co., Sumikanol 620 manufactured by Taoka Chemical Industry Co., Ltd., R-6 manufactured by Uniroyal, and SRF1501 manufactured by Schenectady Chemical Co., Ltd. And Arofine 7209 manufactured by Ashland.

  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 hydroxyl group and those obtained by alkylating a part of the repeating unit of the cresol resin. Specifically, Sumikanol 610 manufactured by Taoka Chemical Industry Co., Ltd., PR-X11061 manufactured by Sumitomo Bakelite Co., Ltd. (cresol component (monomer component), o-cresol, m-cresol, p-cresol) were used. Examples of the synthesized cresol resin include a resin in which the amount of free cresol component (the amount of free monomer component) remaining in the cresol resin is as small as 0.6% by weight in 100% by weight of the cresol resin).

  As a phenol resin, a phenol-formaldehyde condensate is mentioned, for example. 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.

  It is also possible to mix and knead an agent for improving the viscoelastic properties conventionally used in the rubber field. Examples of such an agent include N, N′-bis (2-methyl-2-nitropropyl) -1,6-hexanediamine (“SUMIFINE (registered trademark) 1162” manufactured by Sumitomo Chemical Co., Ltd.), JP-A-63. Dithiouracil compound described in JP-A No. 23942, nitrosoquinoline compounds such as 5-nitroso-8-hydroxyquinoline (NQ-58) described in JP-A-60-82406, “Tacrol (registered trademark) AP, V-200 ”, alkylphenol / sulfur chloride condensates described in JP-A No. 2009-138148, such as“ BALTAC 2, 3, 4, 5, 7, 710 ”manufactured by Penwald, and bis (3-triethoxysilyl) Propyl) tetrasulfide (Degussa “Si-69”), bis (3-triethoxysilylpropyl) disulfide (Degussa) “Si-75”), bis (3-diethoxymethylsilylpropyl) tetrasulfide, bis (3-diethoxymethylsilylpropyl) disulfide, octanethioic acid S- [3- (triethoxysilyl) propyl] ester, octanethioic acid S- [3-{(2-Methyl-1,3-propanedialkoxy) ethoxysilyl} propyl] ester and octanethioic acid S- [3-{(2-methyl-1,3-propanedialkoxy) methylsilyl} propyl ] Ester phenyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, n-oct Rutrimethoxysilane, n-octyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (methoxyethoxy) silane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, 3-methacryloxypropyltrimethoxy Silane, 3-methacryloxypropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-amino Ethyl) -3-aminopropyltriethoxysilane, (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Silane coupling agents such as trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 1,6-bis (N, N′-dibenzylthiocarbamoyldithio) hexane (“BA9188” manufactured by Bayer), 1,6-hexamethylenedithiosulfate disodium salt dihydrate, 1,3-bis (citraconimidomethyl) benzene ( “Perkalink 900” manufactured by Flexis Co., Ltd.), 1-benzoyl-2-phenylhydrazide, 1- or 3-hydroxy-N ′-(1-methylethylidene) -2-naphthoic acid hydrazide, described in JP-A No. 2004-91505 1- or 3-hydroxy-N ′-(1-methylpropylidene) 2-naphthoic acid hydrazide, 1- or 3-hydroxy-N ′-(1,3-dimethylbutylidene) -2-naphthoic acid hydrazide and 1- or 3-hydroxy-N ′-(2-furylmethylene) -2 -Carboxylic acid hydrazide derivatives such as naphthoic acid hydrazide, 3-hydroxy-N '-(1,3-dimethylbutylidene) -2-naphthoic acid hydrazide described in JP-A-2000-190704, 3-hydroxy-N'- (1,3-Diphenylethylidene) -2-naphthoic acid hydrazide and 3-hydroxy-N ′-(1-methylethylidene) -2-naphthoic acid hydrazide, bismercaptooxadiazole compounds described in JP-A-2006-328310 A pyrithione salt compound described in JP2009-40898, JP2006-249361A Cobalt hydroxide compound of distribution according the like.

  Among them, N, N′-bis (2-methyl-2-nitropropyl) -1,6-hexanediamine (“Sumifine (registered trademark) 1162” manufactured by Sumitomo Chemical Co., Ltd.), 5-nitroso-8-hydroxyquinoline ( NQ-58), bis (3-triethoxysilylpropyl) tetrasulfide (“Si-69” manufactured by Degussa), bis (3-triethoxysilylpropyl) disulfide (“Si-75” manufactured by Degussa), 1, 6-bis (N, N′-dibenzylthiocarbamoyldithio) -hexane (“KA9188” manufactured by Bayer), hexamethylenebisthiosulfate disodium salt dihydrate, 1,3-bis (citraconimidomethyl) benzene (Flexera's “Parka Link 900”), Taoka Chemical's “Tacquiroll (registered trademark) AP, V-200”, etc. Le phenol-sulfur chloride condensate is preferred.

  Various compounding agents conventionally used in the rubber field can also be blended. As such a compounding agent, for example, an anti-aging agent such as “Antigen (registered trademark) 6C” manufactured by Sumitomo Chemical Co., Ltd .; oil; fatty acids such as stearic acid; Coumarone resin NG4 (softening point 81) manufactured by Nippon Steel Chemical Co., Ltd. ~ 100 ° C), process resin AC5 (softening point 75 ° C) of Kobe Oil Chemical Co., Ltd .; terpene resins such as terpene resin, terpene / phenol resin, aromatic modified terpene resin; Mitsubishi Gas Rosin derivatives such as Chemical Co., Ltd. “Nikanol (registered trademark) A70” (softening point 70-90 ° C.); Hydrogenated rosin derivatives; Novolac alkylphenol resins; Resole alkylphenol resins; C5 petroleum resins; Liquid polybutadienes; Is mentioned.

  Examples of the oil include process oil and vegetable oil. Examples of the process oil include paraffinic process oil, naphthenic process oil, aromatic process oil, and the like. For example, aromatic oil (“NC-140” manufactured by Cosmo Oil Co., Ltd.), process oil (produced by Idemitsu Kosan Co., Ltd. “ And Diana process PS32 ").

  Examples of the anti-aging agent include those described in pages 436 to 443 of “Rubber Industry Handbook <Fourth Edition>” edited by the Japan Rubber Association. Among them, N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine (6PPD), reaction product of aniline and acetone (TMDQ), poly (2,2,4-trimethyl-1,2-) dihydro Quinoline) (“Antioxidant FR” manufactured by Matsubara Sangyo Co., Ltd.), synthetic wax (paraffin wax, etc.) and vegetable wax are preferably used.

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

  It is also possible to blend and knead a vulcanizing agent such as morpholine disulfide conventionally used in the rubber field.

  Further, a peptizer and a retarder may be blended and kneaded, and various general rubber chemicals and softeners may be blended and kneaded as necessary.

  Examples of the retarder include phthalic anhydride, benzoic acid, salicylic acid, N-nitrosodiphenylamine, N- (cyclohexylthio) -phthalimide (CTP), sulfonamide derivatives, diphenylurea, bis (tridecyl) pentaerythritol-diphosphite, etc. It is preferable to use N- (cyclohexylthio) -phthalimide (CTP).

  The amount of the retarder used is not particularly limited, but is preferably in the range of 0.01 to 1 part by weight per 100 parts by weight of the rubber component. Particularly preferred is 0.05 to 0.5 parts by weight.

The rubber composition of the present invention comprises a compound having an oxyethylene unit having a structure represented by the general formula: —O— (CH ₂ —CH ₂ —O) _q —H [wherein q is an integer of 1 or more]. May be included. Here, in the above formula, q is preferably 1 or more, more preferably 2 or more, and further preferably 3 or more. When q is 0, there is no oxyethylene unit, and there is a tendency that a sufficient electric resistance reduction effect cannot be obtained. 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. Above all, when the oxyethylene unit is graft-polymerized to polyethylene, etc., like a compound that is generally used as a permanent antistatic agent, the surface characteristics of the resulting tire, such as the persistence of the effect of preventing the accumulation of static electricity and the reduction of electrical resistance, are obtained. A compound having an oxyethylene unit at least in the side chain is preferred because of its excellent performance.

  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, polyoxypropylene alkyl ether, Examples include polyoxyethylene alkylamine, polyoxystyrene alkyl ether, polyoxyethylene alkyl amide, and the like.

  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.

  Moreover, when using the compound which has an oxyethylene unit at least in a side chain, it is preferable to use the compound which mainly has polyethylene, a polypropylene, or polystyrene as a main chain.

  As a procedure for kneading each component, a rubber component and a filler are kneaded (hereinafter sometimes referred to as “procedure 1”), and then the composition obtained in procedure 1 and a sulfur component are kneaded. (Hereinafter also referred to as “procedure 2”). Compound (I) is blended in Procedure 1, Procedure 2, or both Procedure 1 and Procedure 2. Compound (I) is preferably blended in Procedure 1. Both the kneaded product obtained in Procedure 1 and the kneaded product obtained in Procedure 2 are rubber compositions of the present invention.

  Compound (I) can be blended in advance with a carrier. Examples of such a carrier include the fillers exemplified above and “inorganic fillers and reinforcing agents” described on pages 510 to 513 of “Rubber Industry Handbook <Fourth Edition>” edited by the Japan Rubber Association. Carbon black, silica, calcined clay and aluminum hydroxide are preferred. The amount of the carrier used is not particularly limited, but is preferably in the range of 10 to 1000 parts by weight per 100 parts by weight of compound (I).

  When blending zinc oxide, blending in Procedure 1 is preferable, and when blending a vulcanization accelerator, blending in Procedure 2 is preferable.

  A vulcanizing agent such as morpholine disulfide is preferably blended in the procedure 2.

  The retarder may be blended and kneaded in Procedure 1, but is preferably blended and kneaded in Procedure 2.

When mix | blending in the procedure 1, 80-200 degreeC is preferable for the temperature conditions at the time of a mixing | blending. More preferably, it is 110-180 degreeC. As for the temperature conditions at the time of the mixing | blending in the procedure 2, 50-100 degreeC is preferable.
The rubber composition obtained in the procedure 2 (that is, the rubber composition obtained by kneading the compound (I), the rubber component, the filler and the sulfur component, and may be hereinafter referred to as “the rubber composition”. )) Is heat treated to obtain a vulcanized rubber. The temperature condition in the heat treatment is preferably 110 to 180 ° C. The heat treatment is usually performed at normal pressure or under pressure.

  For example, a rubber composition processed into a specific shape is obtained from the rubber composition of the present invention, and the rubber composition can be heat-treated to obtain a vulcanized rubber. Here, the “rubber composition processed into a specific state” means, for example, in the field of tires, “the rubber composition coated with a steel cord” “the rubber composition coated with a carcass fiber cord”. “The rubber composition processed into the shape of a tread member” and the like. Belts, carcass, inner liners, sidewalls, treads (cap treads or under treads), band toppings, breakers, breaker edge strips, breaker cushions, wings, bead apex, clinch apex etc. Each member is usually molded together with other members into a tire shape by a method commonly used in the field of tires, that is, the rubber composition is incorporated into the tire, and the state of the raw tire containing the rubber composition Heat treated. Such heat treatment is usually performed under pressure.

  Using the raw tire thus obtained, a tire is produced by a usual method. That is, the rubber composition in the stage before the vulcanization treatment is extruded into a tread member, and is pasted and molded by a usual method on a tire molding machine to form a green tire. A tire can be obtained by heating and pressurizing. Examples of the tire include a pneumatic tire and a solid tire.

  The fuel efficiency of the automobile equipped with the tire thus obtained is improved, and a reduction in fuel consumption can be achieved.

  When compound (I) or a hydrate thereof is added to a rubber composition for tires, viscoelastic properties of a vulcanized rubber obtained by vulcanizing the compound can be improved. Further, the vulcanized rubber can be used not only for the tire applications described above, but also for various anti-vibration rubber applications, various rubber belt applications, vibration damping applications, and seismic isolation rubber applications. 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 is usually obtained by processing the kneaded product into a shape possessed by the anti-vibration rubber and then subjecting it to a heat treatment. Moreover, as a rubber belt use, a power transmission belt, a conveyor belt, a V belt etc. are mentioned, for example.

  The rubber composition of the present invention can be used for a fuel-efficient tire by containing compound (I) or a hydrate thereof. In addition, the rubber composition of the present invention has other general physical properties required for rubber (steering stability, wear resistance, low heat generation, fracture resistance, heat aging resistance, rolling resistance physical properties, hardness, modulus, workability, work Depending on the properties, wet grip performance, run flat durability, wet skid property, and chip cutting properties), the types and amounts of the above components can be appropriately changed and blended.

  In a preferred embodiment, the rubber composition of the present invention preferably contains, as a rubber component, natural rubber alone or a blend of SBR and / or BR containing natural rubber as a main component. In this embodiment, the filler preferably includes carbon black alone or a blend with carbon black containing silica as a main component. Further, N, N′-bis (2-methyl-2-nitropropyl) -1,6-hexanediamine (“Sumifine (registered trademark) 1162” manufactured by Sumitomo Chemical Co., Ltd.), 5-nitroso-8-hydroxyquinoline ( NQ-58), bis (3-triethoxysilylpropyl) tetrasulfide (Si-69), bis (3-triethoxysilylpropyl) disulfide (Si-75), 1,6-bis (N, N′-di) Benzylthiocarbamoyldithio) -hexane ("KA9188" manufactured by Bayer), hexamethylene bisthiosulfate disodium salt dihydrate, 1,3-bis (citraconimidomethyl) benzene ("Parkalink 900" manufactured by Flexis) , Alkylphenol / sulfur chloride condensates such as “Tacchirol (registered trademark) AP, V-200” manufactured by Taoka It is preferable to use a viscoelastic improving agent. Such a rubber composition is suitable as a rubber composition for a tread member suitable for trucks, buses, light trucks, and large construction tires.

  In a preferred embodiment, the rubber composition of the present invention comprises, as a rubber component, a solution-polymerized SBR having a molecular end modified with a silicon compound alone or the above-mentioned terminal-modified solution-polymerized SBR as a main component, an unmodified solution-polymerized SBR, an emulsion. It preferably includes a blend with at least one rubber selected from the group consisting of polymerized SBR, natural rubber and BR. In this embodiment, the filler preferably contains a blend with carbon black containing silica as a main component. Further, N, N′-bis (2-methyl-2-nitropropyl) -1,6-hexanediamine (“Sumifine (registered trademark) 1162” manufactured by Sumitomo Chemical Co., Ltd.), 5-nitroso-8-hydroxyquinoline ( NQ-58), bis (3-triethoxysilylpropyl) tetrasulfide (Si-69), bis (3-triethoxysilylpropyl) disulfide (Si-75), 1,6-bis (N, N′-di) Benzylthiocarbamoyldithio) -hexane ("KA9188" manufactured by Bayer), hexamethylene bisthiosulfate disodium salt dihydrate, 1,3-bis (citraconimidomethyl) benzene ("Parkalink 900" manufactured by Flexis) , Alkylphenol / sulfur chloride condensates such as “Tacchirol (registered trademark) AP, V-200” manufactured by Taoka It is preferable to use a viscoelastic improving agent. Such a rubber composition is suitable as a rubber composition for a tread member suitable for a passenger car tire.

  In a preferred embodiment, the rubber composition of the present invention is a blend of at least one rubber selected from the group consisting of BR as a main component, non-modified solution polymerization SBR, emulsion polymerization SBR and natural rubber as a rubber component. It is preferable to contain. In this embodiment, the filler preferably includes carbon black alone or a blend with silica containing carbon black as a main component. Further, N, N′-bis (2-methyl-2-nitropropyl) -1,6-hexanediamine (“Sumifine (registered trademark) 1162” manufactured by Sumitomo Chemical Co., Ltd.), 5-nitroso-8-hydroxyquinoline ( NQ-58), bis (3-triethoxysilylpropyl) tetrasulfide (Si-69), bis (3-triethoxysilylpropyl) disulfide (Si-75), 1,6-bis (N, N′-di) Benzylthiocarbamoyldithio) -hexane ("KA9188" manufactured by Bayer), hexamethylene bisthiosulfate disodium salt dihydrate, 1,3-bis (citraconimidomethyl) benzene ("Parkalink 900" manufactured by Flexis) , Alkylphenol / sulfur chloride condensates such as “Tacchirol (registered trademark) AP, V-200” manufactured by Taoka It is preferable to use a viscoelastic improving agent. Such a rubber composition is suitable as a rubber composition for a sidewall member.

  In a preferred embodiment, the rubber composition of the present invention preferably contains natural rubber alone or a blend with BR containing natural rubber as a main component as the rubber component. In this embodiment, the filler preferably includes carbon black alone or a blend with silica containing carbon black as a main component. Further, N, N′-bis (2-methyl-2-nitropropyl) -1,6-hexanediamine (“Sumifine (registered trademark) 1162” manufactured by Sumitomo Chemical Co., Ltd.), 5-nitroso-8-hydroxyquinoline ( NQ-58), bis (3-triethoxysilylpropyl) tetrasulfide (Si-69), bis (3-triethoxysilylpropyl) disulfide (Si-75), 1,6-bis (N, N′-di) Benzylthiocarbamoyldithio) -hexane ("KA9188" manufactured by Bayer), hexamethylene bisthiosulfate disodium salt dihydrate, 1,3-bis (citraconimidomethyl) benzene ("Parkalink 900" manufactured by Flexis) , Alkylphenol / sulfur chloride condensates such as “Tacchirol (registered trademark) AP, V-200” manufactured by Taoka It is preferable to use a viscoelastic improving agent. Such a rubber composition is suitable as a rubber composition for carcass and belt members.

  In a preferred embodiment, the rubber composition of the present invention comprises 100 parts by weight of a diene rubber, 0.1 to 10 parts by weight of compound (I) or a hydrate thereof, resorcinol, resorcinol resin, modified resorcinol resin, cresol resin, modified At least one compound selected from the group consisting of a cresol resin, a phenol resin, and a modified phenol resin (methylene acceptor), 0.1 to 5 parts by weight, and a partial condensate of hexamethoxymethylol melamine, hexamethylol melamine It comprises 0.1 to 5 parts by weight of a partial condensate of pentamethyl ether and at least one compound (methylene donor) selected from the group consisting of hexamethylenetetramine. The rubber composition of this embodiment containing a resin component such as a modified resorcinol resin is preferable because it gives a vulcanized rubber having good cord adhesion, elongation at break, and complex elastic modulus. Further, it is preferable to include a partial condensate of hexamethylol melamine pentamethyl ether because the cord and the rubber adhesive layer can be strengthened.

  In a preferred embodiment, the rubber composition of the present invention comprises 100 parts by weight of a diene rubber, 0.1 to 10 parts by weight of compound (I) or a hydrate thereof, an alkylphenol / sulfur chloride condensate, and an organic thiosulfate compound. It comprises at least one vulcanization acceleration auxiliary selected from the group consisting of 0.1 to 5 parts by weight. The rubber composition of this embodiment is preferable because it has good extrudability in the vulcanization process and gives a vulcanized rubber having rigidity and superior fuel efficiency.

  In a preferred embodiment, the rubber composition of the present invention comprises a rubber component comprising 20 to 90 parts by weight of natural rubber and / or isoprene rubber and 10 to 80% by weight of butadiene rubber containing 1,2-syndiotactic polybutadiene crystals, It comprises 100 parts by weight, 0.1 to 10 parts by weight of compound (I) or a hydrate thereof. The rubber composition of this embodiment is preferred because it provides a vulcanized rubber composition having a reduced loss factor (tan δ) and good complex modulus.

  In a preferred embodiment, the rubber composition of the present invention comprises 100 parts by weight of a diene rubber, 0.1 to 10 parts by weight of compound (I) or a hydrate thereof, and a bituminous coal pulverized product 5 having an average particle size of 0.1 mm or less. -70 parts by weight. The rubber composition of this embodiment containing a bituminous coal pulverized product is preferable because it provides a vulcanized rubber composition having good moldability and a reduced loss factor (tan δ).

  In a preferred embodiment, the rubber composition of the present invention comprises 100 parts by weight of a diene rubber, 0.1 to 10 parts by weight of compound (I) or a hydrate thereof, and a DBP (dibutyl phthalate) oil absorption of 5 to 300 ml / 100 g. 5 to 100 parts by weight of carbon black. The rubber composition of this embodiment is preferred because it provides a vulcanized rubber having improved viscoelastic properties.

In a preferred embodiment, the rubber composition of the present invention comprises 50 to 100 parts by weight of a butyl rubber and / or halogenated butyl rubber, and a rubber component containing 0 to 50% by weight of natural rubber and / or isoprene rubber, 100 parts by weight, a compound ( I) or 0.1 to 10 parts by weight of a hydrate thereof, 5 to 100 parts by weight of carbon black having a CTAB surface area of 20 to 60 m ² / g and a particle diameter of 40 to 100 nm. The rubber composition of this embodiment is preferred because it provides a vulcanized rubber having improved viscoelastic properties.

In a preferred embodiment, the rubber composition of the present invention comprises emulsion polymerization styrene butadiene rubber and / or solution polymerization styrene butadiene rubber 100 parts by weight, compound (I) or a hydrate thereof 0.1 to 10 parts by weight, CTAB surface area 60 -180 m < ² > / g, a nitrogen adsorption specific surface area 50-300 m < ² > / g silica, 5-150 weight part is comprised. The rubber composition of this embodiment is preferred because it provides a vulcanized rubber having improved viscoelastic properties.

  In a preferred embodiment, the rubber composition of the present invention is a rubber composition comprising a rubber component, compound (I) or a hydrate thereof, and carbon black, and comprises 100% by weight of the natural rubber in the rubber component. The content is 50% by weight or more, and the content of the compound (I) or hydrate thereof in the rubber composition is 100% by weight based on the total content of carbon black and silica in the rubber composition. The rubber composition is 0.3 to 10 parts by weight. The rubber composition of this embodiment is preferred because it provides a vulcanized rubber having improved viscoelastic properties.

  In a preferred embodiment, the rubber composition of the present invention is a tire rubber composition comprising natural rubber, compound (I) or a hydrate thereof, carbon black and / or silica. The rubber composition of this embodiment is preferred because it provides a vulcanized rubber having improved viscoelastic properties.

In a preferred embodiment, the rubber composition of the present invention comprises natural rubber, compound (I) or a hydrate thereof, and carbon black.
The content of natural rubber in 100% by weight of rubber component is 80% by weight or more,
The tire rubber composition has a total content of Compound (I) or a hydrate thereof of 0.5 to 10 parts by weight with respect to 100 parts by weight of the total of carbon black and silica. The rubber composition of this embodiment is preferred because it provides a vulcanized rubber having improved viscoelastic properties.

In a preferred embodiment, the rubber composition of the present invention comprises natural rubber, compound (I) or a hydrate thereof, and carbon black.
The content of natural rubber in 100% by weight of the rubber component is 20% by weight or more, and the rubber component contains butadiene rubber,
A tire rubber composition in which the total content of compound (I) or a hydrate thereof is 0.15 to 14 parts by weight with respect to 100 parts by weight of carbon black and silica in total. The rubber composition of this embodiment is preferred because it provides a vulcanized rubber having improved viscoelastic properties.

In a preferred embodiment, the rubber composition of the present invention comprises natural rubber, compound (I) or a hydrate thereof, and carbon black.
The content of natural rubber in 100% by weight of rubber component is 80% by weight or more,
The tire rubber composition has a total content of Compound (I) or a hydrate thereof of 0.3 to 10 parts by weight with respect to 100 parts by weight of the total of carbon black and silica. The rubber composition of this embodiment is preferred because it provides a vulcanized rubber having improved viscoelastic properties.

In a preferred embodiment, the rubber composition of the present invention comprises natural rubber, compound (I) or a hydrate thereof, and carbon black.
The content of natural rubber in 100% by weight of the rubber component is 30% by weight or more, and the rubber component includes butadiene rubber,
The tire rubber composition has a total content of compound (I) or a hydrate thereof of 0.18 to 11 parts by weight based on 100 parts by weight of carbon black and silica. The rubber composition of this embodiment is preferred because it provides a vulcanized rubber having improved viscoelastic properties.

  In a preferred embodiment, the rubber composition of the present invention is a tire rubber composition containing a rubber component containing natural rubber and butadiene rubber, compound (I) or a hydrate thereof, and carbon black. The rubber composition of this embodiment is preferred because it provides a vulcanized rubber having improved viscoelastic properties.

In a preferred embodiment, the rubber composition of the present invention comprises a rubber component containing natural rubber and a butadiene rubber synthesized using a rare earth element-based catalyst, compound (I) or a hydrate thereof, carbon black, Formula: R ¹² —S—S—Y—S—S—R ¹³ [wherein Y is an alkylene group having 2 to 10 carbon atoms, and R ¹² and R ¹³ are the same or different and contain a nitrogen atom] It represents a monovalent organic group] and a rubber composition for tires. The rubber composition of this embodiment is preferred because it provides a vulcanized rubber having improved viscoelastic properties.

In a preferred embodiment, the rubber composition of the present invention preferably contains compound (I) or a hydrate thereof with respect to 100 parts by weight of a rubber component containing preferably 50% by weight or more of isoprene-based rubber such as NR and IR. 0.1 to 10 parts by weight, more preferably 0.3 to 3 parts by weight, sulfur preferably 1.5 to 2.9 parts by weight, resorcinol resin, modified resorcinol resin, cresol resin, modified cresol resin, phenol resin, And at least one compound selected from the group consisting of a modified phenolic resin, preferably selected from the group consisting of 1 to 3 parts by weight, a partial condensate of hexamethoxymethylol melamine, and a partial condensate of hexamethylol melamine pentamethyl ether Preferably at least one compound is 0.7-3 parts by weight, silica is preferably 5-17 parts by weight A nitrogen adsorption specific surface area preferably from 10 to 55 parts by weight of carbon black 38~125m ² / g. The rubber composition of the present invention in this embodiment can improve the complex elastic modulus, low exothermic property, elongation at break, suppress the generation of BEL, and provide a vulcanized rubber excellent in fuel efficiency and durability. It is preferably used as a rubber composition for topping. In this case, it is more preferable that the rubber component further contains a styrene butadiene rubber because a tire excellent in reversion resistance, heat resistance, and crack growth resistance can be obtained.

  In a preferred embodiment, the rubber composition of the present invention preferably contains compound (I) or a hydrate thereof with respect to 100 parts by weight of a rubber component containing preferably 50% by weight or more of isoprene-based rubber such as NR and IR. 0.1 to 10 parts by weight, more preferably 0.3 to 3 parts by weight, sulfur preferably 2.0 to 3.99 parts by weight, resorcinol resin, modified resorcinol resin, cresol resin, modified cresol resin, phenol resin, And at least one compound selected from the group consisting of a modified phenolic resin, preferably 0.6 to 4 parts by weight, a partial condensate of hexamethoxymethylol melamine, and a partial condensate of hexamethylol melamine pentamethyl ether Preferably at least one compound selected from 0.6 to 4 parts by weight, cobalt organic acid, Preferably in terms of including 0.05 to 0.30 parts by weight. In this aspect, the rubber composition of the present invention can improve elongation at break while maintaining hardness, adhesion to cords, and workability (sheet rollability), suppress the occurrence of BEL, and has excellent durability. In order to give a vulcanized rubber, it is particularly preferable to use it as a rubber composition for a breaker edge strip. In this case, it is more preferable that the rubber composition of the present invention contains silica because elongation at break and cord adhesion can be improved.

  In a preferred embodiment, the rubber composition of the present invention comprises NR and / or IR, preferably 20 to 90% by weight, and BR containing 1,2-syndiotactic polybutadiene crystals, modified BR, emulsion polymerization SBR and solution polymerization modification. Preferably 100 to 100 parts by weight of the rubber component containing at least one synthetic rubber selected from the group consisting of SBR, preferably 10 to 80% by weight, the compound (I) or a hydrate thereof is preferably 0.1 to 10% by weight. Parts, more preferably 0.3 to 3 parts by weight, preferably 5 to 30 parts by weight of phenolic resin and / or modified phenolic resin, preferably 5 to 8 parts by weight of sulfur, and preferably alkylphenol / sulfur chloride condensate. Contains 0.1 to 3 parts by weight. In this embodiment, the rubber composition of the present invention suppresses reversion, provides a vulcanized rubber excellent in processability, handling stability, fuel efficiency, run flat durability and flat spot riding comfort. It is preferably used as a rubber composition for apex. In this case, it is more preferable to contain 5.1 to 10 parts by weight of zinc oxide because reversion can be further suppressed.

［式（e）中、Ｒ^１及びＲ^２は、同一若しくは異なって、水素原子、分岐若しくは非分岐のアルキル基、分岐若しくは非分岐のアリール基、分岐若しくは非分岐のアルコキシ基、分岐若しくは非分岐のシリルオキシ基、分岐若しくは非分岐のアセタール基、カルボキシル基、メルカプト基又はこれらの誘導体を示す。Ａ’は、分岐若しくは非分岐のアルキレン基、分岐若しくは非分岐のアリーレン基又はこれらの誘導体を示す。］

［式（h）中、Ｙは、分岐若しくは非分岐の炭素数２〜１０のアルキレン基、Ｒ^１２及びＲ^１３は、同一若しくは異なって、チッ素原子を含む１価の分岐若しくは非分岐の有機基を表す］。
ここで、上記式（ｅ）で表される化合物は、下記式（ｉ）で表される化合物であることが好ましい。

上記変性剤は、下記式（ｊ）で表される化合物であることが好ましい。

［式（ｊ）中、Ｒ^７及びＲ^８は、同一又は異なって、分岐若しくは非分岐の炭素数１〜１０の炭化水素基を表し、該炭化水素基は、エーテル、及び３級アミンからなる群より選択される少なくとも１種の基を有してもよい。Ｒ^９及びＲ^１０は、同一若しくは異なって、水素原子、又は分岐若しくは非分岐の炭素数１〜２０の炭化水素基を表し、該炭化水素基は、エーテル、及び３級アミンからなる群より選択される少なくとも１種の基を有してもよい。Ｒ^１１は、分岐若しくは非分岐の炭素数１〜２０の炭化水素基を表し、該炭化水素基は、エーテル、３級アミン、エポキシ、カルボニル、及びハロゲンからなる群より選択される少なくとも１種の基を有してもよい。ｐは１〜６の整数を表す。］
上記活性共役ジエン系重合体の両末端に導入した変性剤は、同一であることが好ましい。
また、この態様における本発明のゴム組成物は、ゴム成分１００重量％中の上記ジエン系重合体の含有量が５重量％以上であることが好ましい。上記共役ジエンモノマーは、１，３−ブタジエン及び／又はイソプレンであり、上記芳香族ビニルモノマーがスチレンであることが好ましい。上記シリカのチッ素吸着比表面積は、４０〜２５０ｍ^２／ｇであることが好ましい。
この態様における本発明のゴム組成物は、トレッド用ゴム組成物として用いられることが好ましい。ここで、上記変性されたジエン系重合体は、１，３−ブタジエン及びスチレンを重合させることにより得られる変性スチレンブタジエンゴムが好適である。 In a preferred embodiment, the rubber composition of the present invention comprises a diene polymer, silica and a compound represented by the following formula (h), and the diene polymer comprises the following (A) and (B): It is a modified diene polymer obtained by reaction, and is a rubber composition for tires containing 5 to 23 parts by weight of the compound represented by the above formula (h) with respect to 100 parts by weight of the rubber component.
(A): an active conjugated diene polymer having an alkali metal end obtained by polymerizing a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer in the presence of (C) below (B): functional group Modifier (C) having: a chemical species obtained by reacting a compound represented by the following formula (e) with an organic alkali metal compound

[In Formula (e), R ¹ and R ² are the same or different and each represents a hydrogen atom, a branched or unbranched alkyl group, a branched or unbranched aryl group, a branched or unbranched alkoxy group, branched or unbranched. A silyloxy group, a branched or unbranched acetal group, a carboxyl group, a mercapto group, or a derivative thereof. A ′ represents a branched or unbranched alkylene group, a branched or unbranched arylene group, or a derivative thereof. ]

[In the formula (h), Y is a branched or unbranched alkylene group having 2 to 10 carbon atoms, R ¹² and R ¹³ are the same or different and are monovalent branched or unbranched organic containing a nitrogen atom. Represents a group].
Here, the compound represented by the above formula (e) is preferably a compound represented by the following formula (i).

The modifier is preferably a compound represented by the following formula (j).

[In formula (j), R ⁷ and R ⁸ are the same or different and each represents a branched or unbranched hydrocarbon group having 1 to 10 carbon atoms, and the hydrocarbon group comprises an ether and a tertiary amine. It may have at least one group selected from the group. R ⁹ and R ¹⁰ are the same or different and each represents a hydrogen atom or a branched or unbranched hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group is selected from the group consisting of ethers and tertiary amines. It may have at least one group. R ¹¹ represents a branched or unbranched hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group is at least one selected from the group consisting of ether, tertiary amine, epoxy, carbonyl, and halogen. It may have a group. p represents an integer of 1 to 6. ]
The modifiers introduced at both ends of the active conjugated diene polymer are preferably the same.
In the rubber composition of the present invention in this embodiment, the content of the diene polymer in 100% by weight of the rubber component is preferably 5% by weight or more. The conjugated diene monomer is 1,3-butadiene and / or isoprene, and the aromatic vinyl monomer is preferably styrene. The nitrogen adsorption specific surface area of the silica is preferably 40 to 250 m ² / g.
The rubber composition of the present invention in this aspect is preferably used as a tread rubber composition. Here, the modified diene polymer is preferably a modified styrene butadiene rubber obtained by polymerizing 1,3-butadiene and styrene.

In a preferred embodiment, the rubber composition of the present invention comprises compound (I) or its hydration with respect to 100 parts by weight of a diene rubber such as NR, IR, BR, SBR, IIR, halogenated IIR, CR, NBR. The product is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 3 parts by weight, the phenol resin and / or the modified phenol resin is preferably 5 to 25 parts by weight, and the sulfur is preferably 5.1 to 7 parts. 0 part by weight, preferably 1.0 to 2.0 parts by weight of hexamethylenetetramine, preferably 2.0 to 5.0 parts by weight of sulfenamide vulcanization accelerator and / or thiazole vulcanization accelerator, And an alkylphenol / sulfur chloride condensate, an organic thiosulfate compound and a general formula: R ¹ —S—S—A—S—S—R ² (wherein A is an alkylene group having 2 to 10 carbon atoms, R ¹ and R ² , Preferably at least one vulcanization acceleration auxiliary selected from the group consisting of compounds represented by each independently represent a monovalent organic group containing a nitrogen atom) contains 0.1 to 5 parts by weight. The rubber composition of the present invention in this aspect has good processability, has a high rigidity and a reduced loss factor, and provides a vulcanized rubber having steering stability and low fuel consumption. More preferably, it is used as a rubber composition for apex.

  In a preferred embodiment, the rubber composition of the present invention is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 3 parts by weight of compound (I) or a hydrate thereof with respect to 100 parts by weight of the rubber component. It preferably contains 5 to 70 parts by weight of a bituminous coal pulverized product having an average particle size of 0.1 mm or less and preferably 1 to 20 parts by weight of a mixed resin. The rubber composition of the present invention in this aspect is particularly preferably used as a rubber composition for an inner liner because it gives a vulcanized rubber having excellent air permeation resistance, low fuel consumption and molding processability. In this case, a rubber composition in which the content of halogenated butyl rubber in 100% by weight of the rubber component is 70% by weight or more is preferable because it gives a vulcanized rubber having superior air permeation resistance.

［式中、Ｒは、それぞれ、同一若しくは異なって炭素数５〜１２のアルキル基を表す。ｘは、それぞれ、同一若しくは異なって、２〜４の整数を表す。ｎは、０〜１０の整数を表す。］
で表されるアルキルフェノール・塩化硫黄縮合物を含み、前記ゴム成分１００重量％中の天然ゴム及びブタジエンゴムの合計含有量が好ましくは３０重量％以上であり、前記ゴム成分１００重量部に対して、化合物（Ｉ）又はその水和物を好ましくは０．１〜１０重量部、より好ましくは０．３〜３重量部、前記アロマオイルを好ましくは１２〜８５重量部、前記シリカを好ましくは１２〜８５重量部、前記アルキルフェノール・塩化硫黄縮合物を好ましくは０．２５〜６．０重量部含み、かつ前記硫黄及び前記アルキルフェノール・塩化硫黄縮合物に含まれる硫黄の合計含有量が０．３〜３重量部であり、前記シリカ及び前記カーボンブラックの合計１００重量％中の該シリカの含有量が４５重量％以上であるゴム組成物である。この態様における本発明のゴム組成物は、耐摩耗性能、氷雪上性能、操縦安定性、ウェットグリップ性能に優れた加硫ゴムを与えるため、特にスタッドレスタイヤ用ゴム組成物として用いることが好ましく、スタッドレスタイヤのトレッド用ゴム組成物として用いることがさらに好ましい。 In a preferred embodiment, the rubber composition of the present invention comprises a rubber component, compound (I) or a hydrate thereof, aroma oil, silica, carbon black, sulfur and the following formula:

[Wherein, R's are the same or different and each represents an alkyl group having 5 to 12 carbon atoms. x is the same or different and represents an integer of 2 to 4; n represents an integer of 0 to 10. ]
And the total content of natural rubber and butadiene rubber in 100% by weight of the rubber component is preferably 30% by weight or more, with respect to 100 parts by weight of the rubber component, The compound (I) or a hydrate thereof is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 3 parts by weight, the aroma oil is preferably 12 to 85 parts by weight, and the silica is preferably 12 to 85 parts by weight, preferably 0.25 to 6.0 parts by weight of the alkylphenol / sulfur chloride condensate, and the total content of sulfur and sulfur contained in the alkylphenol / sulfur chloride condensate is 0.3 to 3 It is a rubber composition in which the content of silica in a total of 100% by weight of the silica and the carbon black is 45% by weight or more. The rubber composition of the present invention in this aspect is preferably used as a rubber composition for studless tires in order to give a vulcanized rubber having excellent wear resistance, performance on snow and snow, handling stability, and wet grip performance. More preferably, it is used as a rubber composition for a tire tread.

［式中、Ｘ^１、Ｘ^２及びＸ^３は、それぞれ独立に、下式（ｇ）で表される基、水酸基、ヒドロカルビル基又は置換ヒドロカルビル基を表し、Ｘ^１、Ｘ^２及びＸ^３の少なくとも１つが、下式（ｇ）で表される基又は水酸基である。］

［式中、Ｒ^３及びＲ^４は、それぞれ独立に、炭素原子数が１〜６のヒドロカルビル基、炭素原子数が１〜６の置換ヒドロカルビル基、シリル基又は置換シリル基を表し、Ｒ^３及びＲ^４は結合して窒素原子と共に環構造を形成していてもよい。］
この態様において、上記式（ｇ）のＲ^３及びＲ^４は炭素原子数１〜６のヒドロカルビル基であることが好ましく、上記式（ｆ）のＸ^１、Ｘ^２及びＸ^３の２つが式（ｇ）で表される基又は水酸基であることが好ましい。また、共役ジエン系重合体のビニル結合量が、共役ジエンに基づく構成単位の含有量を１００モル％として、１０モル％以上８０モル％以下であることが好ましい。
この態様における本発明のゴム組成物によれば、天然ゴムと、エポキシ化天然ゴムと、特定の共役ジエン系重合体と、カーボンブラック及び／又はシリカとを所定量配合したゴム組成物であるので、低燃費性、ウェットグリップ性能及び耐摩耗性がバランス良く改善された空気入りタイヤを提供できる。 In a preferred embodiment, the rubber composition of the present invention is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 10 parts by weight of a rubber component, carbon black and / or silica, compound (I) or a hydrate thereof. Containing 3 parts by weight, out of 100% by weight of the rubber component, the content of natural rubber is 5 to 50% by weight, the content of epoxidized natural rubber is 0.3 to 10% by weight, and a structural unit based on a conjugated diene And a constituent unit represented by the following formula (f), wherein the content of the conjugated diene polymer obtained by modifying at least one end of the polymer is 5% by weight or more, The present invention relates to a rubber composition having a total content of carbon black and silica of 3 to 100 parts by weight based on 100 parts by weight of the rubber component.

[Wherein, X ¹ , X ² and X ³ each independently represent a group represented by the following formula (g), a hydroxyl group, a hydrocarbyl group or a substituted hydrocarbyl group, and at least ^one of X ¹ , X ² and X ³ One is a group or a hydroxyl group represented by the following formula (g). ]

Wherein, R ³ and R ⁴ are each independently a hydrocarbyl group having 1 to 6 carbon atoms, carbon atoms represent a 1-6 substituted hydrocarbyl group, a silyl group or a substituted silyl group, R ³ and R ⁴ may be bonded to form a ring structure with the nitrogen atom. ]
In this embodiment, R ³ and R ⁴ in the above formula (g) are preferably hydrocarbyl groups having 1 to 6 carbon atoms, and ^two of X ¹ , X ² and X ^{3 in} the above formula (f) are represented by the formula ( It is preferably a group represented by g) or a hydroxyl group. Moreover, it is preferable that the vinyl bond amount of a conjugated diene polymer is 10 mol% or more and 80 mol% or less by making content of the structural unit based on a conjugated diene into 100 mol%.
According to the rubber composition of the present invention in this aspect, it is a rubber composition containing a predetermined amount of natural rubber, epoxidized natural rubber, a specific conjugated diene polymer, and carbon black and / or silica. Further, it is possible to provide a pneumatic tire with improved fuel economy, wet grip performance and wear resistance in a well-balanced manner.

  In a preferred embodiment, the rubber composition of the present invention is preferably 0.1 to 10 parts by weight of compound (I) or a hydrate thereof with respect to 100 parts by weight of diene rubbers such as NR, IR and BR. More preferably, it contains 0.3 to 3 parts by weight of a compound having an oxyethylene unit (for example, Sumigard 300G manufactured by Sumitomo Chemical Co., Ltd.) in an amount of 1.0 to 7.5 parts by weight. When the content of the compound having an oxyethylene unit is less than 1.0 part by weight, the effect of reducing electric resistance is insufficient. When the content of the compound having an oxyethylene unit exceeds 7.5 parts by weight, the reinforcing property is lowered and the effect of reducing electric resistance is small. Since the rubber composition of the present invention in this embodiment contains a predetermined amount of a compound having a diene rubber and an oxyethylene unit, it can reduce rolling resistance and electrical resistance and improve crack resistance. It is preferably used as a rubber composition for walls and a rubber composition for clinch apex. When the rubber composition of the present invention in this embodiment is used as a rubber composition for clinch apex, the rubber composition of the present invention further contains 5 parts by weight or less of carbon black with respect to 100 parts by weight of diene rubber. Is preferable because sufficient reinforcing properties can be obtained.

  In a preferred embodiment, the rubber composition of the present invention comprises a surfactant, preferably a nonionic surfactant or a cationic surfactant, more preferably a nonionic interface having polyoxyethylene groups and hydrocarbon groups. In the presence of an activator or a cationic surfactant having a quaternary ammonium group and a hydrocarbon group, compound (I) or a hydrate thereof, natural rubber latex, and a fine particle silica dispersion having an average particle size of 1 μm or less, including. In addition to having low fuel consumption, the rubber composition of the present invention in this embodiment contains a surfactant, so that silica is finely dispersed to give a vulcanized rubber having excellent low heat buildup and reinforcement.

In a preferred embodiment, the rubber composition of the present invention comprises natural rubber, compound (I) or a hydrate thereof, and carbon black, and the content of natural rubber in 100% by weight of the rubber component is 50% by weight. As mentioned above, it is preferable that it is a rubber composition whose sum total content of compound (I) or its hydrate is 0.3-10 weight part with respect to a total of 100 weight part of carbon black and a silica. In this embodiment, the rubber composition of the present invention has the formula R ¹² —S—S—Y—S—S—R ^{13 wherein} Y is an alkylene group having 2 to 10 carbon atoms, and R ¹² and R ¹³ are These are the same or different and represent a monovalent organic group containing a nitrogen atom. It is preferable that the compound represented by this is included. Further, the rubber composition of the present invention in this embodiment preferably contains butadiene rubber, and the content of carbon black is preferably 30 to 70 parts by weight with respect to 100 parts by weight of the rubber component. The rubber composition of the present invention in this aspect is preferably used as a rubber composition for tire treads because it can improve fuel economy and mechanical strength in a well-balanced manner.

  In a preferred embodiment, the rubber composition of the present invention comprises natural rubber, compound (I) or a hydrate thereof, and carbon black and / or silica. In the rubber composition of the present invention in this embodiment, the content of natural rubber in 100% by weight of the rubber component is preferably 10 to 90% by weight, and preferably contains butadiene rubber. In the rubber composition of the present invention in this aspect, the total content of compound (I) or a hydrate thereof is preferably 0.2 to 10 parts by weight with respect to 100 parts by weight of the total of carbon black and silica. . Moreover, it is preferable that content of carbon black is 10-90 weight part with respect to 100 weight part of rubber components. Moreover, it is also preferable that content of a silica is 5-90 weight part with respect to 100 weight part of rubber components. The rubber composition of the present invention in this aspect can improve fuel economy, mechanical strength, and processability in a well-balanced manner, and can be used for tire components (particularly, sidewalls) to reduce fuel consumption and mechanical strength. Gives pneumatic tires with excellent durability

In a preferred embodiment, the rubber composition of the present invention comprises natural rubber, compound (I) or a hydrate thereof, and carbon black, and the content of natural rubber in 100% by weight of the rubber component is 80% by weight. As mentioned above, it is a rubber composition whose total content of compound (I) or its hydrate is 0.5 to 10 parts by weight with respect to 100 parts by weight of carbon black and silica in total. In this embodiment, the rubber composition of the present invention has the formula R ¹² —S—S—Y—S—S—R ^{13 wherein} Y is an alkylene group having 2 to 10 carbon atoms, and R ¹² and R ¹³ are The same or different and represents a monovalent organic group containing a nitrogen atom. It is preferable that the compound represented by this is included. In this embodiment, the carbon black content is preferably 20 to 50 parts by weight with respect to 100 parts by weight of the rubber component. The rubber composition of the present invention in this aspect is preferably used as a rubber composition for a tire breaker cushion because it can improve mechanical strength and fuel efficiency.

  In a preferred embodiment, the rubber composition of the present invention comprises natural rubber, compound (I) or a hydrate thereof, and carbon black. In the rubber composition of the present invention in this embodiment, the content of natural rubber in 100% by weight of the rubber component is preferably 20% by weight or more, and preferably contains butadiene rubber. In this embodiment, the total content of compound (I) or a hydrate thereof is preferably 0.15 to 14 parts by weight with respect to 100 parts by weight of the total of carbon black and silica. Moreover, it is preferable that content of carbon black is 15-100 weight part with respect to 100 weight part of rubber components. The rubber composition of the present invention in this aspect is preferably used as a rubber composition for a base tread because it can improve fuel economy, mechanical strength, and processability in a well-balanced manner.

In a preferred embodiment, the rubber composition of the present invention comprises natural rubber, compound (I) or a hydrate thereof, and carbon black, and the content of natural rubber in 100% by weight of the rubber component is 80% by weight. As mentioned above, it is a rubber composition whose total content of compound (I) or its hydrate is 0.3 to 10 parts by weight with respect to 100 parts by weight of carbon black and silica in total. In this embodiment, the rubber composition of the present invention has the formula R ¹² —S—S—Y—S—S—R ^{13 wherein} Y is an alkylene group having 2 to 10 carbon atoms, and R ¹² and R ¹³ are The same or different and represents a monovalent organic group containing a nitrogen atom. It is preferable that the compound represented by this is included. In this embodiment, the carbon black content is preferably 30 to 60 parts by weight with respect to 100 parts by weight of the rubber component. The rubber composition of the present invention in this aspect can improve mechanical strength and fuel efficiency, and is preferably used as a rubber composition for a base tread.

  In a preferred embodiment, the rubber composition of the present invention is a rubber composition containing natural rubber, compound (I) or a hydrate thereof, and carbon black. In this embodiment, the content of natural rubber in 100% by weight of the rubber component is preferably 30% by weight or more. Moreover, it is preferable that the rubber composition of this invention in this aspect contains a butadiene rubber. Moreover, it is preferable that the total content of compound (I) or a hydrate thereof is 0.18 to 11 parts by weight with respect to 100 parts by weight of the total of carbon black and silica. In the rubber composition of the present invention in this aspect, the carbon black content is preferably 10 to 90 parts by weight with respect to 100 parts by weight of the rubber component. The rubber composition of the present invention in this aspect is preferably used as a rubber composition for covering a tire cord because it has good processability and can improve fuel economy and durability. And / or more preferably used as a rubber composition for car casting. Further, according to the rubber composition of the present invention in this aspect, it has good processability, can improve fuel economy and durability, and is used for each member of a tire (particularly, a breaker and a carcass). Gives pneumatic tires with excellent fuel efficiency and durability.

  In a preferred embodiment, the rubber composition of the present invention comprises a rubber component containing natural rubber and butadiene rubber, compound (I) or a hydrate thereof, and carbon black. In this embodiment, the content of natural rubber in 100% by weight of the rubber component is preferably 60% by weight or more, and the content of butadiene rubber is preferably 5 to 40% by weight. Moreover, it is preferable that the total content of compound (I) or its hydrate in the rubber composition is 0.05 to 10 parts by weight with respect to 100 parts by weight of the total of carbon black and silica. Further, the butadiene rubber is preferably a butadiene rubber synthesized using a rare earth element-based catalyst. In the rubber composition of the present invention in this embodiment, the total content of natural rubber and butadiene rubber in 100% by weight of the rubber component is preferably 100% by weight. Moreover, it is preferable that content of carbon black is 10-90 weight part with respect to 100 weight part of rubber components. The rubber composition of the present invention in this embodiment can improve fuel economy and mechanical strength in a well-balanced manner, and is preferably used as a rubber composition for treads.

In a preferred embodiment, the rubber composition of the present invention comprises a rubber component containing natural rubber and a butadiene rubber synthesized using a rare earth element-based catalyst, compound (I) or a hydrate thereof, carbon black, Formula R ¹² —S—S—Y—S—S—R ^{13 wherein} Y is an alkylene group having 2 to 10 carbon atoms, and R ¹² and R ¹³ are the same or different and contain a nitrogen atom. Represents a valent organic group. And a compound represented by the formula: In this embodiment, the content of natural rubber in 100% by weight of the rubber component is preferably 60% by weight or more, and the content of butadiene rubber synthesized using a rare earth element-based catalyst is preferably 5 to 40% by weight. Moreover, it is preferable that total content of compound (I) or its hydrate is 0.05-10 weight part with respect to a total of 100 weight part of carbon black and a silica. In the rubber composition of the present invention in this aspect, the total content of butadiene rubber synthesized using a natural rubber and a rare earth element-based catalyst in 100% by weight of the rubber component is preferably 100% by weight. Moreover, it is preferable that content of carbon black is 10-90 weight part with respect to 100 weight part of rubber components. The content of the compound represented by the formula R ¹² —S—S—Y—S—S—R ¹³ is preferably 0.1 to 8 parts by weight with respect to 100 parts by weight of the rubber component. The rubber composition of the present invention in this aspect can improve fuel economy, mechanical strength, and wear resistance in a well-balanced manner while maintaining good vulcanization stability, and can be used as a rubber composition for tire treads. preferable.

  EXAMPLES Hereinafter, although an Example, a comparative example, etc. are given and this invention is demonstrated concretely, this invention is not limited to these.

窒素雰囲気下、反応容器に１，４−フェニレンジアミン２５．１７ｇ（０．２３３ｍｏｌ）とテトラヒドロフラン２３０mlを仕込んだ。そこへ氷冷下、無水マレイン酸２２．８４ｇ（０．２３３ｍｏｌ）をテトラヒドロフラン５０ｍｌに溶解した溶液を約１時間で滴下した後、室温で一晩撹拌した。反応終了後、析出した結晶を濾取し、テトラヒドロフラン４０ｍｌで２回洗浄し、４０℃で５時間乾燥して粗製の(２Ｚ)−４−[(４−アミノフェニル)アミノ]−４−オキソ−２−ブテン酸を橙色の粉末として４６．９２ｇ得た。粗製の(２Ｚ)−４−[(４−アミノフェニル)アミノ]−４−オキソ−２−ブテン酸４６．９２ｇにメタノール２５０ｍｌを加えて５０℃で１時間撹拌し冷却後、ろ過しメタノール２０ｍｌで２回洗浄した。得られた結晶を乾燥して(２Ｚ)−４−[(４−アミノフェニル)アミノ]−４−オキソ−２−ブテン酸：

を黄橙色粉末として４２．６７ｇ得た。収率８８．８％。
次に、窒素雰囲気下、反応容器に１，４−フェニレンジアミン１５．００ｇ（１３８．７ｍｍｏｌ）とテトラヒドロフラン２５５mlを仕込んだ。そこへ氷冷下、無水マレイン酸９．０７ｇ（９２．５ｍｍｏｌ）をテトラヒドロフラン４５ｍｌに溶解した溶液を約３時間で滴下した後、室温で一晩撹拌した。反応終了後、析出した結晶を濾取し、テトラヒドロフラン３０ｍｌで洗浄し、４０℃で乾燥して粗製の(２Ｚ)−４−[(４−アミノフェニル)アミノ]−４−オキソ−２−ブテン酸を橙色の粉末として１８．１４ｇ得た。粗製の(２Ｚ)−４−[(４−アミノフェニル)アミノ]−４−オキソ−２−ブテン酸１８．１４ｇに水３６ｍｌを加えて０〜１０℃に冷却し、５Ｎ水酸化ナトリウム水溶液１７．５９ｍｌを滴下した。その後、減圧下に溶媒を留去して得られた残渣にエタノール２７０ｍｌを加えて７０℃で１時間撹拌し、室温まで冷却後、固体をろ過してメタノール２５ｍｌで２回洗浄した。得られた固体を４５℃で２時間乾燥してナトリウム(２Ｚ)−４−[(４−アミノフェニル)アミノ]−４−オキソ−２−ブテン酸を淡褐白色粉末として１６．２ｇ得た。収率７６．８％
Ｈ１−ＮＭＲ（２７０ＭＨｚ，ＤＭＳＯ−ｄ６）δｐｐｍ：１４．５（１Ｈ，s）,７．３（２Ｈ，ｄ，Ｊ＝８．９Ｈｚ），６．５（２Ｈ, ｄ，Ｊ＝８．６Ｈｚ），６．１（１Ｈ，ｄ，Ｊ＝１３．５Ｈｚ），５．６（１Ｈ，ｄ，Ｊ＝１３．２Ｈｚ），４．８（２Ｈ、ｓ）。 Example 1: Preparation of sodium (2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoic acid

Under a nitrogen atmosphere, a reaction vessel was charged with 25.17 g (0.233 mol) of 1,4-phenylenediamine and 230 ml of tetrahydrofuran. A solution prepared by dissolving 22.84 g (0.233 mol) of maleic anhydride in 50 ml of tetrahydrofuran was added dropwise thereto in about 1 hour under ice cooling, and the mixture was stirred overnight at room temperature. After completion of the reaction, the precipitated crystals were collected by filtration, washed twice with 40 ml of tetrahydrofuran, dried at 40 ° C. for 5 hours, and crude (2Z) -4-[(4-aminophenyl) amino] -4-oxo- 46.92 g of 2-butenoic acid was obtained as an orange powder. 250 ml of methanol was added to 46.92 g of crude (2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoic acid, stirred at 50 ° C. for 1 hour, cooled, filtered, and 20 ml of methanol. Washed twice. The obtained crystals were dried to give (2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoic acid:

Was obtained as a yellow-orange powder. Yield 88.8%.
Next, 15.00 g (138.7 mmol) of 1,4-phenylenediamine and 255 ml of tetrahydrofuran were charged in a reaction vessel under a nitrogen atmosphere. A solution prepared by dissolving 9.07 g (92.5 mmol) of maleic anhydride in 45 ml of tetrahydrofuran was added dropwise thereto in about 3 hours under ice cooling, and the mixture was stirred overnight at room temperature. After completion of the reaction, the precipitated crystals were collected by filtration, washed with 30 ml of tetrahydrofuran, dried at 40 ° C. and crude (2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoic acid. Was obtained as an orange powder. 36. Water (36 ml) was added to crude (2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoic acid (18.14 g), cooled to 0 to 10 ° C., and 5N aqueous sodium hydroxide solution 17. 59 ml was added dropwise. Thereafter, 270 ml of ethanol was added to the residue obtained by distilling off the solvent under reduced pressure, followed by stirring at 70 ° C. for 1 hour. After cooling to room temperature, the solid was filtered and washed twice with 25 ml of methanol. The obtained solid was dried at 45 ° C. for 2 hours to obtain 16.2 g of sodium (2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoic acid as a pale brown white powder. Yield 76.8%
H1-NMR (270 MHz, DMSO-d6) δ ppm: 14.5 (1H, s), 7.3 (2H, d, J = 8.9 Hz), 6.5 (2H, d, J = 8.6 Hz) , 6.1 (1H, d, J = 13.5 Hz), 5.6 (1 H, d, J = 13.2 Hz), 4.8 (2H, s).

窒素雰囲気下、反応容器に(２Ｚ)−４−[(４−アミノフェニル)アミノ]−４−オキソ−２−ブテン酸１０．４９ｇ（含量８６％、純分として９．０２ｇ（４７．３ｍｍｏｌ））と水３０ｍｌを仕込んだ。そこへ、１ｍｏｌ／Ｌ水酸化ナトリウム水溶液４７．３ｍｌ（４７．３ｍｍｏｌ）を加えた。反応終了後、溶液を濃縮乾固して得られた固体に、テトラヒドロフラン３０ｍｌを加えて室温で３０分撹拌後、析出した結晶を濾取、乾燥してナトリウム(２Ｚ)−４−[(４−アミノフェニル)アミノ]−４−オキソ−２−ブテン酸二水和物を黄色固体として１１．２８ｇ得た。収率９０％
Ｈ１−ＮＭＲ（２７０ＭＨｚ，ＤＭＳＯ−ｄ６）δ_ｐｐｍ：１４．６（１Ｈ，s）,７．３（２Ｈ，ｄ，Ｊ＝８．９Ｈｚ），6.5（２Ｈ，ｄ,Ｊ＝８．９Ｈｚ），６．１（１Ｈ，ｄ，Ｊ＝１３．５Ｈｚ），５．６（１Ｈ，ｄ，Ｊ＝１３．５Ｈｚ），４．８（２Ｈ、ｓ），３．３（４Ｈ，ｓ） Example 2-1 Preparation of sodium (2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoic acid dihydrate

(2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoic acid 10.49 g (content 86%, pure content 9.02 g (47.3 mmol)) ) And 30 ml of water. Thereto was added 47.3 ml (47.3 mmol) of a 1 mol / L sodium hydroxide aqueous solution. After completion of the reaction, 30 ml of tetrahydrofuran was added to the solid obtained by concentrating the solution to dryness, and the mixture was stirred at room temperature for 30 minutes. The precipitated crystals were collected by filtration, dried and sodium (2Z) -4-[(4- 11.28 g of aminophenyl) amino] -4-oxo-2-butenoic acid dihydrate was obtained as a yellow solid. Yield 90%
H1-NMR (270 MHz, DMSO-d6) δ _ppm : 14.6 (1H, s), 7.3 (2H, d, J = 8.9 Hz), 6.5 (2H, d, J = 8.9 Hz), 6.1 (1H, d, J = 13.5 Hz), 5.6 (1 H, d, J = 13.5 Hz), 4.8 (2H, s), 3.3 (4H, s)

Example 2-2: Preparation of sodium (2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoic acid dihydrate 1,4-phenylenediamine in a reaction vessel under nitrogen atmosphere 211.3 g (1.95 mol) and 3900 ml of tetrahydrofuran were charged. A solution prepared by dissolving 127.2 g (1.30 mol) of maleic anhydride in 600 ml of tetrahydrofuran was added dropwise thereto in about 3.3 hours under ice cooling, and the mixture was stirred overnight at room temperature. After completion of the reaction, the precipitated crystals were collected by filtration, washed twice with 280 ml of tetrahydrofuran, and dried to obtain crude (2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoic acid. As a yellow-orange powder, 259.2 g was obtained. 520 ml of water was added to 259.2 g of crude (2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoic acid, cooled to 0-10 ° C., 237 ml of 5N aqueous sodium hydroxide solution, Subsequently, 6.5 ml of 1N sodium hydroxide aqueous solution was dripped. Thereafter, 200 ml of 2-propanol was added to the residue obtained by distilling off the solvent under reduced pressure, and the solvent was again distilled off under reduced pressure. To the obtained tan solid was added 800 ml of tetrahydrofuran and stirred overnight at room temperature. The solid was collected by filtration, washed 4 times with 100 ml of tetrahydrofuran, dried at 45 ° C. for 5 hours, and sodium (2Z) -4-[(4 297.7 g of -aminophenyl) amino] -4-oxo-2-butenoic acid dihydrate was obtained as a yellow powder. Yield 86.7%.
H ¹ -NMR (270 MHz, DMSO-d6) δ _ppm : 14.6 (1H, s), 7.3 (2H, d, J = 8.9 Hz), 6.5 (2H, d, J = 8. 9 Hz), 6.1 (1 H, d, J = 13.5 Hz), 5.6 (1 H, d, J = 13.5 Hz), 4.8 (2 H, s), 3.3 (4 H, s) .

Example 3: Production of rubber composition <Procedure 1>
Using a Banbury mixer (600 ml Lab Plast Mill manufactured by Toyo Seiki Co., Ltd.), 100 parts by weight of natural rubber (RSS # 1), 45 parts by weight of HAF (Asahi Carbon Co., Ltd., trade name “Asahi # 70”), 3 parts by weight of stearic acid , 5 parts by weight of zinc oxide, 1 part by weight of an antioxidant (N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine: trade name “Antigen (registered trademark) 6C” manufactured by Sumitomo Chemical Co., Ltd.) 1 part by weight of sodium (2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoic acid obtained in Example 1 was kneaded and mixed to obtain a rubber composition. This procedure 1 was carried out by kneading for 5 minutes at a rotational speed of a mixer of 50 rpm for 5 minutes after charging various components, and the rubber temperature at that time was 160 to 170 ° C.
<Procedure 2>
The rubber composition obtained by the procedure 1, 1 part by weight of a vulcanization accelerator (N-cyclohexyl-2-benzothiazolylsulfenamide) and sulfur 2 at a temperature of 60 to 80 ° C. in an open roll machine. A rubber composition was obtained by kneading and blending with parts by weight.

Example 4: Production of vulcanized rubber The rubber composition obtained in the procedure 2 of Example 3 was vulcanized at 145 ° C to obtain a vulcanized rubber.

Example 5: Production of rubber composition In Example 3, the sodium (2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoic acid obtained in Example 2 above was used instead of sodium (2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoic acid. A rubber composition was obtained in the same manner as in Example 3 except that 2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoic acid dihydrate was used.

Example 6: Production of vulcanized rubber The rubber composition obtained in the procedure 2 of Example 5 was vulcanized at 145 ° C to obtain a vulcanized rubber.

Reference example 1
A rubber composition was obtained in the same manner as in Example 3, except that sodium (2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoic acid was not used.

Reference example 2
The rubber composition obtained in Procedure 2 of Reference Example 1 was vulcanized at 145 ° C. to obtain a vulcanized rubber.

(1) Scorch time The scorch time was measured at 125 ° C. in accordance with JIS-K6300-1.
A larger scorch time value indicates that rubber scoring is less likely to occur and processing stability is better.
The rubber composition obtained in Reference Example 1 was used as a control, the scorch time of the rubber composition obtained in Reference Example 1 was set to 100, and the relative value of the scorch time was displayed as an index for the rubber compositions obtained in Examples 3 and 5. did. The results are shown in Table 1.

(2) Viscoelastic properties Viscoelastic properties were measured using a viscoelastic analyzer manufactured by Ueshima Seisakusho Co., Ltd. under the following conditions.
Condition: Temperature -5 ° C to 80 ° C (Temperature increase rate: 2 ° C / min)
Initial strain 10%, dynamic strain 2.5%, frequency 10Hz
Using the vulcanized rubber obtained in Reference Example 2 as a control, the rate of decrease in viscoelastic properties (tan δ at 60 ° C.) of the vulcanized rubber obtained in Examples 4 and 6 with respect to the vulcanized rubber obtained in Reference Example 2 ( %). The results are shown in Table 2. The reduction rate (%) was calculated based on the following formula.

Example 7: Production of rubber composition <Procedure 1>
Using a Banbury mixer (600 ml Lab Plast Mill manufactured by Toyo Seiki Co., Ltd.), 100 parts by weight of natural rubber (RSS # 1), 45 parts by weight of HAF (Asahi Carbon Co., Ltd., trade name “Asahi # 70”), 3 parts by weight of stearic acid , 5 parts by weight of zinc oxide, 1 part by weight of an antioxidant (N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine: trade name “Antigen (registered trademark) 6C” manufactured by Sumitomo Chemical Co., Ltd.) 0.5 parts by weight of sodium (2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoic acid dihydrate obtained in Example 2 above was kneaded and blended to obtain a rubber composition. Obtained. This procedure 1 was carried out by kneading for 5 minutes at a rotational speed of a mixer of 50 rpm for 5 minutes after charging various components, and the rubber temperature at that time was 160 to 170 ° C.
<Procedure 2>
The rubber composition obtained by the procedure 1, 1 part by weight of a vulcanization accelerator (N-cyclohexyl-2-benzothiazolylsulfenamide) and sulfur 2 at a temperature of 60 to 80 ° C. in an open roll machine. A rubber composition was obtained by kneading and blending with parts by weight.

Example 8: Production of vulcanized rubber The rubber composition obtained in the procedure 2 of Example 7 was vulcanized at 145 ° C to obtain a vulcanized rubber.

Example 9 Production of Rubber Composition Except that 1 part by weight of sodium (2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoic acid dihydrate was used in Example 7. A rubber composition was obtained in the same manner as in Example 7.

Example 10: Production of vulcanized rubber The rubber composition obtained in the procedure 2 of Example 9 was vulcanized at 145 ° C to obtain a vulcanized rubber.

Example 11 Production of Rubber Composition Except that 2 parts by weight of sodium (2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoic acid dihydrate was used in Example 7. A rubber composition was obtained in the same manner as in Example 7.

Example 12: Production of vulcanized rubber The rubber composition obtained in the procedure 2 of Example 11 was vulcanized at 145 ° C to obtain a vulcanized rubber.

Reference example 3
A rubber composition was obtained in the same manner as in Example 7, except that sodium (2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoic acid dihydrate was not used. Got.

Reference example 4
The rubber composition obtained in Procedure 2 of Reference Example 3 was vulcanized at 145 ° C. to obtain a vulcanized rubber.

(1) Scorch time The scorch time was measured at 125 ° C. in accordance with JIS-K6300-1.
A larger scorch time value indicates that rubber scoring is less likely to occur and processing stability is better.
The rubber composition obtained in Reference Example 3 was used as a control, the scorch time of the rubber composition obtained in Reference Example 3 was set to 100, and the rubber composition obtained in Examples 7, 9 and 11 was subjected to the relative value of the scorch time. The index was displayed. The results are shown in Table 3.

(2) Viscoelastic properties Viscoelastic properties were measured under the following conditions using a viscoelastic analyzer manufactured by Ueshima Seisakusho.
Condition: Temperature -5 ° C to 80 ° C (Temperature increase rate: 2 ° C / min)
Initial strain 10%, dynamic strain 2.5%, frequency 10Hz
Decrease in viscoelastic properties (tan δ at 60 ° C.) with respect to the vulcanized rubber obtained in Reference Example 4 with respect to the vulcanized rubber obtained in Examples 8, 10 and 12 using the vulcanized rubber obtained in Reference Example 4 as a control. The rate (%) was measured. The results are shown in Table 4.

Example 13: Production of rubber composition <Procedure 1>
Using a Banbury mixer (600 ml Lab Plast Mill manufactured by Toyo Seiki Co., Ltd.), 80 parts by weight of natural rubber (RSS # 1), 20 parts by weight of polybutadiene rubber (trade name “BR01” manufactured by JSR), FEF (manufactured by Asahi Carbon Co., Ltd., Product name “Asahi # 60”) 40 parts by weight, heavy calcium carbonate 40 parts by weight, stearic acid 3 parts by weight, zinc oxide 5 parts by weight, anti-aging agent (N-phenyl-N′-1,3-dimethylbutyl- 1 part by weight of p-phenylenediamine (6PPD): trade name “Antigen (registered trademark) 6C” manufactured by Sumitomo Chemical Co., Ltd., 1 part by weight of the anti-aging agent Polymreized-2.2.4-trimethy-1.2-dihydroquinoline (TMDQ) and the above 2 parts by weight of sodium (2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoic acid dihydrate obtained in Example 2 was kneaded to obtain a kneaded product. In this step, kneading was performed at a mixer set temperature of 120 ° C. and a mixer rotation speed of 50 rpm for 5 minutes after charging various chemicals and fillers. The temperature of the kneaded product at the end of kneading was 171 ° C.
<Procedure 2>
The rubber composition obtained by the procedure 1, the vulcanization accelerator N-cyclohexyl-2-benzothiazolesulfenamide (CBS) 1 part by weight, and sulfur at a temperature of 60 to 80 ° C. in an open roll machine 2 parts by weight were kneaded and blended to obtain a rubber composition.

Example 14: Production of vulcanized rubber The rubber composition obtained in the procedure 2 of Example 13 was vulcanized at 145 ° C to obtain a vulcanized rubber.

Reference Example 5
A rubber composition was obtained in the same manner as in Example 13 except that sodium (2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoic acid dihydrate was not used. Got.

Reference Example 6
The rubber composition obtained in Procedure 2 of Reference Example 5 was vulcanized at 145 ° C. to obtain a vulcanized rubber.

The dynamic viscoelastic properties were measured and the dynamic magnification was calculated as follows.
(1) Dynamic viscoelastic properties
Using viscoelasticity measuring device RSA-3 manufactured by TA INSTRUMENTS, dynamic viscoelastic properties were measured under the following conditions.
Condition: Temperature -40 to 80 ° C
Dynamic strain 0.1%, frequency 1-10Hz
(2) Dynamic magnification From the result obtained from (1), the frequency dependence (master curve) at a reference temperature of 22 ° C. is obtained, the complex elastic modulus at a frequency of 1 Hz is the static elastic modulus, and the complex elastic modulus at 100 Hz. Was calculated from the formula (1) as the dynamic elastic modulus.
Dynamic magnification = Dynamic elastic modulus (Pa) / Static elastic modulus (Pa) Expression (1)
Using the rubber composition obtained in Reference Example 6 as a control, the dynamic magnification of the rubber composition obtained in Example 14 was reduced by 4%, and an improvement in the dynamic magnification was confirmed.

Example 15: Production of rubber composition <Procedure 1>
Using a Banbury mixer (600 ml Lab Plast Mill manufactured by Toyo Seiki Co., Ltd.), 100 parts by weight of styrene / butadiene copolymer rubber SBR # 1502 (manufactured by Sumitomo Chemical Co., Ltd.), ISAF-HM (manufactured by Asahi Carbon Co., Ltd., trade name “Asahi # 80”) ) 45 parts by weight, stearic acid 2 parts by weight, zinc oxide 3 parts by weight, sodium (2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoic acid 1 part by weight, anti-aging agent ( N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine (6PPD): 1 part by weight of trade name “Antigen (registered trademark) 6C” manufactured by Sumitomo Chemical Co., Ltd. and wax (“OZOACE manufactured by Nippon Seiwa) −0355 ”) 2 parts by weight are kneaded and mixed to obtain a rubber composition. This step is carried out by kneading for 5 minutes at a rotational speed of a mixer of 50 rpm for 5 minutes after charging each component, and the rubber temperature at that time is 160 to 175 ° C.
<Procedure 2>
The rubber composition obtained by the procedure 1, 3 parts by weight of sulfur accelerator N-cyclohexyl-2-benzothiazolylsulfenamide (CBS) and sulfur at a temperature of 60 to 80 ° C. in an open roll machine 2 parts by weight are kneaded and blended to obtain a rubber composition.

Example 16: Production of vulcanized rubber The rubber composition obtained in the procedure 2 of Example 15 is heat-treated at 145 ° C to obtain a vulcanized rubber. Such vulcanized rubber is suitable for cap treads.

Example 17: Production of rubber composition <Procedure 1>
Using a Banbury mixer (600 ml Lab Plast Mill manufactured by Toyo Seiki Co., Ltd.), 100 parts by weight of styrene / butadiene copolymer rubber SBR # 1502 (manufactured by Sumitomo Chemical Co., Ltd.), ISAF-HM (manufactured by Asahi Carbon Co., Ltd., trade name “Asahi # 80”) ) 35 parts by weight, stearic acid 2 parts by weight, zinc oxide 3 parts by weight, sodium (2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoic acid 1 part by weight, anti-aging agent ( N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine (6PPD): 1 part by weight of trade name “Antigen (registered trademark) 6C” manufactured by Sumitomo Chemical Co., Ltd. and wax (“OZOACE manufactured by Nippon Seiwa) −0355 ”) 2 parts by weight are kneaded and mixed to obtain a rubber composition. This step is carried out by kneading for 5 minutes at a rotational speed of a mixer of 50 rpm for 5 minutes after charging each component, and the rubber temperature at that time is 160 to 175 ° C.
<Procedure 2>
The rubber composition obtained by the procedure 1 and 2 parts by weight of a vulcanization accelerator N-cyclohexyl-2-benzothiazolylsulfenamide (CBS) at a temperature of 60 to 80 ° C. in an open roll machine. A rubber composition is obtained by kneading and blending 0.5 parts by weight of a sulfur accelerator diphenylguanidine (DPG), 0.8 parts by weight of a vulcanization accelerator dibenzothiazyl disulfide (MBTS) and 1 part by weight of sulfur.

Example 18: Production of vulcanized rubber For undertread A vulcanized rubber is obtained by heat-treating the rubber composition obtained in Procedure 2 of Example 17 at 145 ° C. Such vulcanized rubber is suitable for undertread.

Example 19: Production of rubber composition <Procedure 1>
Using a Banbury mixer (600 ml Lab Plast Mill manufactured by Toyo Seiki Co., Ltd.), 100 parts by weight of natural rubber (RSS # 1), 45 parts by weight of HAF (Asahi Carbon Co., Ltd., trade name “Asahi # 70”), 3 parts by weight of stearic acid , 5 parts by weight of zinc oxide, 2 parts by weight of sodium (2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoic acid, hydrous silica (“Nipsil (manufactured by Tosoh Silica Co., Ltd.) (Registered trademark) AQ "10 parts by weight, anti-aging agent FR (" Antioxidant FR "manufactured by Matsubara Sangyo Co., Ltd.) 2 parts, and 2 parts by weight of resorcinol were kneaded and mixed to obtain a rubber composition. It was carried out by kneading for 5 minutes at a rotation speed of a mixer of 50 rpm after the addition, and the rubber temperature at that time was 160 to 175 ° C.
<Procedure 2>
Rubber composition obtained by procedure 1, 2 parts by weight of cobalt naphthenate, vulcanization accelerator N, N-dicyclohexyl-2-benzothiazolylsulfene at 60-80 ° C. in an open roll machine A rubber composition was obtained by kneading and blending 0.7 parts by weight of amide (DCBS), 5 parts by weight of sulfur and 4 parts by weight of a methoxylated methylol melamine resin (“SUMIKANOL 507AP” manufactured by Sumitomo Chemical Co., Ltd.).

Example 20: Production of vulcanized rubber The rubber composition obtained in the procedure 2 of Example 19 was heat-treated at 150 ° C to obtain a vulcanized rubber.

Reference Example 7
A rubber composition was obtained in the same manner as in Example 19 except that sodium (2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoic acid was not used.

Reference Example 8
The rubber composition obtained in Procedure 2 of Reference Example 7 was vulcanized at 150 ° C. to obtain a vulcanized rubber.

Example 21: Production of condensate of resorcin and acetone A 1000 ml separable flask equipped with a thermometer, a stirrer and a condenser was charged with 88.1 g (0.80 mol) of resorcin, and the inside of the flask was purged with nitrogen, followed by acetone 81 .3 g (1.40 mol) and 264 g of toluene were charged, and the temperature was raised to 40 ° C. Thereto was charged 2.31 g of p-toluenesulfonic acid hydrate, and the resulting mixture was heated to an internal temperature of 65 ° C. and kept for 7 hours.
Then, after cooling to 60 degreeC of internal temperature, it neutralized with 10% sodium hydroxide aqueous solution, and charged the acetone 58.1g (1.00 mol), and dissolved the reaction substance completely. Furthermore, 220 g of hot water was charged at the same temperature, and the pH was adjusted to alkaline (9.0) with a 10% aqueous sodium hydroxide solution, and then unreacted resorcin was removed by liquid separation washing. Separation and washing were repeated until the content of resorcin was 1% or less, followed by drying at 80 ° C. for 12 hours under reduced pressure of 1 KPa or less to obtain 113 g of a resorcin-acetone condensate.

The softening point was carried out according to JIS K 6220-1.
<GPC analysis conditions>
Column: TOSOH TSGel Super HZ2000 (4.6mmφx150cm) and two TOSOH TSGel Super HZ1000 (4.6mmφx150cm) connection temperature: 40 ° C
Mobile phase: Tetrahydrofuran Detector: RI
The percentage content of each elution peak, 2,4,4-trimethyl-2'4'7-trihydroxyflavan and resorcin was used as the content.

Softening point 116 ° C
First eluting peak: 16.3%
Weight average molecular weight of first elution peak: 1030
Second eluting peak: 19.7%
Third elution peak: 30.2%
2,4,4-trimethyl-2'4'7-trihydroxyflavan: 31.1%
Resorcin: 0.5%

Example 22: Production of rubber composition <Procedure 1>
Using a Banbury mixer (600 ml Lab Plast Mill manufactured by Toyo Seiki Co., Ltd.), 100 parts by weight of natural rubber (RSS # 1), 45 parts by weight of HAF (Asahi Carbon Co., Ltd., trade name “Asahi # 70”), 3 parts by weight of stearic acid , 5 parts by weight of zinc oxide, 2 parts by weight of sodium (2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoic acid, hydrous silica (“Nipsil (manufactured by Tosoh Silica Co., Ltd.) (Registered trademark) AQ "10 parts by weight, anti-aging agent FR (" Antioxidant FR "manufactured by Matsubara Sangyo Co., Ltd.) 2 parts, 2 parts by weight of the condensate of resorcin and acetone obtained in Example 21 were kneaded and mixed. This process was carried out by kneading at 50 rpm for 5 minutes after each component was added, and the rubber temperature at that time was 160 to 175 ° C.
<Procedure 2>
Rubber composition obtained by procedure 1, 2 parts by weight of cobalt naphthenate, vulcanization accelerator N, N-dicyclohexyl-2-benzothiazolylsulfene at 60-80 ° C. in an open roll machine A rubber composition was obtained by kneading and blending 0.7 parts by weight of amide (DCBS), 5 parts by weight of sulfur and 4 parts by weight of a methoxylated methylol melamine resin (“SUMIKANOL 507AP” manufactured by Sumitomo Chemical Co., Ltd.).

Example 23: Production of vulcanized rubber The rubber composition obtained in the procedure 2 of Example 22 was heat-treated at 150 ° C to obtain a vulcanized rubber.

Reference Example 9
A rubber composition was obtained in the same manner as in Example 22 except that sodium (2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoic acid was not used.

Reference Example 10
The rubber composition obtained in Procedure 2 of Reference Example 9 was vulcanized at 150 ° C. to obtain a vulcanized rubber.

(1) Scorch time Based on JIS-K6300-1, the scorch time was measured at 135 ° C.
A larger scorch time value indicates that rubber scoring is less likely to occur and processing stability is better.
The rubber composition obtained in Reference Example 8 was used as a control, the scorch time of the rubber composition obtained in Reference Example 8 was set to 100, and the relative value of the scorch time was displayed as an index for the rubber compositions obtained in Examples 19 and 22. did. The results are shown in Table 5.

(2) Viscoelastic properties Viscoelastic properties were measured under the following conditions using a viscoelastic analyzer manufactured by Ueshima Seisakusho.
Condition: Temperature -5 ° C to 80 ° C (Temperature increase rate: 2 ° C / min)
Initial strain 10%, dynamic strain 2.5%, frequency 10Hz
Using the vulcanized rubber obtained in Reference Example 8 and Reference Example 10 as controls, the viscoelastic properties of the vulcanized rubber obtained in Example 20 and Example 23 with respect to the vulcanized rubber obtained in Reference Example 8 and Reference Example 10, respectively. The reduction rate (%) of (tan δ at 60 ° C.) was measured. The results are shown in Table 6.

Example 24: Production of rubber composition <Procedure 1>
Using a Banbury mixer (600 ml Lab Plast Mill manufactured by Toyo Seiki), halogenated butyl rubber ("Br-IIR2255" manufactured by ExxonMobil) 100 parts by weight, GPF 60 parts by weight, stearic acid 1 part by weight, zinc oxide 3 parts by weight, 1 part by weight of sodium (2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoic acid and 10 parts by weight of paraffin oil (“Diana Process Oil” manufactured by Idemitsu Kosan Co., Ltd.) A rubber composition is obtained. This step is carried out by kneading for 5 minutes at a rotational speed of a mixer of 50 rpm for 5 minutes after charging each component, and the rubber temperature at that time is 160 to 175 ° C.
<Procedure 2>
The rubber composition obtained by the procedure 1 in an open roll machine at a temperature of 60 to 80 ° C., 1 part by weight of an antioxidant (condensation product of aniline and acetone (TMDQ)), a vulcanization accelerator dibenzothiazyl disulfide (MBTS) 1 part by weight and 2 parts by weight of sulfur are kneaded and mixed to obtain a rubber composition.

Example 25: Production of vulcanized rubber A vulcanized rubber is obtained by heat-treating the rubber composition obtained in the procedure 2 of Example 24 at 145 ° C. Such vulcanized rubber is suitable for an inner liner.

Example 26: Production of rubber composition <Procedure 1>
Using a Banbury mixer (600 ml Labo Plast Mill manufactured by Toyo Seiki Co., Ltd.), 40 parts by weight of natural rubber (RSS # 3), 60 parts of polybutadiene rubber (“BR150B” manufactured by Ube Industries), 50 parts by weight of FEF, and 2.5 parts by weight of stearic acid Parts, zinc oxide 3 parts by weight, sodium (2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoic acid 1 part by weight, anti-aging agent (N-phenyl-N′-1, 3-dimethylbutyl-p-phenylenediamine (6PPD): 2 parts by weight of trade name “Antigen (registered trademark) 6C” manufactured by Sumitomo Chemical Co., Ltd., 10 parts by weight of aromatic oil (“NC-140” manufactured by Cosmo Oil Co., Ltd.) And 2 parts by weight of wax (“Sannok (registered trademark) wax” manufactured by Ouchi Shinsei Chemical Co., Ltd.) are kneaded and blended to obtain a rubber composition. This step is carried out by kneading for 5 minutes at a rotational speed of a mixer of 50 rpm for 5 minutes after charging each component, and the rubber temperature at that time is 160 to 175 ° C.
<Procedure 2>
The rubber composition obtained by the procedure 1 and the vulcanization accelerator N-tert-butyl-2-benzothiazolylsulfenamide (BBS) 0.75 parts by weight in an open roll machine at a temperature of 60 to 80 ° C. And 1.5 parts by weight of sulfur are kneaded and mixed to obtain a rubber composition.

Example 27: Production of vulcanized rubber A vulcanized rubber is obtained by heat-treating the rubber composition obtained in Procedure 2 of Example 26 at 145 ° C. Such vulcanized rubber is suitable for side walls.

Example 28: Production of rubber composition <Procedure 1>
Using a Banbury mixer (600 ml Labo Plast Mill manufactured by Toyo Seiki Co., Ltd.), 70 parts by weight of natural rubber (TSR20), 30 parts by weight of styrene / butadiene copolymer rubber SBR # 1502 (manufactured by Sumitomo Chemical), N339 (manufactured by Mitsubishi Chemical) 60 parts by weight, stearic acid 2 parts by weight, zinc oxide 5 parts by weight, process oil ("Diana Process PS32" manufactured by Idemitsu Kosan Co., Ltd.) and sodium (2Z) -4-[(4-aminophenyl) amino]- 1 part by weight of 4-oxo-2-butenoic acid is kneaded and mixed to obtain a rubber composition. This step is carried out by kneading for 5 minutes at a rotational speed of a mixer of 50 rpm for 5 minutes after charging each component, and the rubber temperature at that time is 160 to 175 ° C.
<Procedure 2>
The rubber composition obtained by the procedure 1 at a temperature of 60 to 80 ° C. in an open roll machine, the vulcanization accelerator N-tert-butyl-2-benzothiazolylsulfenamide (BBS) 1 part by weight, sulfur 3 parts by weight, anti-aging agent (N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine (6PPD): trade name “Antigen (registered trademark) 6C” manufactured by Sumitomo Chemical Co., Ltd.) and 1 part by weight A rubber composition is obtained by kneading and blending 1 part by weight of an antioxidant (condensation product of aniline and acetone (TMDQ)).

Example 29: Production of vulcanized rubber A vulcanized rubber is obtained by heat-treating the rubber composition obtained in the procedure 2 of Example 25 at 145 ° C. Such vulcanized rubber is suitable for carcass.

Example 30: Production of rubber composition <Procedure 1>
Using a Banbury mixer (600 ml Laboplast Mill manufactured by Toyo Seiki Co., Ltd.), 100 parts by weight of styrene / butadiene copolymer rubber SBR # 1500 (manufactured by JSR), silica (trade name: “Ultrasil (registered trademark) VN3-G” Degussa 78.4 parts by weight, carbon black (trade name “N-339” manufactured by Mitsubishi Chemical Corporation), 6.4 parts by weight, silane coupling agent (bis (3-triethoxysilylpropyl) tetrasulfide: trade name “ 6.4 parts by weight of Si-69 (manufactured by Degussa), 47.6 parts by weight of process oil (trade name “NC-140” manufactured by Cosmo Oil), anti-aging agent (N-phenyl-N′-1,3- Dimethylbutyl-p-phenylenediamine (6PPD): trade name “Antigen (registered trademark) 6C” manufactured by Sumitomo Chemical Co., Ltd.) 1.5 parts by weight, zinc oxide 2 parts by weight, 2 parts by weight of stearic acid and 3 parts by weight of sodium (2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoic acid are kneaded and mixed to obtain a rubber composition. This step is operated in a temperature range of 70 ° C. to 120 ° C., and is carried out by kneading at a rotational speed of a mixer of 80 rpm for 5 minutes after charging each component, and subsequently kneading at a rotational speed of a mixer of 100 rpm for 5 minutes. .
<Procedure 2>
The rubber composition obtained by the procedure 1 and the vulcanization accelerator N-cyclohexyl-2-benzothiazolylsulfenamide (CBS) 1 part by weight at a temperature of 30 to 80 ° C. in an open roll machine, vulcanization 1 part by weight of accelerator diphenylguanidine (DPG), 1.5 parts by weight of wax (trade name “SANNOC (registered trademark) N” manufactured by Ouchi Shinsei Chemical Co., Ltd.) and 1.4 parts by weight of sulfur are kneaded and blended. A composition is obtained.

Example 31: Production of vulcanized rubber A vulcanized rubber is obtained by heat-treating the rubber composition obtained in the procedure 2 of Example 30 at 160 ° C. Such vulcanized rubber is suitable for cap treads.

Example 32: Manufacture of rubber composition In Example 30, solution polymerization SBR ("Asaprene (registered trademark)" manufactured by Asahi Kasei Chemicals Co., Ltd.) is used instead of styrene / butadiene copolymer rubber SBR # 1500 (manufactured by JSR). A rubber composition is obtained in the same manner as in Example 28 except for the above.

Example 33: Production of vulcanized rubber The rubber composition obtained in the procedure 2 of Example 32 is heat-treated at 160 ° C to obtain a vulcanized rubber. Such vulcanized rubber is suitable for cap treads.

Example 34: Production of rubber composition In Example 30, SBR # 1712 (manufactured by JSR) was used in place of styrene-butadiene copolymer rubber SBR # 1500 (manufactured by JSR), and the amount of process oil used was 21 wt. The rubber composition is obtained in the same manner as in Example 28 except that the timing at which the zinc oxide is charged is changed to Procedure 2.

Example 35: Production of vulcanized rubber A vulcanized rubber is obtained by heat-treating the rubber composition obtained in the procedure 2 of Example 34 at 160 ° C. Such vulcanized rubber is suitable for cap treads.

Example 36: Production of rubber composition <Procedure 1>
Using a Banbury mixer (600 ml Lab Plast Mill manufactured by Toyo Seiki Co., Ltd.), 80 parts by weight of natural rubber (RSS # 1), 20 parts by weight of polybutadiene rubber (trade name “BR01” manufactured by JSR), FEF (manufactured by Asahi Carbon Co., Ltd., Product name “Asahi # 60”) 40 parts by weight, heavy calcium carbonate 40 parts by weight, stearic acid 3 parts by weight, zinc oxide 5 parts by weight, anti-aging agent (N-phenyl-N′-1,3-dimethylbutyl- 1 part by weight of p-phenylenediamine (6PPD): trade name “Antigen (registered trademark) 6C” manufactured by Sumitomo Chemical Co., Ltd., 1 part by weight of polymreized-2.2.4-trimethy-1.2-dihydroquinoline (TMDQ) and sodium 2 parts by weight of (2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoic acid is kneaded and mixed to obtain a rubber composition. The process yielded This step is carried out by kneading for 5 minutes at a rotational speed of a mixer of 50 rpm for 5 minutes after charging each component, and the rubber temperature at that time is 160 to 175 ° C.
<Procedure 2>
Rubber composition obtained according to procedure 1, 1 part by weight of vulcanization accelerator N-cyclohexyl-2-benzothiazole sulfenamide (CBS), and sulfur at a temperature of 60-80 ° C. in an open roll machine 2 parts by weight are kneaded and blended to obtain a rubber composition.

Example 37: Production of vulcanized rubber The rubber composition obtained in the procedure 2 of Example 36 is heat-treated at 145 ° C to obtain a vulcanized rubber. Such vulcanized rubber is suitable as an anti-vibration rubber.

Example 38: Production of rubber composition <Procedure 1>
Using a Banbury mixer (600 ml Lab Plast Mill manufactured by Toyo Seiki Co., Ltd.), 50 parts by weight of natural rubber (RSS # 1), 50 parts by weight of styrene-butadiene copolymer rubber SBR # 1500 (manufactured by JSR), HAF (manufactured by Asahi Carbon Co., Ltd.) , Trade name "Asahi # 70") 50 parts by weight, stearic acid 2 parts by weight, zinc oxide 3 parts by weight, anti-aging agent Polymreized-2.2.4-trimethy-1.2-dihydroquinoline (TMDQ) 2 parts by weight and sodium (2Z) A rubber composition is obtained by kneading and blending 2 parts by weight of -4-[(4-aminophenyl) amino] -4-oxo-2-butenoic acid. The process yielded This step is carried out by kneading for 5 minutes at a rotational speed of a mixer of 50 rpm for 5 minutes after charging each component, and the rubber temperature at that time is 160 to 175 ° C.
<Procedure 2>
A rubber composition obtained according to procedure 1 at a temperature of 60 to 80 ° C. in an open roll machine, and 1.5 parts by weight of a vulcanization accelerator Nt-butyl-2-benzothiazolesulfenamide (NS); Then, 2 parts by weight of sulfur is kneaded and mixed to obtain a rubber composition.

Example 39: Production of vulcanized rubber The rubber composition obtained in the procedure 2 of Example 38 is heat-treated at 145 ° C to obtain a vulcanized rubber. Such vulcanized rubber is suitable as a rubber belt.

The raw materials used in Examples 40 to 222 below are shown in Tables 7 to 14 below.
[Rubber component]

〔filler〕

〔sulfur〕

[Vulcanization accelerator]

[Vulcanization acceleration aid]

〔resin〕

[Other additives 1]

[Other additives 2]

(Rubber composition for band topping)
Examples 40-57
In accordance with the formulation shown in Tables 15 and 16 (the amount of sulfur in the table indicates the amount of the sulfur component), using a 1.7 L Banbury mixer, among the blended materials, sulfur, vulcanization accelerator and methylene donor (HMMM) Knead | mixing materials other than Sumikanol 507A, HMT) until it becomes 180 degreeC, and a kneaded material is obtained. Next, sulfur, a vulcanization accelerator, and a methylene donor (HMMM, Sumikanol 507A, HMT) are added to the obtained kneaded product, and kneaded to 105 ° C. using a biaxial open roll, and unvulcanized rubber A composition is obtained.

(Rubber composition for breaker edge strip)
Examples 58-73
In accordance with the formulation shown in Tables 17 and 18 (the amount of sulfur in the table indicates the amount of the sulfur component), using a 1.7 L Banbury mixer, among the blended materials, sulfur, vulcanization accelerator and methylene donor (HMMM) Knead | mixing materials other than Sumikanol 507A, HMT) until it becomes 180 degreeC, and a kneaded material is obtained. Next, sulfur, a vulcanization accelerator, and a methylene donor (HMMM, Sumikanol 507A, HMT) are added to the obtained kneaded product, and kneaded to 105 ° C. using a biaxial open roll, and unvulcanized rubber A composition is obtained.

  For a rubber component containing a predetermined amount of isoprene-based rubber, from compound (I) or a hydrate thereof, sulfur, resorcinol resin, modified resorcinol resin, cresol resin, modified cresol resin, phenol resin, and modified phenol resin At least one compound selected from the group consisting of: a partial condensate of hexamethoxymethylol melamine; and at least one compound selected from the group consisting of a partial condensate of hexamethylol melamine pentamethyl ether; and an organic acid cobalt In the embodiment including a predetermined amount, the elongation at break (when new) and the elongation at break (after thermal oxidative degradation) can be improved while maintaining hardness, adhesion, and workability (sheet rollability), and BEL is generated. Can be suppressed and has excellent durability.

Examples 74-86
According to the formulation shown in Tables 19 and 20, using a Banbury mixer, compound (I) or a hydrate thereof, a vulcanization accelerator, HMT, sulfur, a vulcanization accelerator and a chemical other than CTP are kneaded, A kneaded product is obtained. Next, using an open roll, a vulcanization accelerator, HMT, sulfur, a vulcanization accelerator and CTP are added and kneaded to the obtained kneaded product to obtain an unvulcanized rubber composition. Such a rubber composition of the present invention suppresses reversion, has excellent processability, provides a vulcanized rubber excellent in handling stability, fuel efficiency, run flat durability and flat spot riding comfort. The rubber composition of the present invention is preferably used for, for example, a bead apex.

Examples 87-95
In accordance with the formulation shown in Table 21, using a Banbury mixer, chemicals other than sulfur, a vulcanization accelerator, and an organic crosslinking agent are kneaded at 165 ° C. for 4 minutes to obtain a kneaded product. Next, using an open roll, sulfur, a vulcanization accelerator, and an organic crosslinking agent are added to the obtained kneaded product, and kneaded at 80 ° C. for 4 minutes to obtain an unvulcanized rubber composition.
In addition, the diene polymer (modified diene polymer) shown in Table 21 can be obtained according to the following production examples.

[Various chemicals used in production examples]
Cyclohexane: manufactured by Tokyo Chemical Industry Co., Ltd. (purity 99.5% or more)
Styrene: Tokyo Chemical Industry Co., Ltd. (purity 99% or more)
1,3-butadiene: Tokyo Chemical Industry Co., Ltd. N, N, N ′, N′-tetramethylethylenediamine: Wako Pure Chemical Industries, Ltd. n-butyllithium: Wako Pure Chemical Industries, Ltd. 1, 3-Divinylbenzene in hexane solution (1.6M): Tokyo Chemical Industry Co., Ltd. Isopropanol: Wako Pure Chemical Industries, Ltd. 2,6-tert-butyl-p-cresol: Wako Pure Chemical Industries, Ltd. Tetraglycidyl-1,3-bisaminomethylcyclohexane: Wako Pure Chemical Industries, Ltd. (modifier)
Methanol: manufactured by Kanto Chemical Co., Ltd. [Production Example 1: Preparation of polymerization initiator]
To a 100 ml pressure-resistant container sufficiently purged with nitrogen, 10 ml of a 1,3-divinylbenzene hexane solution (1.6 M) is added, and 20 ml of an n-butyllithium hexane solution (1.6 M) is added dropwise at 0 ° C. A polymerization initiator solution is obtained by stirring for a period of time.
[Production Example 2: Preparation of diene polymer (modified diene polymer)]
To a 1000 ml pressure vessel fully purged with nitrogen, add 600 ml of cyclohexane, 0.12 mol of styrene, 0.8 mol of 1,3-butadiene, 0.7 mmol of N, N, N ′, N′-tetramethylethylenediamine, and further manufacture Add 1.5 ml of the polymerization initiator solution obtained in Example 1 and stir at 40 ° C. After 3 hours, 1.0 mmol of tetraglycidyl-1,3-bisaminomethylcyclohexane as a modifier is added and stirred. After 1 hour, 3 ml of isopropanol is added to stop the polymerization. After adding 1 g of 2,6-tert-butyl-p-cresol to the reaction solution, reprecipitation treatment with methanol is performed, followed by drying by heating to modify a diene polymer (having two or more modified sites (terminals etc.)). Diene polymer) is obtained.

Examples 96-101
In accordance with the formulation shown in Table 22, using a Banbury mixer, sulfur, vulcanization accelerators (1) to (4), HMT and vulcanization accelerator (1), and N-cyclohexylthio-phthalamide (CTP) A chemical other than the above is kneaded to obtain a kneaded product. Next, using an open roll, sulfur, vulcanization acceleration auxiliary (1) to (4), HMT and vulcanization accelerator (1), and CTP are added and kneaded to the obtained kneaded product, An unvulcanized rubber composition is obtained.
Such an unvulcanized rubber composition can be used as a rubber composition for bead apex in order to provide a vulcanized rubber having good extrudability and rigidity, steering stability and low fuel consumption. preferable.

Examples 102-110
In accordance with the formulation shown in Table 23, materials other than sulfur and a vulcanization accelerator are kneaded for 4 minutes at 150 ° C. using a 1.7 L Banbury mixer to obtain a kneaded product. Next, sulfur and a vulcanization accelerator are added to the obtained kneaded product, and kneaded for 3 minutes at 80 ° C. using an open roll to obtain an unvulcanized rubber composition.
Such an unvulcanized rubber composition is preferably used as a rubber composition for an inner liner in order to give a vulcanized rubber having improved air permeation resistance, low fuel consumption and molding processability.

Examples 111-116
Using a Banbury mixer, the amount of chemicals shown in Step 1 of Table 24 is added and kneaded for 5 minutes so that the discharge temperature is about 150 ° C. Then, sulfur, a vulcanization accelerator, and a vulcanization acceleration auxiliary of the blending amount shown in Step 2 are added to the mixture obtained in Step 1, and using an open roll for about 3 minutes under the condition of about 80 ° C. By kneading, an unvulcanized rubber composition is obtained.
Such an unvulcanized rubber composition is preferably used as a rubber composition for a tread in order to give a vulcanized rubber having improved wear resistance, performance on ice and snow, operational stability, and wet grip performance. In particular, it is more preferable to use it as a tread rubber composition for studless tires.

Production Examples 3 to 23
Polymers 1-21 used in the following Examples 117-141 are produced according to the method described in Production Examples 3-23 shown below.
(Production Example 3: Synthesis of Polymer 1)
5. The inside of a stainless steel polymerization reactor having an internal volume of 20 liters was washed, dried, and replaced with dry nitrogen, hexane (specific gravity 0.68 g / cm ³ ) 10.2 kg, 1,3-butadiene 547 g, styrene 173 g, tetrahydrofuran 6. 1 ml and ethylene glycol diethyl ether 5.0 ml are charged into the polymerization reaction vessel. Next, 11.1 mmol of bis (diethylamino) methylvinylsilane and 13.1 mmol of n-butyllithium are added as a cyclohexane solution and an n-hexane solution, respectively, to initiate polymerization.
The stirring rate is 130 rpm, the temperature in the polymerization reactor is 65 ° C., and copolymerization of 1,3-butadiene and styrene is performed for 3 hours while continuously supplying the monomer into the polymerization reaction vessel. The supply amount of 1,3-butadiene in the total polymerization is 821 g, and the supply amount of styrene is 259 g.
Next, the obtained polymer solution is stirred at a stirring speed of 130 rpm, and 11.1 mmol of 3-diethylaminopropyltriethoxysilane is added and stirred for 15 minutes. 20 ml of hexane solution containing 0.54 ml of methanol is added to the polymer solution, and the polymer solution is further stirred for 5 minutes.
2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer GM) was added to the polymer solution. 8 g, 0.9 g of pentaerythrityl tetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer TP-D) was added, and then the polymer was removed from the polymer solution by steam stripping. Collect 1

(Production Example 4: Synthesis of Polymer 2)
The inside of a stainless steel polymerization reactor having an internal volume of 20 liters was washed, dried, and replaced with dry nitrogen, hexane (specific gravity 0.68 g / cm 3) 10.2 kg, 1,3-butadiene 547 g, styrene 173 g, tetrahydrofuran 6.1 ml Then, 5.0 ml of ethylene glycol diethyl ether is charged into the polymerization reaction vessel. Next, 11.0 mmol of bis (diethylamino) methylvinylsilane and 14.3 mmol of n-butyllithium are added as a cyclohexane solution and an n-hexane solution, respectively, to initiate polymerization.
The stirring rate is 130 rpm, the temperature in the polymerization reactor is 65 ° C., and copolymerization of 1,3-butadiene and styrene is performed for 3 hours while continuously supplying the monomer into the polymerization reaction vessel. The supply amount of 1,3-butadiene in the total polymerization is 821 g, and the supply amount of styrene is 259 g.
Next, the obtained polymer solution is stirred at a stirring speed of 130 rpm, and 11.0 mmol of 1,3-dimethyl-2-imidazolidinone is added and stirred for 15 minutes. 20 ml of hexane solution containing 0.54 ml of methanol is added to the polymer solution, and the polymer solution is further stirred for 5 minutes.
2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer GM) was added to the polymer solution. 8 g, 0.9 g of pentaerythrityl tetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer TP-D) was added, and then the polymer was removed from the polymer solution by steam stripping. Collect 2

(Production Example 5: Synthesis of Polymer 3)
The inside of a stainless steel polymerization reactor having an internal volume of 20 liters was washed, dried, and replaced with dry nitrogen, hexane (specific gravity 0.68 g / cm 3) 10.2 kg, 1,3-butadiene 547 g, styrene 173 g, tetrahydrofuran 6.1 ml Then, 5.0 ml of ethylene glycol diethyl ether is charged into the polymerization reaction vessel. Next, 10.5 mmol of bis (diethylamino) methylvinylsilane and 14.9 mmol of n-butyllithium are added as a cyclohexane solution and an n-hexane solution, respectively, to initiate polymerization.
The stirring rate is 130 rpm, the temperature in the polymerization reactor is 65 ° C., and copolymerization of 1,3-butadiene and styrene is performed for 3 hours while continuously supplying the monomer into the polymerization reaction vessel. The supply amount of 1,3-butadiene in the total polymerization is 821 g, and the supply amount of styrene is 259 g.
Next, the obtained polymer solution is stirred at a stirring speed of 130 rpm, and 10.5 mmol of N- (3-dimethylaminopropyl) acrylamide is added and stirred for 15 minutes. 20 ml of hexane solution containing 0.54 ml of methanol is added to the polymer solution, and the polymer solution is further stirred for 5 minutes.
2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer GM) was added to the polymer solution. 8 g, 0.9 g of pentaerythrityl tetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer TP-D) was added, and then the polymer was removed from the polymer solution by steam stripping. 3 is collected.

(Production Example 6: Synthesis of Polymer 4)
5. The inside of a stainless steel polymerization reactor having an internal volume of 20 liters was washed, dried, and replaced with dry nitrogen, hexane (specific gravity 0.68 g / cm ³ ) 10.2 kg, 1,3-butadiene 547 g, styrene 173 g, tetrahydrofuran 6. 1 ml and ethylene glycol diethyl ether 5.0 ml are charged into the polymerization reaction vessel. Next, 16.0 mmol of bis (diethylamino) methylvinylsilane and 18.5 mmol of n-butyllithium are added as a cyclohexane solution and an n-hexane solution, respectively, to initiate polymerization.
The stirring rate is 130 rpm, the temperature in the polymerization reactor is 65 ° C., and copolymerization of 1,3-butadiene and styrene is performed for 3 hours while continuously supplying the monomer into the polymerization reaction vessel. The supply amount of 1,3-butadiene in the total polymerization is 821 g, and the supply amount of styrene is 259 g.
Next, the obtained polymer solution is stirred at a stirring speed of 130 rpm, and 4.0 mmol of 1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate is added and stirred for 15 minutes. 20 ml of hexane solution containing 0.80 ml of methanol is added to the polymer solution, and the polymer solution is further stirred for 5 minutes.
2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer GM) was added to the polymer solution. 8 g, 0.9 g of pentaerythrityl tetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer TP-D) was added, and then the polymer was removed from the polymer solution by steam stripping. 4 is collected.

(Production Example 7: Synthesis of polymer 5)
5. The inside of a stainless steel polymerization reactor having an internal volume of 20 liters was washed, dried, and replaced with dry nitrogen, hexane (specific gravity 0.68 g / cm ³ ) 10.2 kg, 1,3-butadiene 547 g, styrene 173 g, tetrahydrofuran 6. 1 ml and ethylene glycol diethyl ether 5.0 ml are charged into the polymerization reaction vessel. Next, 11.5 mmol of bis (diethylamino) methylvinylsilane and 14.1 mmol of n-butyllithium are added as a cyclohexane solution and an n-hexane solution, respectively, to initiate polymerization.
The stirring rate is 130 rpm, the temperature in the polymerization reactor is 65 ° C., and copolymerization of 1,3-butadiene and styrene is performed for 3 hours while continuously supplying the monomer into the polymerization reaction vessel. The supply amount of 1,3-butadiene in the total polymerization is 821 g, and the supply amount of styrene is 259 g.
Next, the obtained polymer solution is stirred at a stirring speed of 130 rpm, 11.5 mmol of N, N-dimethylformamide dimethyl acetal is added and stirred for 15 minutes. 20 ml of hexane solution containing 0.54 ml of methanol is added to the polymer solution, and the polymer solution is further stirred for 5 minutes.
2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer GM) was added to the polymer solution. 8 g, 0.9 g of pentaerythrityl tetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer TP-D) was added, and then the polymer was removed from the polymer solution by steam stripping. Collect 5

(Production Example 8: Synthesis of Polymer 6)
The inside of the stainless steel polymerization reactor having an internal volume of 5 liters was washed, dried, and replaced with dry nitrogen, 2.55 kg of hexane (specific gravity 0.68 g / cm ³ ), 137 g of 1,3-butadiene, 43 g of styrene, tetrahydrofuran 1. 0 ml and 1.0 ml of ethylene glycol diethyl ether are charged into the polymerization reaction vessel. Next, 3.6 mmol of n-butyllithium is added as an n-hexane solution, and 1,3-butadiene and styrene are copolymerized for 2.5 hours. During the polymerization, the stirring speed is 130 rpm, the temperature in the polymerization reactor is 65 ° C., and the monomer is continuously fed into the polymerization reaction vessel. The supply amount of 1,3-butadiene is 169 g, and the supply amount of styrene is 101 g.
After the polymerization for 2.5 hours, 11.1 mmol of 3-diethylaminopropyltriethoxysilane was added as a cyclohexane solution to the polymerization reactor at a stirring speed of 130 rpm and a polymerization reactor internal temperature of 65 ° C., and stirred for 30 minutes. To do.
Next, 20 ml of hexane solution containing 0.14 ml of methanol is put into the polymerization reactor, and the polymer solution is stirred for 5 minutes.
2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer GM) was added to the polymer solution. 8 g, 0.9 g of pentaerythrityl tetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer TP-D) was added, and then the polymer was removed from the polymer solution by steam stripping. 6 is collected.

(Production Examples 9-13: Synthesis of Polymers 7-11)
Polymers 7 to 11 are obtained by the same formulation as polymers 1 to 5 except that 11.1 mmol of bis {di (n-butyl) amino} methylvinylsilane is used instead of 11.1 mmol of bis (diethylamino) methylvinylsilane.

(Production Examples 14 to 23: Synthesis of Polymers 12 to 21)
Instead of steam stripping, the polymer solution was polymerized according to the same formulation as the polymers 1-5 and polymers 7-11 except that the polymer solution was evaporated at room temperature for 24 hours and further dried under reduced pressure at 55 ° C. for 12 hours. Get ~ 21.

Examples 117-141
According to the blending contents shown in Tables 25 to 27, materials other than sulfur and a vulcanization accelerator are kneaded for 5 minutes at 150 ° C. using a 1.7 L Banbury mixer to obtain a kneaded product. Next, sulfur and a vulcanization accelerator are added to the obtained kneaded product, and kneaded for 5 minutes at 80 ° C. using an open roll to obtain an unvulcanized rubber composition.

Examples 142-146
According to the formulation shown in Table 28, a chemical other than sulfur and a vulcanization accelerator is kneaded for 5 minutes at 150 ° C. using a Banbury mixer to obtain a kneaded product. Next, sulfur and a vulcanization accelerator are added to the kneaded product obtained, and kneaded for 5 minutes at 80 ° C. using a biaxial open roll to obtain an unvulcanized rubber composition.
Such an unvulcanized rubber composition is preferably used as a rubber composition for clinch apex in order to give a vulcanized rubber having reduced rolling resistance and electric resistance and improved crack resistance.

Examples 147-150
(Preparation of silica dispersion)
85.5 g of pure water was added to 4.5 g of wet silica (Tokuyama Tokuseal USG, average particle size: 18 nm, N ₂ SA: 170 m ^{2 /} g) to prepare a 5% silica suspension. The mixture is stirred and sonicated for 10 minutes to obtain a silica dispersion.
(Preparation of silica / natural rubber composite)
Silica dispersion is added to 16.7 g of natural rubber latex (high ammonia type, rubber solid content concentration 60% by weight), and 0.45 g of the following surfactants (1) to (5) are further added, for 1 hour. Mix and stir. After stirring, sulfuric acid is added to adjust the pH to 5 to 7 to obtain a coagulated product. The obtained solidified product is filtered and dried to obtain silica / natural rubber composites 1 to 5 (referred to as “composites 1 to 5” in Table 29).
Surfactant (1): Huntsman Corp. of _{teric 16A29 (CH 3 (C 2} H 4) 16 (OC 2 H 4) 29 -OH)
Surfactant (2): PD-430 (R- (OC ₄ H ₈ ) _p (OC ₂ H ₄ ) _q —OH: R = long chain alkyl group) manufactured by Kao Corporation
Surfactant (3): manufactured by Kao Corp. of _{Emulgen420 (C 8 H 17 CH =} CHC 8 H 16 (OC 2 H 4) r -OH)
Surfactant (4): Si363 manufactured by Evonik Degussa
Surfactant (5): Hexadecyltrimethylammonium bromide (Wako Pure Chemical Industries, Ltd.)
(Preparation of rubber composition)
In accordance with the formulation shown in Table 29, chemicals other than sulfur and a vulcanization accelerator are kneaded using a 1.7 L Banbury mixer. Next, using a roll, sulfur and a vulcanization accelerator are added and kneaded into the obtained kneaded product to obtain an unvulcanized rubber composition.

Examples 151-161
In accordance with the formulation shown in Table 30, materials other than sulfur (3), vulcanizing agent (1) and vulcanization accelerator (1) were kneaded for 5 minutes at 150 ° C. using a 1.7 L Banbury mixer. To obtain a kneaded product. Next, sulfur, vulcanizing agent 1 and vulcanization accelerator are added to the obtained kneaded product, and kneaded for 5 minutes under the condition of 80 ° C. using an open roll to obtain an unvulcanized rubber composition.
Since such an unvulcanized rubber composition gives a vulcanized rubber having good fuel economy and mechanical strength, it is preferable to use it as a tire composition, particularly as a rubber composition for a tread.

Examples 162-173
In accordance with the formulation shown in Tables 31 and 32, materials other than sulfur and a vulcanization accelerator are kneaded for 3 minutes at 150 ° C. using a 1.7 L Banbury mixer to obtain a kneaded product. Next, sulfur and a vulcanization accelerator are added to the obtained kneaded product, and kneaded for 5 minutes under a condition of 80 ° C. using a biaxial open roll to obtain an unvulcanized rubber composition.

Examples 174-181
In accordance with the formulation shown in Table 33, materials other than sulfur, vulcanizing agent 1 and vulcanization accelerator are kneaded for 5 minutes at 150 ° C. using a 1.7 L Banbury mixer to obtain a kneaded product. Next, sulfur, vulcanizing agent 1 and vulcanization accelerator are added to the obtained kneaded product, and kneaded for 5 minutes under the condition of 80 ° C. using an open roll to obtain an unvulcanized rubber composition.

Examples 182-190
According to the formulation shown in Table 34, materials other than sulfur and a vulcanization accelerator are kneaded for 3 minutes at 150 ° C. using a 1.7 L Banbury mixer to obtain a kneaded product. Next, sulfur and a vulcanization accelerator are added to the obtained kneaded product, and kneaded for 5 minutes at 80 ° C. using an open roll to obtain an unvulcanized rubber composition.

Examples 191 to 200
In accordance with the formulation shown in Table 35, materials other than sulfur, vulcanizing agent 1 and vulcanization accelerator are kneaded for 5 minutes at 150 ° C. using a 1.7 L Banbury mixer to obtain a kneaded product. Next, sulfur, vulcanizing agent 1 and vulcanization accelerator are added to the obtained kneaded product, and kneaded for 5 minutes under the condition of 80 ° C. using an open roll to obtain an unvulcanized rubber composition.

Examples 201-214
According to the formulation shown in Tables 36 and 37, materials other than sulfur and a vulcanization accelerator are kneaded for 3 minutes at 150 ° C. using a 1.7 L Banbury mixer to obtain a kneaded product. Next, sulfur and a vulcanization accelerator are added to the obtained kneaded product, and kneaded for 5 minutes under a condition of 80 ° C. using a biaxial open roll to obtain an unvulcanized rubber composition.

Examples 215-219
According to the formulation shown in Table 38, materials other than sulfur and a vulcanization accelerator are kneaded for 3 minutes at 150 ° C. using a 1.7 L Banbury mixer to obtain a kneaded product. Next, sulfur and a vulcanization accelerator are added to the obtained kneaded product, and kneaded for 5 minutes under a condition of 80 ° C. using a biaxial open roll to obtain an unvulcanized rubber composition.

Examples 220-222
In accordance with the formulation shown in Table 39, materials other than sulfur, vulcanizing agent 1 and vulcanization accelerator are kneaded for 3 minutes at 150 ° C. using a 1.7 L Banbury mixer to obtain a kneaded product. Next, sulfur, vulcanizing agent 1 and vulcanization accelerator are added to the obtained kneaded product, and kneaded for 5 minutes under a condition of 80 ° C. using a biaxial open roll to obtain an unvulcanized rubber composition. obtain.

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

Claims (2)

Formula (I):

Or a hydrate thereof.   A rubber composition comprising the compound according to claim 1 or a hydrate thereof and a rubber component.